Method of filling recessed features on substrate using metal sequential penetration synthesis process

Abstract

Methods of filling recessed features on a substrate using a metal sequential penetration synthesis process are disclosed. The disclosed method includes forming an organic layer within the recessed feature and introducing a metal species into the organic layer to allow formation of a metal seed layer. A bulk metal layer may then be formed from the metal seed layer to fill the recessed features.

Description

Technical Field

[0001] This disclosure generally relates to the field of semiconductor processing methods and related structures, and also to the field of device and integrated circuit manufacturing. More specifically, this disclosure generally relates to a method for filling recessed features on a substrate using a metal sequential infiltration synthesis process. Background Art

[0002] The manufacturing processes used to form device structures (such as transistors, memory elements, and integrated circuits) are extensive and can include deposition, etching, thermal, photolithography, and doping processes.

[0003] A particular manufacturing process involves depositing material into recessed features on a substrate, thereby filling the recessed features (or gaps) with material; this process is often referred to as "gap filling." For example, a non-planar substrate may include multiple recessed features, such as vertical recessed features disposed between protrusions on the substrate surface or serrated recessed features formed in the substrate surface.

[0004] As the geometry of semiconductor devices shrinks and high aspect ratio features become increasingly common in device structures such as DRAM, flash memory, and logic, filling numerous recessed features with materials possessing desired properties has become increasingly complex.

[0005] Deposition methods such as high-density plasma (HDP), sub-atmospheric pressure chemical vapor deposition (SACVD), and low-pressure chemical vapor deposition (LPCVD) have been used in gap-filling processes; however, these and other processes often fail to achieve the desired gap-filling results. Therefore, methods are desired to fill recessed features on substrates with materials possessing improved properties, such as metals.

[0006] Any discussion set forth in this section (including discussions of problems and solutions) is included in this disclosure merely for the purpose of providing background to this disclosure and should not be construed as an admission that any or all of the discussions were known at the time the invention was made or otherwise constituted prior art. Summary of the Invention

[0007] This summary presents a simplified description of the selected concepts, which will be described in further detail below. This summary is not intended to require the identification of key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0008] Various embodiments of this disclosure relate to methods for filling recessed features on a substrate and methods for gap-filling recessed features on a substrate from bottom to top.

[0009] According to an example of this disclosure, a method for filling a recessed feature on a substrate is provided. The method includes placing the substrate including the recessed feature in a reaction chamber. In such a method, the recessed feature includes a sidewall surface, a top surface, and a bottom surface. In such a method, the bottom surface includes a first material, and the sidewall surfaces include a second material different from the first material. The method further includes selectively forming an organic layer on the first material relative to the second material, and performing a metal sequential infiltration synthesis process to introduce a metallic substance into the organic layer, thereby forming a metal-infiltrated layer. The method further includes removing the organic components of the metal-infiltrated layer to form a metal seed layer on the bottom surface, and directly forming a bulk metal layer on the metal seed layer, wherein the bulk metal layer fills the recessed feature.

[0010] In some embodiments, selectively forming an organic layer on a first material relative to a second material includes selectively passivating the surface of a second material relative to the surface of the first material by introducing a passivating agent into a reaction chamber; and depositing an organic layer on the surface of the first material.

[0011] In some embodiments, the organic layer is selectively formed with a selectivity of more than 50%.

[0012] In some embodiments, the passivating agent comprises an alkylaminosilane. In some embodiments, the alkylaminosilane comprises at least one of the following: allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trimethylchlorosilane, and combinations thereof.

[0013] In some embodiments, the method further includes heat-treating the organic layer in an ammonia (NH3) environment prior to performing the metal sequential infiltration synthesis process.

[0014] In some embodiments, performing a metal sequential percolation synthesis process includes introducing a metal precursor into a reaction chamber, the metal precursor comprising a metallic substance. In some embodiments, the metallic substance is selected from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum.

[0015] In some embodiments, performing the metal sequential percolation synthesis process further includes introducing a second precursor into the reaction chamber, the second precursor comprising hydrogen or ammonia.

[0016] In some embodiments, removing the organic components of the metal penetration layer includes a plasma etching process.

[0017] In some embodiments, forming a bulk metal layer directly on a metal seed layer comprises depositing the bulk metal layer through a cyclic deposition process.

[0018] In some embodiments, the bulk metal layer includes titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum. In some embodiments, the bulk metal layer is the same as the metal seed layer. In some embodiments, the bulk metal layer is different from the metal seed layer.

[0019] According to another example of this disclosure, a method for bottom-up gap filling of a recessed feature on a substrate is provided. The method includes placing a substrate including the recessed feature in a reaction chamber. The recessed feature includes a bottom surface comprising a silicon-germanium layer and a sidewall surface comprising a silicon layer. The method further includes passivating the sidewall surface comprising the silicon layer by introducing a passivating agent into the reaction chamber. The method further includes depositing an organic layer on the silicon-germanium layer disposed at the bottom surface of the recessed feature. The method further includes performing at least one permeation cycle of a sequential permeation synthesis (SIS) sequence to introduce a metallic material into the organic layer, thereby forming a metal-permeated layer. Each permeation cycle includes introducing a metal precursor comprising a metallic material selected from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum into the reaction chamber. The method further includes removing the organic components of the metal-permeated layer, thereby forming a metal seed layer on the silicon-germanium layer disposed at the bottom surface of the recessed feature. The method further includes depositing a bulk metal layer directly on the metal seed layer using a cyclic deposition process, wherein the bulk metal layer fills the recessed feature without forming seams.

[0020] In some embodiments, the passivating agent comprises an alkylaminosilane selected from allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trimethylchlorosilane, and combinations thereof.

[0021] In some embodiments, the organic layer comprises polyimide.

[0022] In some embodiments, the method further includes thermally annealing the organic layer in an ammonia (NH3) environment prior to performing at least one percolation cycle of a sequential percolation synthesis (SIS) sequence.

[0023] In some embodiments, the metal seed layer is a molybdenum seed layer, and the bulk metal layer is a bulk molybdenum layer. In some embodiments, the metal seed layer is a titanium seed layer, and the bulk metal layer is a bulk molybdenum layer.

[0024] For the purpose of summarizing the advantages of the present invention and its implementation relative to prior art, certain objects and advantages of the present invention have been described above. It should be understood, of course, that not all of these objects or advantages may be achieved according to any particular embodiment of the present invention. Therefore, for example, those skilled in the art will recognize that the present invention may be implemented or performed in a manner that achieves or optimizes one or more advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0025] All these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, and the invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0026] To facilitate the identification of any particular element or action in the discussion, one or more of the most significant digits in the reference numerals refer to the figure number in which the element was first introduced.

[0027] A more complete understanding of embodiments of this disclosure can be derived by referring to the detailed description and claims when considered in conjunction with the following illustrative drawings.

[0028] Figure 1 Exemplary methods according to one or more embodiments of this disclosure are shown.

[0029] Figure 2 A view of a structure formed according to one or more embodiments of the present disclosure is shown.

[0030] Figure 3 A view showing an additional structure formed according to one or more embodiments of the present disclosure.

[0031] Figure 4 A view of another structure formed according to one or more embodiments of the present disclosure is shown.

[0032] Figure 5 A view is shown of yet another structure formed according to one or more embodiments of the present disclosure.

[0033] Figure 6 A view is shown of yet another structure formed according to one or more embodiments of the present disclosure.

[0034] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the embodiments illustrated in this disclosure. Detailed Implementation

[0035] The following description of exemplary embodiments of the methods and compositions is merely illustrative and intended for purposes of explanation only. The following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having indicated features or steps is not intended to exclude other embodiments having additional features or steps, or other embodiments including different combinations of said features or steps.

[0036] In this disclosure, "gas" can include materials that are gaseous at ambient temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and can consist of a single gas or a mixture of gases, depending on the circumstances. Gases other than process gases (i.e., gases introduced without passing through gas distribution components, other gas distribution devices, etc.) can be used, for example, to seal the reaction space, and can include sealing gases. Precursors and reactants can be gases. Exemplary sealing gases include rare gases, nitrogen, etc. In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, and particularly to a compound that constitutes the membrane matrix or the main framework of the membrane; the term "reactant" can be used interchangeably with the term "precursor."

[0037] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films can be formed by means of methods according to embodiments of the invention. A substrate may comprise a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or III-V semiconductor materials), and may comprise one or more layers overlying or underlying the bulk material. Furthermore, a substrate may include various features, such as recesses, protrusions, etc., formed within or on at least a portion of the layers of the substrate. For example, a substrate may comprise a bulk semiconductor material and an insulating or dielectric material layer covering at least a portion of the bulk semiconductor material. Furthermore, the term "substrate" can refer to any one or more underlying materials that can be used or on which devices, circuits, or films can be formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous. A substrate can be in any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. Substrates can be made of materials such as silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. The continuous substrate may extend beyond the boundary of the processing chamber, where the deposition process takes place, and the continuous substrate may move through the processing chamber such that the process continues until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate feed system, thereby allowing the continuous substrate to be manufactured and output in any suitable form. Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, meshes, flexible materials, bundles of continuous filaments or fibers (i.e., ceramic fibers or polymer fibers). The continuous substrate may also include a carrier or sheet on which a non-continuous substrate is mounted.

[0038] As used herein, the terms "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, partially or entirely molecular layers, partially or entirely atomic layers, or atomic and / or molecular clusters. A film or layer can include or may consist at least partially of a plurality of dispersed atoms on a substrate surface, and / or can be embedded in a substrate and / or embedded in a device fabricated on that substrate. A film or layer can include a material or layer having pinholes and / or isolation islands. A film or layer can be at least partially continuous. A film or layer can be patterned, e.g., subdivided, and can be included in multiple semiconductor devices. A film or layer can be selectively grown on some portions of a substrate and not on others.

[0039] The term “cyclic deposition process” or “cyclic deposition process” can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclic CVD components.

[0040] The term "atomic layer deposition" can refer to a vapor phase deposition process in which deposition cycles, typically multiple consecutive cycles, are performed in a processing chamber. As used herein, the term atomic layer deposition is also intended to include processes specified by related terms such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed using alternating pulses of precursor / reactant gases and purge gases (e.g., inert carrier gases). The pulses may include exposing the substrate to a precursor or reactant. This can be accomplished, for example, by introducing the precursor or reactant into a reaction chamber in which the substrate is present. Alternatively or concurrently, exposing the substrate to a precursor may include moving the substrate to a location in the substrate processing system where the reactant or precursor is present.

[0041] Typically, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other material) and forms a monolayer or sub-monolayer of material that does not readily react with another precursor (i.e., a self-limiting reaction). Subsequently, a reactant (e.g., another precursor or reactive gas) can be introduced into the processing chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant may be able to further react with the precursor. During one or more cycles, such as during each step of each cycle, a purging step may be used to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber.

[0042] As used herein, "precursor" includes a gas or a material that can be converted into a gaseous state and can be represented by a chemical formula comprising elements that can be incorporated during the deposition process described herein. Furthermore, the terms "precursor" and "reactant" can refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction to produce another compound. Precursors typically contain portions at least partially incorporated into the compound or element produced by the chemical reaction in question. The resulting compound or element can then be deposited on a substrate. Reactants can be elements or compounds that are not significantly incorporated into the resulting compound or element. However, in some embodiments, reactants may also contribute to the resulting compound or element.

[0043] As used herein, "structure" can be or includes a substrate as described herein. A structure can include one or more layers covering or within a substrate, such as one or more layers formed according to the methods described herein. All or part of the means can be included within or on the structure.

[0044] As used herein, the term "recessed feature" can refer to an opening or cavity disposed between surfaces that are not planar. For example, the term "recessed feature" can refer to an opening or cavity disposed between opposing sidewalls or protrusions extending vertically from a substrate surface or between opposing inclined sidewalls of a recess extending vertically into the substrate surface.

[0045] As used herein, the term "seam" can refer to a gap line or one or more separate voids formed by adjacent edges in a gap-filling metal. The presence of a "seam" can be confirmed using high-magnification microscopy methods, such as scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM), where a "seam" is considered to be present if observation shows a clear vertical gap line or one or more vertical voids in a recessed feature filled with gap-filling metal.

[0046] Numerous example materials are given throughout the embodiments of this disclosure. It should be noted that the chemical formulas given for each example material should not be interpreted as limiting, and the non-limiting example materials given should not be limited by the given example stoichiometry.

[0047] In this disclosure, any two numbers of a variable may constitute a working range of the variable, and any range indicated may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and include equivalents, and in some embodiments may refer to an average, median, representative value, multi-value, etc. Furthermore, in this disclosure, the terms “comprising,” “consisting of,” and “having” may, in some embodiments, independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of.” The meaning of any definition in this disclosure does not necessarily exclude the common and conventional meaning in some embodiments. In some cases, percentages indicated herein may be relative or absolute percentages.

[0048] In this specification, it should be understood that the terms "on" or "above" can be used to describe relative positional relationships. Another element, film, or layer may be directly on the mentioned layer, or another layer (intermediate layer) or element may be inserted therebetween, or a layer may be disposed on the mentioned layer but not completely cover the surface of the mentioned layer. Therefore, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it should be understood that the terms "below," "under," or "beneath" will be interpreted as relative concepts.

[0049] Various embodiments of this disclosure relate to methods for filling recessed features on a substrate using a metal sequential infiltration synthesis process, and related structures formed by such methods.

[0050] Switch to the attached image. Figure 1 An exemplary process 100 is illustrated. In brief, process 100 includes placing a substrate including a recessed feature in a reaction chamber (step 102). The recessed feature includes a bottom surface, sidewall surfaces, and a top surface. The bottom surface includes a first material, and the sidewall surfaces include a second material, wherein the first material is different from the second material. An organic layer is then selectively formed on the first material relative to the second material (e.g., on the bottom surface of the recessed feature relative to the sidewall surfaces of the recessed feature) (step 104). The organic layer is then subjected to a metal sequential infiltration synthesis process to introduce a metallic substance into the organic layer, thereby forming a metal-infiltrated layer (step 114). Subsequently, the organic components of the metal-infiltrated layer are removed (step 122), and a metal seed layer is formed on the bottom surface of the recessed feature (i.e., on the first material). The metal seed layer serves as a nucleation layer, thereby allowing the formation of a bulk metal layer on the metal seed layer (step 124). The bulk metal layer fills the recessed feature from the bottom up, and in doing so, fills the recessed feature without forming seams.

[0051] More specifically, this disclosure provides a method for filling recessed features on a substrate. Specifically, the disclosed method fills the recessed features via a bottom-up gap-filling process, wherein the recessed features are initially filled from the bottom surface of the recessed features by a metallic gap-filling material. Benefits of the bottom-up gap-filling process may include reducing or even eliminating the formation of seams within the metallic gap-filling material. Furthermore, the method disclosed herein can fill recessed features that include a material different from the sidewall surfaces and / or top surface in the base (i.e., the bottom surface) of the recessed features. Such selective metallic gap-filling processes can greatly simplify semiconductor device and integrated circuit fabrication by eliminating the need for, for example, additional photolithography and etching steps.

[0052] Based on the examples in this disclosure, Figure 2 A structure 200 including a substrate 202 (as described in detail above) and a recessed feature 204 is illustrated. In some embodiments, structure 200 may include a portion of a device structure, such as a partially fabricated device structure. In such embodiments, structure 200 may include a partially fabricated logic device, memory device, integrated circuit, etc. Although structure 200 is illustrated as including a single recessed feature 204, it should be understood that the provided methods are not limited thereto, and a substrate including multiple recessed features can be filled using the methods disclosed herein. It should also be noted that... Figure 2 The cross-sectional profile of the recessed feature 204 shown is exemplary, and the methods disclosed herein include filling the recessed feature with alternative cross-sectional profiles, including but not limited to curved, fan-shaped, V-shaped, tapered, recessed, and through-silicon via structures. The recessed feature 204 may also include high aspect ratio features, such as trench structures, vertical gaps, and / or fin structures. When referring to a recessed feature with a high aspect ratio, the recessed feature 204 has an aspect ratio (e.g., the ratio of height to width) greater than 2:1, greater than 5:1, greater than 10:1, greater than 25:1, greater than 50:1, or greater than 100:1.

[0053] Based on the examples in this disclosure, Figure 2 An exemplary recessed feature 204 includes a bottom surface 206, a sidewall surface 208, and a top surface 210. In such an example, the bottom surface 206 includes a first material 212 and the sidewall surfaces (or multiple sidewall surfaces) include a second material 214, wherein the first material 212 is different from the second material 214. Figure 2 As shown, the entire extent of the bottom surface 206 comprises the first material 212. However, in some embodiments, a portion of the bottom surface 206 comprises the first material 212 (e.g., the middle portion of the bottom surface), and the remaining portion of the bottom surface comprises a different material (e.g., such as a second material 214). Furthermore, as... Figure 2As shown, the top surface 210 includes a second material 214. However, in some embodiments, the top surface 210 may include one or more dissimilar materials other than the second material 214 and / or the first material 212.

[0054] According to an example of this disclosure, the first material 212 (i.e., the material at the bottom of the recessed feature 204) comprises a germanium-containing layer. In such an example, the germanium-containing layer may comprise a silicon-germanium layer. As used herein, the term "silicon-germanium layer" may refer to a material layer comprising silicon and germanium, and may be represented as Si 1-x Ge x The first material comprises a silicon and germanium material having the composition described herein, wherein 1 ≥ x ≥ 0, or 0.8 ≥ x ≥ 0.1, or 0.6 ≥ x ≥ 0.2, or comprising a silicon and germanium material having the composition described herein. Furthermore, the term "silicon-germanium" may be represented as SiGe and may also include one or more dopants, such as boron. In some embodiments, the first material comprises a SiGe layer having the following germanium compositions: greater than 0.01, greater than 0.05, greater than 0.1, greater than 0.2, greater than 0.3, greater than 0.4, greater than 0.5, greater than 0.6, or greater than 0.7. In some embodiments, the first material comprises a SiGe layer having the following germanium compositions: less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3, less than 0.2, or less than 0.1.

[0055] According to examples of this disclosure, the second material 214 comprises a material different from the first material 212. As a non-limiting example, the first material 212 may comprise a silicon-germanium layer, and the second material 214 may comprise one or more of a silicon layer, a silicon oxide layer, and a silicon nitride layer. In some embodiments, the first material 212 comprises a silicon-germanium layer having a first component (e.g., a first germanium content), and the second material 212 comprises a silicon-germanium layer having a second component (e.g., a second germanium content), wherein the first component differs from the second component (i.e., the first material 212 has a germanium content different from that of the second material 214). In some embodiments, the first material 212 comprises a germanium-containing material and the second material 214 comprises a germanium-free material, i.e., the second material contains no or substantially no elemental germanium.

[0056] Turn again Figure 1 Process 100, step 102 includes placing a substrate (e.g., such as...) Figure 2The recessed feature 204 is disposed in the reaction chamber. The reaction chamber may be configured to perform all or part of the remaining steps of process 100. Reactors and associated reaction chambers capable of performing the gap-filling process of this disclosure may include reaction chambers configured to perform cyclic processes, such as reaction chambers configured to perform atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PEALD), cyclic chemical vapor deposition (CCVD), and sequential permeation synthesis (SIS) type processes, and reaction chambers configured to introduce reactants in a cyclic manner. For example, in some embodiments, the gap-filling process of this disclosure may be performed within a semiconductor processing apparatus configured for atomic layer deposition.

[0057] In some embodiments, the reaction chamber for performing the gap filling process of this disclosure may be or include a configuration for performing process 100 ( Figure 1 The reaction chamber of an atomic layer deposition reactor system is used for the processing steps of plasma deposition. The reaction chamber can be a standalone chamber or part of a cluster of equipment. The reaction chamber can be a batch processing equipment. In some embodiments, a flow reactor can be used. In some embodiments, a spray head reactor can be utilized. In some embodiments, a space-separated reactor can be used. In some embodiments, a single-wafer reactor capable of mass production can be utilized. In other embodiments, a batch reactor comprising multiple substrates can be utilized. For embodiments in which a batch reactor is used, the number of substrates can range from 10 to 200, or 50 to 150, or even 100 to 130. In some embodiments, the reaction chamber can be configured as a thermal reactor—without plasma excitation equipment. In some embodiments, the reaction chamber can be configured to perform both plasma and thermal processes.

[0058] According to an example of this disclosure, process 100 continues to step 104, which includes selectively forming an organic layer on the first material relative to the second material. In other words, the organic layer is preferentially formed on the bottom surface of the recessed feature relative to the sidewall surface, as discussed in more detail below. According to an example of this disclosure, the step of selectively forming the organic layer (step 104) may include multiple sub-steps, such as sub-steps 106 and 108, as described in detail below.

[0059] According to an example of this disclosure, sub-step 106 includes selectively passivating the surface of the second material (e.g., the sidewall surface of the recessed feature) relative to the surface of the first material (e.g., the bottom surface of the recessed feature). Selective passivation can be achieved by introducing a passivating agent into the reaction chamber and contacting the substrate with the passivating agent. For example, contacting the substrate with the passivating agent can be performed at a temperature below 400°C (e.g., the substrate temperature), such as at a temperature between 100°C and 400°C. In some embodiments, the passivating agent is pulsed into the reaction chamber. In such examples, selectively passivating the second material (e.g., the sidewall surface of the recessed feature) can include introducing one or more pulses of the passivating agent into the reaction chamber (with or without an intermediate purge cycle). In some embodiments, the passivating agent can be introduced into the reaction chamber (i.e., pulsed in the reaction chamber) once or more, two or more times, five or more times, ten or more times, twenty or more times, thirty or more times, forty or more times, or fifty or more times.

[0060] In some embodiments, the selectivity of the passivating agent is inherent and does not require prior or additional processing steps that are more convenient to perform on the substrate. For example, the selectivity of the passivating agent may be inherent to a certain material or material composition. As a non-limiting example, since the bottom surface includes a germanium-containing layer (e.g., SiGe) and the sidewall surfaces include a germanium-free layer (e.g., Si, SiO2, Si3N4, etc.), the passivating agent can selectively passivate the sidewall surfaces of the recessed structure relative to the bottom surface of the recessed structure.

[0061] In some embodiments, the passivating agent comprises a vapor-phase passivating agent. In alternative embodiments, the passivating agent may comprise a liquid passivating agent, for example, applied to the substrate by spin coating.

[0062] According to examples of this disclosure, the passivating agent may include an alkylsilane. In such examples, the passivating agent may include an alkylaminosilane. In specific examples, the alkylaminosilane includes at least one of the following: allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trimethylchlorosilane, and combinations thereof. In some embodiments, the alkylaminosilane comprises N-(trimethylsilyl)dimethylamine (TMSDMA) or 1,1,1-trimethoxy-N,N-dimethylsilaneamine.

[0063] According to an example of this disclosure, after the sub-step (sub-step 106) of selectively passivating the sidewall surface of the recessed feature, a subsequent sub-step includes depositing an organic layer on the surface of the first material (e.g., on the bottom surface of the recessed feature).

[0064] The deposition of the organic layer according to the method of this disclosure can be performed via a cyclic vapor deposition process. For example, the deposition of the organic layer can be a molecular layer deposition (MLD) process. The deposition of the organic layer includes providing a first organic precursor into a reaction chamber and providing a second organic precursor into a reaction chamber. Providing the first organic precursor and providing the second organic precursor can define a deposition cycle. The deposition cycle can be repeated until an organic layer of suitable thickness has been deposited on the surface of the first material (e.g., on the bottom surface of the recessed feature). As a result of a previous passivation process, the first and second organic precursors selectively form an organic layer on the first material. In some embodiments, the organic layer is an organic polymer. In some embodiments, the organic polymer includes polyimide.

[0065] In sub-step 108, various precursors can be used to deposit the organic layer. As a non-limiting example, the first organic precursor may include a diamine. In such examples, the first organic precursor may be, for example, 1,6-diaminohexane, 1,3-diaminopentane, a triamine (such as tris(2-aminoethyl)amine), or a cyclic compound containing at least two primary amine groups (such as 1,4-diaminocyclohexane or p-phenylenediamine). In some embodiments, the substrate is contacted with the first organic precursor before it contacts the second organic precursor. Thus, in some embodiments, the substrate may be contacted with the diamine before it contacts the second organic precursor. In some embodiments, the second organic precursor is capable of reacting with the adsorbate of the first organic precursor under deposition conditions. For example, in some embodiments, the second organic precursor is an acid anhydride, such as furan-2,5-dione (maleic anhydride). The acid anhydride may be a dianhydride, such as pyromellitic dianhydride (PMDA). In some embodiments, the second organic precursor may be any other monomer having two reactive groups that will react with the first organic precursor.

[0066] In alternative examples of this disclosure, the organic layer may be replaced by an inorganic layer. In such examples, the deposited layer to be subsequently infiltrated may contain a metal oxide. In some embodiments, the metal oxide is formed by a selective deposition process comprising a metal reactant and an oxidant. In alternative embodiments, the metal oxide is formed by infiltrating a metal substance into an organic layer, wherein oxygen within the organic layer reacts with the infiltrated metal to form the metal oxide.

[0067] The combination of selective passivation (sub-step 106) and organic layer deposition (sub-step 108) allows the organic layer to be selectively formed on the first material (i.e., the bottom surface of the recessed feature) relative to the second material (i.e., the sidewall surface of the recessed feature). For example, in some embodiments, the selective passivation process results in delayed nucleation of the organic layer on the sidewalls of the recessed feature, thereby resulting in the selective formation of the organic layer on the bottom surface of the recessed feature.

[0068] When material is selectively formed or deposited on the first surface of a substrate relative to the second surface, the selectivity can be given as a percentage calculated as [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). When material is deposited on the second surface, the calculation is reversed accordingly.

[0069] In some embodiments, the selectivity of the organic layer formed on the first material (i.e., the bottom surface of the recessed feature) is at least about 30%. In some embodiments, the selectivity is at least 50%. In some embodiments, the selectivity is at least 75% or greater than 85%. In some embodiments, the selectivity is at least 90% or at least 93%. In some embodiments, the selectivity is at least 95% or at least 98%. In some embodiments, the selectivity is at least 99% or even at least 99.5%. In embodiments, the selectivity can vary within the duration or thickness of the deposition. It should be noted that a partially selective process can produce a fully selective structure by post-deposition etching, which removes all deposited material from above the second material without removing the entire deposited material from above the second material.

[0070] Deposition can be measured in any of a variety of ways. In some embodiments, deposition can be given as a measured thickness of the deposited material (e.g., an organic layer). In some embodiments, deposition can be given as a measured amount of deposited material. Sometimes, selectivity (e.g., after one of at least two surfaces of a substrate has been treated with a passivating agent) can be measured as nucleation delay, expressed as the number of deposition cycles before the deposition of an organic layer is observed on different surfaces. In such cases, the term "selectivity window" can be used to describe the difference in the number of cycles on different surfaces before the deposition of an organic layer is observed.

[0071] You can refer to this. Figure 3 Further explanation is given of the selective formation of the organic layer as described above (i.e., step 104 and related sub-steps). According to examples of this disclosure, Figure 3 Structure 300 is shown, which includes (after selective deposition of an organic layer) Figure 2 The structure 200. For example... Figure 3As shown, structure 300 includes an organic layer 302 disposed above (e.g., on) the first material 212, and specifically, the organic layer is disposed on the bottom surface 206 of the recessed feature 204. Conversely, the organic layer 302 is not disposed above (e.g., on) the second material 214, and particularly, the organic layer 302 is not disposed on the sidewall surface 208 of the recessed feature 204. In some embodiments, the top surface 210 of the recessed feature 204 also lacks the organic layer 302, such as... Figure 3 As shown.

[0072] After forming an organic layer on the bottom surface of the recessed feature (i.e., on the first material), the organic layer may optionally be heat-treated before infiltration with a metallic substance. For example, heat treatment of the organic layer can increase the mass absorption of the organic layer, i.e., heat treatment increases the likelihood that a metallic substance will infiltrate and remain in the organic layer. Therefore, in some embodiments, method 100 may optionally include the step of heat-treating the organic layer in an ammonia environment (step 110). For example, the organic layer may be heated in an ammonia environment to a temperature below 500°C, below 400°C, below 300°C, below 200°C, or between 200°C and 500°C. In a particular example, process 100 may optionally include heat-treating the organic layer in an ammonia (NH3) environment before performing a metal sequential infiltration synthesis process.

[0073] Embodiments of this disclosure further include forming a metal seed layer on the bottom surface of the recessed feature (i.e., on the first material). In short, the metal seed layer is formed by introducing a metallic substance (e.g., multiple metallic substances) into a previously formed organic layer. Introducing the metallic substance into the organic layer can be achieved by optionally thermally treating the organic layer (as described above) and employing a permeation process (e.g., a metal sequential permeation synthesis process) to inject metal atoms into the framework of the organic layer, thereby forming a metal permeation layer. As a non-limiting example, the metal sequential permeation synthesis process of this disclosure may include adsorbing at least a portion of a metal precursor into the organic layer (e.g., dissolving and / or diffusing the metal precursor into the organic layer). The metal precursor then interacts with the organic layer (e.g., through reversible complex formation and / or irreversible chemical reactions), and this interaction between the metal precursor and the organic layer causes the metallic substance provided from the metal precursor to be retained within the organic layer, forming the metal permeation layer. Subsequently, the organic components of the metal permeation layer can be removed, thereby leaving a metal seed layer on the bottom surface of the recessed feature.

[0074] The metal sequential infiltration synthesis process (also referred to herein as the metal SIS process) according to the method of this disclosure is performed in... Figure 1As illustrated in step 114, step 114 includes sub-step 116 and optional sub-step 118. According to an example of this disclosure, the metal SIS process (step 114) includes at least one permeation cycle performing a metal sequential permeation synthesis process to introduce a metallic material (e.g., multiple metallic materials) into an organic layer, thereby forming a metal-permeated layer. In such an example, each permeation cycle includes at least introducing a metal precursor containing the metallic material into the reaction chamber (sub-step 116). In some embodiments, each permeation cycle may optionally include introducing a second precursor (e.g., an additional precursor and / or co-reactant) into the reaction chamber (sub-step 118). The metallic precursor and optional second precursor can be introduced into the reaction chamber by pulsed precursors into the reaction chamber, where they contact the surface of the substrate, including the organic layer. The metallic precursor and optional second precursor can be purged from the reaction chamber—e.g., after each pulse and / or upon completion of sub-step 116, sub-step 118, and / or after each permeation cycle. In some embodiments, sub-steps 116 and 118 can be repeated as shown in SIS loop 120. For example, a permeation cycle can be performed one or more times, two or more times, three or more times, five or more times, ten or more times, 25 or more times, or between one and 25 times. Furthermore, sub-steps 116 and 118 can be started and / or terminated in any order. Additionally, each permeation cycle may include repeating sub-step 116 and / or sub-step 118 multiple times before proceeding to subsequent sub-steps in the permeation cycle. In some embodiments, each permeation may also include one or more additional sub-steps that may be performed during each permeation cycle or during selected permeation cycles in a sequence.

[0075] As described above, the metal precursor comprises a metallic material that is introduced (e.g., infiltrated) into the organic layer and will subsequently form a metal seed layer.

[0076] According to examples of this disclosure, the metal precursor comprises a metallic substance from one or more transition metals. In some embodiments, the metal precursor comprises a metallic substance selected from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum. In a particular example, the metal precursor comprises a titanium substance (i.e., elemental titanium). In another example, the metal precursor contains a molybdenum substance (i.e., elemental molybdenum). In some embodiments, the metal precursor comprises a metal halide precursor. In some embodiments, the metal halide precursor comprises at least one of a metal fluoride, a metal chloride, a metal bromide, or a metal bromide. In some embodiments, the metal chloride precursor comprises a metal chloride oxide precursor. In some embodiments, the metal precursor comprises a metal-organic precursor, wherein the metal-organic precursor comprises one or more of the metallic substances disclosed above. In a particular example, the metallic substance is introduced directly without the need to introduce a second precursor (e.g., another precursor or co-reactant). In such examples, the step of introducing the metal precursor into the reaction chamber (sub-step 116) can be performed multiple times with or without an intermediate purging cycle. As a non-limiting example, the metal precursor may comprise a titanium material that permeates into the organic layer by introducing at least one of TiCl4, TiI4, TiF4, or a titanium metal-organic precursor into the reaction chamber. As another non-limiting example, the metal precursor may comprise a molybdenum material that permeates into the organic layer by introducing at least one of MoCl5, MoF6, MoO2Cl2, MoOCl4, or a molybdenum metal-organic precursor into the reaction chamber.

[0077] According to another example of this disclosure, a second precursor (e.g., another precursor or co-reactant) may optionally be introduced into the reaction chamber via sub-step 118, wherein the second precursor comprises a reducing agent. In such an example, the reducing agent may include a synthesis gas (H2+N2), ammonia (NH3), hydrazine (N2H4), molecular hydrogen (H2), hydrogen atoms (H), hydrogen plasma, alcohol, aldehyde, carboxylic acid, borane, or amine.

[0078] You can refer to this. Figure 4 The metal penetration layer is further illustrated by the optional thermal process (step 110) and metal SIS process (step 112) described above. According to the examples of this disclosure, Figure 4 Structure 400 is shown, which includes (after the formation of the metal penetration layer) Figure 3 The structure is 300. For example... Figure 4As shown, structure 400 includes a metal penetration layer 402 disposed above (e.g., on) the first material 212, and specifically, the metal penetration layer 402 is disposed on the bottom surface 206 of the recessed feature 204. In contrast, the metal penetration layer 402 is not disposed above (e.g., on) the second material 214, and specifically, the metal penetration layer 402 is not disposed on the sidewall surface 208 of the recessed feature 204, excluding the portion of the sidewall surface / second material directly at the bottom surface 206 of the recessed feature 204. In some embodiments, the top surface 210 of the recessed feature 204 also lacks the metal penetration layer 402, such as... Figure 4 As shown.

[0079] After introducing the metallic material into the organic layer to form a metal-permeable layer, the method of this disclosure can continue by removing the organic components from the metal-permeable layer. Removing the organic components from the permeable layer while retaining the metallic material (e.g., all or part) results in the formation of a metal seed layer on the bottom surface of the recessed feature (i.e., on the first material).

[0080] Therefore, according to an example of this disclosure, process 100 includes removing organic components from the metal penetration layer, thereby forming a metal seed layer on the bottom surface of the recessed feature (step 122). In such an example, the process for removing organic components includes a thermal process and / or a plasma process.

[0081] In some embodiments, the thermal process for removing organic components includes heating the metal penetration layer to a temperature between 80°C and 600°C, between 100°C and 400°C, or between 120°C and 300°C (i.e., substrate temperature).

[0082] In some embodiments, a plasma process (e.g., a plasma etching process) for removing organic components includes providing plasma within a reaction chamber, which contacts the metal-permeable layer and removes (i.e., etches) the organic components. Oxygen- or hydrogen-containing plasma can be used to remove the organic components from the metal-permeable layer. For example, a plasma generator can be used to excite oxygen to effectively remove the organic components. The plasma generator can be supplied with oxygen (O2) or hydrogen (H2), or alternatively, a mixture of hydrogen (H2) or oxygen (O2) and nitrogen (N2). In a particular example, the plasma etchant used to remove the organic components from the metal-permeable layer may include at least one of an oxygen-excited substance or a nitrogen-excited substance.

[0083] As previously described, the removal of the organic components from the metal-permeable layer forms a metal seed layer on the bottom surface of the recessed feature. The metal seed layer is composed of a metallic substance pre-introduced into the organic layer during the metal SIS process (step 114). Therefore, the metal seed layer may comprise one or more of the aforementioned metals. For example, in some embodiments, the metal seed layer comprises a transition metal. In some embodiments, the metal seed layer is composed of one or more metals derived from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum. In a particular example, the metal seed layer comprises titanium (i.e., a titanium seed layer). In another example, the metal seed layer comprises molybdenum (i.e., a molybdenum seed layer).

[0084] As described above, a metal seed layer is formed by removing organic components from the metal penetration layer (via step 122), which can be referenced. Figure 5 Further explanation. Based on the examples in this disclosure, Figure 5 Structure 500 is shown, which includes (after the formation of the metal seed layer) Figure 4 The structure 400. For example... Figure 5 As shown, structure 500 includes a metal seed layer 502 disposed above (e.g., on) the first material 212 at the bottom of the recessed feature 204, and specifically, the metal seed layer 502 is disposed on the bottom surface 206 of the recessed feature 204. In some embodiments, the metal seed layer 502 is a continuous layer, such as... Figure 5 As shown. In an alternative embodiment, the metal seed layer 502 is a discontinuous layer. In some embodiments, the metal seed layer 502 is disposed on the entirety or most of the first material 212, such as Figure 5 As shown. In an alternative embodiment, the metal seed layer 502 is disposed over a portion of the first material 212. As a non-limiting example, the metal seed layer 502 may be disposed primarily on the middle portion (not shown) of the first material 212 at the base of the recessed feature 204.

[0085] After forming a metal seed layer on the first material at the bottom surface of the recessed feature, the method of this disclosure can continue by depositing a bulk metal layer directly on the metal seed layer, wherein the bulk metal layer fills the recessed feature. In some embodiments, the bulk metal layer is deposited using a cyclic deposition process, wherein the bulk metal layer fills the recessed feature without forming seams. In some embodiments, the bulk metal layer is deposited using a selective cyclic deposition process.

[0086] Therefore, according to an example of the invention, the formation of the bulk metal layer includes depositing the bulk metal layer through a cyclic deposition process. Figure 1In process 100, steps 124 and related sub-steps 126 and 128, in some embodiments, the cyclic deposition process includes an atomic layer deposition process. In a particular example, the cyclic deposition process is a selective deposition process (e.g., selective ALD), in which a bulk metal layer is selectively and / or preferentially deposited within the recessed feature, thereby achieving bottom-up gap filling of the recessed feature. In such examples, the selectivity of the cyclic deposition process can be achieved by the inherent surface properties of the bulk metal deposition on the metal seed layer relative to other surfaces in and near the recessed feature. As a non-limiting example, the selective cyclic deposition process can selectively deposit a bulk metal layer on the metal seed layer relative to other materials of the substrate (e.g., silicon, silicon oxide, and / or silicon nitride). In some embodiments, the selectivity of the bulk metal layer formed on the metal seed layer (i.e., the bottom surface of the recessed feature) is at least about 30%. In some embodiments, the selectivity is at least 50%. In some embodiments, the selectivity is at least 75% or greater than 85%. In some embodiments, the selectivity is at least 90% or at least 93%. In some embodiments, the selectivity is at least 95% or at least 98%. In some embodiments, the selectivity is at least 99% or even at least 99.5%. In embodiments, the selectivity may vary with the duration or thickness of the deposition. It should be noted that a partially selective process can produce a fully selective structure by post-deposition etching, which removes all deposited material from above the second material without removing the entire deposited material within the recessed feature.

[0087] Based on the examples in this disclosure, and referring to Figure 1The step of selectively depositing a bulk metal layer includes performing at least one deposition cycle (step 124) of a cyclic deposition process, wherein each deposition cycle includes introducing a first bulk metal precursor into a reaction chamber to form an absorbed metal material on a metal seed layer (sub-step 126), and introducing a second bulk metal precursor into the reaction chamber to react with the absorbed material to form a bulk metal layer on the metal seed layer (sub-step 128). Sub-steps 126 and 128 may be repeated as shown in deposition cycle loop 130. In a particular example, the deposition cycle (e.g., sub-steps 126 and 128) includes an intermediate purge cycle. In another example, the deposition cycle (e.g., sub-steps 126 and 128) is repeated until a sufficient bulk metal layer is selectively deposited to fill the recessed feature. In such an example, the recessed feature is filled from bottom to top (i.e., starting from the metal seed layer), and by doing so, the bulk metal layer set within and filling the recessed feature is seamless. In another embodiment, substeps 126 and 128 can be started and / or terminated in any order. Furthermore, the selective cyclic deposition process (step 124) may include one or more (e.g., 1-10 or 1-5) substeps 126 and / or 128 preceding another of steps 126 or 128. In some embodiments, each deposition cycle may also include one or more additional substeps that may be performed during each deposition cycle or during a sequence of selective deposition cycles.

[0088] According to examples of this disclosure, the bulk metal layer may include at least one metal as previously described with reference to a metal seed layer. In specific examples, the bulk metal layer includes titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum. In such examples, the first bulk metal precursor may include a precursor described with reference to a metal precursor used during the metal SIS process (114). For example, in specific examples, the first bulk metal precursor includes at least one of a metal halide (e.g., a metal chloride or metal chloride) and an organometallic compound. As a non-limiting example, the bulk metal layer is titanium, and the first bulk metal precursor is at least one of TiCl4, TiI4, TiF4, and a titanium organometallic precursor. As a further non-limiting example, the bulk metal layer is molybdenum, and the first bulk metal precursor is at least one of MoCl5, MoF6, MoO2Cl2, MoOCl4, and a molybdenum organometallic precursor. According to examples of this disclosure, the second bulk metal precursor (e.g., an additional precursor or co-reactant) includes a reducing agent. In such examples, the reducing agent may include syngas (H2+N2), ammonia (NH3), hydrazine (N2H4), molecular hydrogen (H2), hydrogen atom (H), hydrogen plasma, alcohol, aldehyde, carboxylic acid, borane, or amine.

[0089] As mentioned above, the metal seed layer can be used as a nucleation layer (or a series of nucleation sites) for bulk metal layers.

[0090] In some embodiments, the metal seed layer is a first metal, and the bulk metal layer is the same metal (i.e., also the first metal). In a particular example, the metal seed layer is a titanium seed layer, and the bulk metal layer is also a bulk titanium layer. In another example, the metal seed layer is a molybdenum seed layer, and the bulk metal layer is also a molybdenum layer, i.e., a bulk molybdenum layer. In yet another example, the metal seed layer includes a ruthenium-containing layer (e.g., ruthenium tantalum nitride), and the bulk metal layer is also a ruthenium-containing layer.

[0091] In some embodiments, the seed metal layer is a first metal, and the bulk metal layer is a different second metal (i.e., the seed metal layer and the bulk metal layer are composed of different metals). In a particular example, the seed metal layer is a titanium layer, and the bulk metal layer is also a molybdenum layer. In another example, the seed metal layer includes a ruthenium-containing layer (e.g., ruthenium tantalum nitride), and the bulk metal layer is a ruthenium-free layer.

[0092] You can refer to this. Figure 6 Further explanation is provided regarding the formation of a bulk metal layer via a selective cyclic deposition process (step 124), as described above. According to examples of this disclosure, Figure 6 This shows the process including the formation of the bulk metal layer. Figure 5 (The structure of 500 is the structure of 600.) Figure 6 As shown, structure 600 includes a bulk metal layer 602 disposed above (e.g., on) a metal seed layer. Furthermore, the bulk metal layer 602 is shown to completely fill the recessed feature 204 without forming seams within the recessed feature 204, and is not deposited on the top surface 210 of the recessed feature.

[0093] For the purpose of summarizing the advantages of the present invention and its implementation relative to prior art, certain objects and advantages of the present invention have been described above. It should be understood, of course, that not all of these objects or advantages may be achieved according to any particular embodiment of the present invention. Therefore, for example, those skilled in the art will recognize that the present invention may be implemented or performed in a manner that achieves or optimizes one or more advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0094] All these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, and the invention is not limited to any particular embodiment disclosed.

Claims

1. A method for filling a recessed feature on a substrate, the method comprising: A substrate including a recessed feature is placed in a reaction chamber. The recessed feature includes a sidewall surface, a top surface, and a bottom surface, wherein the bottom surface includes a first material, and the sidewall surface includes a second material different from the first material. An organic layer is selectively formed on the first material relative to the second material; A metal sequential infiltration synthesis process is performed to introduce metallic substances into the organic layer, thereby forming a metal infiltration layer; The organic components of the metal penetration layer are removed, thereby forming a metal seed layer on the bottom surface; as well as A bulk metal layer is formed directly on the metal seed layer, wherein the bulk metal layer fills the recessed features.

2. The method according to claim 1, wherein, Selectively forming the organic layer on the first material relative to the second material includes: By introducing a passivating agent into the reaction chamber, the surface of the second material is selectively passivated relative to the surface of the first material; and An organic layer is deposited on the surface of the first material.

3. The method according to claim 2, wherein, The organic layer is selectively formed with a selectivity of more than 50%.

4. The method according to claim 3, wherein, The passivating agent includes alkylaminosilane.

5. The method according to claim 4, wherein, The alkylaminosilane comprises at least one of the following: allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trimethylchlorosilane, and combinations thereof.

6. The method of claim 1, further comprising heat-treating the organic layer in an ammonia (NH3) environment prior to performing the metal sequential permeation synthesis process.

7. The method according to claim 1, wherein, Performing the metal sequential percolation synthesis process includes introducing a metal precursor into the reaction chamber, the metal precursor comprising the metal substance.

8. The method according to claim 7, wherein, The metallic substance is selected from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum.

9. The method according to claim 7, wherein, Performing the metal sequential percolation synthesis process also includes introducing a second precursor into the reaction chamber, the second precursor comprising hydrogen or ammonia.

10. The method according to claim 1, wherein, Removing the organic components from the metal-permeable layer includes a plasma etching process.

11. The method according to claim 1, wherein, Forming the bulk metal layer directly on the metal seed layer includes depositing the bulk metal layer through a cyclic deposition process.

12. The method according to claim 11, wherein, The bulk metal layer includes titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum.

13. The method according to claim 11, wherein, The bulk metal layer is the same as the metal seed layer.

14. The method according to claim 11, wherein, The bulk metal layer is different from the metal seed layer.

15. A method for bottom-up gap filling of recessed features on a substrate, the method comprising: A substrate including a recessed feature is placed in the reaction chamber, the recessed feature including a bottom surface containing a silicon-germanium layer and a sidewall surface containing a silicon layer; The sidewall surfaces, including the silicon layer, are passivated by introducing a passivating agent into the reaction chamber; An organic layer is deposited on a silicon-germanium layer located on the bottom surface of the recessed feature; Perform at least one permeation cycle of a sequential permeation synthesis (SIS) sequence to introduce a metallic substance into an organic layer, thereby forming a metal permeation layer, wherein each permeation cycle includes introducing a metal precursor containing a metallic substance into a reaction chamber, the metallic substance being selected from titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum; The organic components of the metal penetration layer are removed, thereby forming a metal seed layer on the silicon-germanium layer disposed on the bottom surface of the recessed feature; as well as A bulk metal layer is deposited directly on the metal seed layer using a cyclic deposition process, wherein the bulk metal layer fills the depression features without forming seams.

16. The method according to claim 15, wherein, The passivating agent comprises an alkylaminosilane selected from allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilaneamine, trimethylchlorosilane, and combinations thereof.

17. The method according to claim 16, wherein, The organic layer contains polyimide.

18. The method of claim 17, further comprising thermally annealing the organic layer in an ammonia (NH3) environment prior to performing at least one permeation cycle of the sequential permeation synthesis (SIS) sequence.

19. The method according to claim 18, wherein, The metal seed layer is a molybdenum seed layer, and the bulk metal layer is a bulk molybdenum layer.

20. The method according to claim 18, wherein, The metal seed layer is a titanium seed layer, and the bulk metal layer is a bulk molybdenum layer.

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