Methods of forming structures on substrates and related methods of filling recessed features

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 to the field of device and integrated circuit manufacturing. More specifically, this disclosure generally relates to methods for forming structures on a substrate using a sequential permeation synthesis process, and to related methods for filling recessed features on a substrate using such a sequential permeation synthesis process. Background Technology

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

[0003] As semiconductor devices adopt ever-shrinking feature sizes, the photolithography process used to manufacture such devices becomes increasingly complex and prohibitively expensive. Therefore, methods for forming features on substrates with a reduced number of photolithography steps, or even without any photolithography process at all, have become increasingly attractive.

[0004] Certain manufacturing processes that can benefit from photolithography-free processes involve patterning and 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 disposed between protrusions on the substrate surface, such as vertical recessed features, or serrated recessed features formed in the substrate surface.

[0005] For example, high-density plasma (HDP), sub-atmospheric pressure chemical vapor deposition (SACVD), and low-pressure chemical vapor deposition (LPCVD) deposition methods have been used in gap-filling processes, but these and other processes often fail to achieve the desired gap-filling results. Therefore, methods are desired for forming structures on substrates and for filling recessed features using a reduced number of photolithography processes or even without photolithography.

[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 forming structures on a substrate using a sequential permeation synthesis process. Furthermore, various embodiments relate to methods for filling (or at least partially filling) recessed features on a substrate using a sequential permeation synthesis process. Additionally, various embodiments relate to methods for forming semiconductor structures with a reduced number of photolithography processes.

[0009] In one aspect, a method for forming a structure on a substrate is provided, the method comprising: at a substrate in a reaction chamber, the substrate including a photosensitive layer on a surface of the substrate; irradiating a selected region of the photosensitive layer with electromagnetic radiation to form a first region having a first -OH group concentration and a second region having a second -OH group concentration, wherein the first -OH group concentration is greater than the second -OH group concentration; performing a sequential permeation synthesis process to form a first permeated photosensitive layer in the first region, a non-permeable layer disposed below the first permeated photosensitive layer, and a second permeated photosensitive layer in the second region; removing the first permeated photosensitive layer; removing the non-permeable layer; and removing residual components of the second permeated photosensitive layer to form a metal-containing layer on the surface of the substrate.

[0010] In some embodiments, performing a sequential percolation synthesis process includes performing one or more repeated percolation cycles, each percolation cycle including at least introducing a first reactant containing a metallic substance into a reaction chamber.

[0011] In some embodiments, each permeation cycle further includes introducing a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, or a carbon reactant.

[0012] In some embodiments, the metallic material includes one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum.

[0013] In some embodiments, removing the first permeable photosensitive layer includes contacting the first permeable photosensitive layer with an etchant to expose the non-permeable layer.

[0014] In some embodiments, removing the residual components of the non-permeable layer and the second permeable photosensitive layer includes contacting the non-permeable layer and the second permeable photosensitive layer with plasma generated by oxygen-containing gas.

[0015] On another front, a method for filling a recessed feature on a substrate is provided, the method comprising: at a substrate in a reaction chamber, the substrate including the recessed feature and a photosensitive layer disposed above the recessed feature; irradiating the photosensitive layer with electromagnetic radiation of a wavelength equal to or less than the upper dimension of the recessed feature, thereby forming a first region having a first -OH group concentration and a second region having a second -OH group concentration in the photosensitive layer, wherein the first -OH group concentration is greater than the second -OH group concentration; performing a sequential permeation synthesis process, thereby forming a first permeated photosensitive layer in the first region, forming a non-permeable layer disposed below the first permeated photosensitive layer, and forming a second permeated photosensitive layer in the second region; removing the first permeated photosensitive layer; removing the non-permeable layer; removing residual components of the second permeated photosensitive layer to form a metal-containing layer disposed on the lower surface of the recessed feature; and directly forming a host layer on the metal-containing layer, wherein the host layer fills the recessed feature.

[0016] In some embodiments, performing a sequential percolation synthesis process includes performing one or more repeated percolation cycles, each percolation cycle including at least introducing a first reactant containing a metal precursor into a reaction chamber, the metal precursor comprising a metallic substance.

[0017] In some embodiments, each permeation cycle further includes introducing a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, or a carbon reactant.

[0018] In some embodiments, the metallic material includes one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum.

[0019] In some embodiments, the photosensitive layer includes an organic layer.

[0020] In some embodiments, the residual component includes a residual organic component, and removing the residual organic component includes contacting the residual organic component with a plasma generated by an oxygen-containing gas.

[0021] In some embodiments, forming the host layer directly on the metal-containing layer includes depositing the host layer through a cyclic deposition process.

[0022] In some embodiments, the host layer comprises one or more of a metal, a metal oxide, a metal nitride, and a metal carbide.

[0023] In some embodiments, both the body layer and the metal-containing layer contain metallic materials.

[0024] In some embodiments, the host layer is different from the metal-containing layer.

[0025] In some embodiments, the method further includes heat-treating the photosensitive layer in an ammonia (NH3) environment prior to performing the sequential permeation synthesis process.

[0026] On the other hand, a photolithography-free method for bottom-up gap filling of a recessed feature is provided. The method includes: at a substrate in a reaction chamber, the substrate including an organic photosensitive layer disposed on the recessed feature, wherein the recessed feature includes an upper dimension, a lower surface, and an upper surface; irradiating the organic photosensitive layer with electromagnetic radiation of a wavelength equal to or less than the upper dimension of the recessed feature, thereby forming a first region having a first -OH group concentration and a second region having a second -OH group concentration in the organic photosensitive layer, wherein the first -OH group concentration is greater than the second -OH group concentration; and heat treatment in an ammonia (NH3) environment. An organic photosensitive layer is formed; at least one permeation cycle of a sequential permeation synthesis (SIS) sequence is performed to introduce a metallic material into the organic photosensitive layer, thereby forming a first metal permeation layer in a first region, a second metal permeation region in a second region, and a non-permeation layer, wherein the metallic material includes one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum; the first metal permeation layer is contacted with an etchant to remove the first metal permeation layer; the residual organic components of the non-permeation layer and the second metal permeation region are contacted with plasma generated by oxygen reactants, thereby filling the recessed feature at least partially with a metal-containing layer.

[0027] In some embodiments, the metal layer fills the recessed features onto the upper surface without forming a seam.

[0028] In some embodiments, the metal-containing layer partially fills the recessed feature, and the host layer is deposited on the metal-containing layer to fill the recessed feature onto the upper surface without forming a seam.

[0029] For the purpose of outlining embodiments of this disclosure and their advantages, certain objects and advantages of such embodiments have been described above. It should be understood, of course, that not all such objects or advantages may be achieved according to any particular embodiment of this disclosure. Therefore, for example, those skilled in the art will recognize that embodiments of this disclosure may be implemented or performed in a manner that achieves or optimizes one or more advantages taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0030] All these embodiments are intended to fall within the scope of this disclosure. 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 this disclosure is not limited to any particular embodiment disclosed. Attached Figure Description

[0031] 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.

[0032] 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.

[0033] Figure 1 A method for forming a structure on a substrate according to one or more embodiments of the present disclosure is illustrated.

[0034] Figure 2 Structures according to one or more embodiments of this disclosure are shown.

[0035] Figure 3 Structures according to one or more embodiments of this disclosure are shown.

[0036] Figure 4 Structures according to one or more embodiments of this disclosure are shown.

[0037] Figure 5 Structures according to one or more embodiments of this disclosure are shown.

[0038] Figure 6 Structures according to one or more embodiments of this disclosure are shown.

[0039] Figure 7 Structures according to one or more embodiments of this disclosure are shown.

[0040] Figure 8 A method for filling a recessed feature according to one or more embodiments of the present disclosure is shown.

[0041] Figure 9 Structures according to one or more embodiments of this disclosure are shown.

[0042] Figure 10 Structures according to one or more embodiments of this disclosure are shown.

[0043] Figure 11 Structures according to one or more embodiments of this disclosure are shown.

[0044] Figure 12 Structures according to one or more embodiments of this disclosure are shown.

[0045] Figure 13 Structures according to one or more embodiments of this disclosure are shown.

[0046] Figure 14 Structures according to one or more embodiments of this disclosure are shown.

[0047] 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

[0048] 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.

[0049] 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" is used interchangeably with the term "precursor."

[0050] 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.

[0051] 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 comprise or be composed of a plurality of dispersed atoms on a substrate surface, and / or can be embedded in or on a substrate and / or embedded in a device fabricated on the 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.

[0052] 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.

[0053] 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, 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.

[0054] 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) to form a monolayer or submonolayer of material that is not readily reactive with additional precursors (i.e., self-limiting reaction). Subsequently, a reactant (e.g., another precursor or reactive gas) may 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.

[0055] As used herein, "structure" can be or includes a substrate as described herein. A structure may 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 a device may be included within or on the structure.

[0056] As used herein, the term "recessed feature" can refer to an opening or cavity disposed between surfaces of a non-planar surface. For example, the term "recessed feature" can refer to an opening or cavity disposed between opposing sidewalls or protrusions extending vertically from the surface of a substrate, or between opposing inclined sidewalls of a recess extending vertically into the surface of a substrate.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] In this specification, it will 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.

[0061] Various embodiments relate to methods for forming structures on a substrate and related methods for filling recessed features on a substrate using a sequential permeation synthesis process, as well as related structures formed by such methods.

[0062] Switch to the attached image. Figure 1An exemplary method 100 is illustrated. In short, method 100 includes a substrate comprising a photosensitive layer (step 102). Selected regions of the photosensitive layer are then irradiated with electromagnetic radiation to form a first region having a first -OH group concentration and a second region having a second -OH group concentration, wherein the first -OH group concentration is greater than the second -OH group concentration (step 104). A sequential permeation synthesis process is then performed to form a first permeated photosensitive layer in the first region, a non-permeable layer disposed beneath the first permeated photosensitive layer, and a second permeated photosensitive layer in the second region (step 106). Method 100 can continue by removing the first permeated photosensitive layer (step 114) and removing the non-permeable layer (step 116). Method 100 may further include removing residual components of the second permeated photosensitive layer to form a metal-containing layer on the surface of the substrate (step 118).

[0063] Based on the examples in this disclosure, Figure 2 The substrate 200 on which the photosensitive layer 304 is formed is shown, such as Figure 3 The structure 300 is shown. In some embodiments, structure 300 may include a portion of a device structure, such as a partially fabricated device structure. In such embodiments, structure 300 may include a partially fabricated logic device, memory device, integrated circuit, etc. In some embodiments, photosensitive layer 304 may include at least one of a high-resolution polymeric resist or a hard mask material. According to examples of this disclosure, the photosensitive layer may include an organic photosensitive layer. In one aspect, the photosensitive layer may include at least one of poly(methyl methacrylate) (PMMA), polystyrene, poly(styrene-block-methyl methacrylate) (PS-b-PMMA), deep ultraviolet (UV) photoresist, 193nm photoresist (immersion (193i) and non-immersion (193)), and extreme UV photoresist. In some embodiments, the photosensitive layer may include a first component and a second component, wherein the first component may have at least a first oriented self-assembly (DSA) polymer, and the second component may have a second oriented self-assembly polymer, wherein the first and second oriented self-assembly polymers may be made of PMMA, polystyrene (PS), and other polymers. On the other hand, the photosensitive layer may include a hard mask comprising at least one of spin-coated glass, spin-coated carbon layer, silicon nitride layer, anti-reflective coating, or amorphous carbon layer. The spin-coated glass or spin-coated carbon layer can be provided by spin-coating the glass or carbon layer onto the substrate to provide the hard mask material. In some embodiments, the photosensitive layer may be formed on the substrate by a deposition process (e.g., atomic layer deposition).

[0064] Turn to Figure 1Method 100, step 104 includes irradiating a selected area of ​​the photosensitive layer with electromagnetic (EM) radiation. According to an example of this disclosure, a substrate having the photosensitive layer thereon can be disposed within a device configured for irradiating the photosensitive layer with electromagnetic radiation. In one aspect, irradiating the selected area of ​​the photosensitive layer may include using an irradiation device, such as an extreme ultraviolet lithography device, a directional writing device, etc. In another aspect, irradiating the selected area of ​​the photosensitive layer can be performed without requiring such complex irradiation equipment and processes, as referenced below. Figure 8 Method 800 is discussed. In various embodiments, the photosensitive layer can be irradiated with electromagnetic radiation with wavelengths less than 1000 nm, less than 750 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 100 nm, less than 50 nm, less than 25 nm, less than 15 nm, or equal to or less than 13.5 nm. In various embodiments, the photosensitive layer can be irradiated with electromagnetic radiation with wavelengths between 13.5 nm and 1000 nm.

[0065] According to embodiments of this disclosure, irradiating a selected area of ​​the photosensitive layer with electromagnetic radiation can result in the formation of a first region having a first -OH group concentration and a second region having a second -OH group concentration. In such embodiments, the first -OH group concentration may be greater than the second -OH group concentration.

[0066] Figure 4 Structure 400 is shown, illustrating the selective irradiation of the photosensitive layer 304 using electromagnetic radiation 406, and Figure 5 Structure 500 is shown when the selective irradiation step (e.g., step 104 of method 100) is completed. Figure 5 As shown, through electromagnetic radiation 406 ( Figure 4 Selective irradiation of the photosensitive layer 304 results in the formation of a first region 508 and a second region 510. Figure 5 According to an example of this disclosure, the first region 508 corresponds to the region of the photosensitive layer 304 exposed to electromagnetic radiation 406 (e.g., ...). Figure 4 As shown), and the second region 510 corresponds to the region of the photosensitive layer 304 that is not exposed to electromagnetic radiation 406. In such an example, the first region 508 receives electromagnetic radiation with a higher illuminance (E) compared to the second region 510. While not bound by any theory or mechanism, it has been found that irradiating a selected region of the photosensitive layer with electromagnetic radiation results in a higher illuminance (E) in the irradiated region of the photosensitive layer (i.e.,...). Figure 5 The first region 508) forms with the region (i.e. Figure 5 The second region 510 is either an unirradiated region or a region exposed to electromagnetic radiation with a lower illuminance than the first region 508, compared to a region with a higher concentration of hydroxyl groups.

[0067] Method 100 may proceed to step 106, which includes performing a sequential permeation synthesis process. According to examples of this disclosure, performing a sequential permeation synthesis process may form a first permeation photosensitive layer in a first region, a non-permeable layer disposed below the first permeation photosensitive layer, and a second permeation photosensitive layer in a second region. Not bound by any theory or mechanism, but it has been found that regions with higher concentrations of hydroxyl groups (e.g., Figure 5 The first region 508) forms a surface shell of the permeating material during permeation, while regions with a lower concentration of hydroxyl groups (e.g.) Figure 5 The second region (510) can be completely or more completely permeated with permeable substances.

[0068] More specifically, and according to examples of this disclosure, a sequential infiltration synthesis process (step 106) can be used to introduce a metallic substance into the photosensitive layer, and this can be achieved by optionally heat-treating the photosensitive layer (as described below) and using an infiltration process to inject metal atoms into the framework of the photosensitive layer. As a non-limiting example, the sequential infiltration synthesis process may include adsorbing at least a portion of a metal precursor into the photosensitive layer (e.g., dissolving and / or diffusing the metal precursor into the photosensitive layer). The metal precursor can then interact with the photosensitive layer (e.g., through reversible complex formation and / or irreversible chemical reactions), and this interaction between the metal precursor and the photosensitive layer results in the retention of the metallic substance provided by the metal precursor within the photosensitive layer, forming an infiltrated layer. As described above, the first region 508 and the second region 510 are infiltrated to different degrees depending on the concentration of -OH groups in the first and second regions.

[0069] Sequential permeation synthesis (also referred to as the SIS process in this paper) in Figure 1 As illustrated in step 106, step 106 includes sub-step 108 and optional sub-step 110. According to an example of this disclosure, the SIS process (step 106) includes performing one or more repeated permeation cycles, each permeation cycle including the introduction of a first reactant containing a metallic substance into the reaction chamber (sub-step 108). In some embodiments, each permeation cycle may optionally include the introduction of a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, or a carbon reactant.

[0070] According to examples of this disclosure, a first reactant (e.g., a metal precursor comprising a metallic substance) and an optional second reactant can be introduced into the reaction chamber by pulses of one or more reactants into the reaction chamber, wherein they contact the surface of the substrate, including the photosensitive layer. The first reactant and the optional second reactant can be purged from the reaction chamber—e.g., after each pulse and / or upon completion of sub-step 108, sub-step 110, and / or after each permeation cycle. In some embodiments, sub-steps 108 and 110 can be repeated as shown in loop 112. For example, the 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 one to 25 times. Furthermore, sub-steps 108 and 110 can be started and / or terminated in any order. Additionally, each permeation cycle may include multiple repetitions of sub-steps 108 and / or 110 prior to proceeding to subsequent sub-steps of the permeation cycle. In some embodiments, each permeation cycle may also include one or more additional sub-steps that can be performed during each permeation cycle or during selected permeation cycles in a sequence.

[0071] According to examples of this disclosure, the first reactant may comprise a metal precursor containing a metallic substance. In some embodiments, the metallic substance may comprise a half-metallic substance, such as silicon and germanium. In some embodiments, the metallic substance may comprise an elemental metallic substance. In such embodiments, the metallic substance may be selected from one or more transition metals. In some embodiments, the metallic precursor contains a metallic substance comprising one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, and molybdenum. In a particular example, the metallic precursor comprises an aluminum substance (i.e., elemental aluminum). In another example, the metallic precursor comprises a titanium substance (i.e., elemental titanium). In another example, the metallic precursor comprises a molybdenum substance (i.e., elemental molybdenum). In some embodiments, the metallic 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 metallic precursor comprises a metal organometallic precursor, wherein the metal organometallic 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 reactant. In such an example, the step of introducing the metal precursor into the reaction chamber (sub-step 108) can be performed multiple times with or without an intermediate purging cycle.

[0072] As a non-limiting example, the metal precursor may comprise an aluminum material that permeates into the photosensitive layer by introducing at least one of trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), aluminum dimethylisopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropanol)aluminum (TIPA), and triethylaluminum (TEA) into the reaction chamber.

[0073] As a further 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.

[0074] As another non-limiting example, the metal precursor may contain a molybdenum substance 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.

[0075] According to another example of this disclosure, a second reactant may optionally be introduced into the reaction chamber via sub-step 110. In such examples, the second reactant may include one or more of an oxygen reactant, a nitrogen reactant, a carbon reactant, and a reducing agent. In some embodiments, the oxygen reactant may include, but is not limited to, water, hydrogen peroxide, and mixtures thereof. In some embodiments, the nitrogen reactant may include, but is not limited to, ammonia (NH3), hydrazine (N2H4), alkyl hydrazine derivatives, and mixtures thereof. In some embodiments, the carbon reactant may include, but is not limited to, acetylene, ethylene, alkyl halide compounds, olefin halide compounds, metal alkyl compounds, and mixtures thereof. Exemplary alkyl halogenated compounds include CX4, CHX3, CH2X2, CH3X, wherein X ═ F, Cl, Br, or I. Exemplary olefin halogenated compounds include C2H3X, C2H2X2, C2HX3, and C2X4, wherein X ═ F, Cl, Br, or I. Exemplary alkyne halogenated compounds include C2X2 and HC2X, wherein X ═ F, Cl, Br, or I. In some embodiments, the permeated carbon component may be provided as a component of the first reactant. For example, the first reactant may include a compound comprising a metallic substance and a carbon component, such as when an organometallic / organometallic compound is used as the first reactant. In such an example, the introduction of the carbon reactant into the reaction chamber may be performed via sub-steps 108 and / or 110 of the SIS process (step 106). In some embodiments, the reducing agent may include, but is not limited to, synthesis gas (H2+N2), ammonia (NH3), hydrazine (N2H4), molecular hydrogen (H2), hydrogen atoms (H), hydrogen plasma, alcohols, aldehydes, carboxylic acids, boranes, amines, and mixtures thereof.

[0076] According to an example of this disclosure, performing a sequential permeation synthesis process (step 106) can result in the formation of a first permeation photosensitive layer in a first region, the formation of a non-permeation layer disposed below the first permeation photosensitive layer, and the formation of a second permeation photosensitive layer in a second region. Figure 6 It shows the results including after infiltration. Figure 5 The structure of 500 is the same as the structure of 600. For example... Figure 6As shown, structure 600 includes a first permeable photosensitive layer 614 (i.e., the surface corresponding to the first region) and a second permeable photosensitive layer 616 (i.e., corresponding to the second region). In some embodiments, a non-permeable layer 612 may be disposed below the first permeable photosensitive layer 614.

[0077] According to the examples in this disclosure, method 100 ( Figure 1 The process further includes removing the first permeated photosensitive layer (step 114). In such an example, the first permeated photosensitive layer 614 can be removed by contacting it with an etchant. In some embodiments, the etchant can be one or more of a wet etchant, a vapor-phase etchant, or a plasma-based etchant. In some embodiments, the first permeated photosensitive layer can be removed by an atomic layer etching (ALE) process. In some embodiments, the etchant can include a halide-based etchant, such as a chlorine- or fluorine-based etchant.

[0078] According to the examples in this disclosure, method 100 ( Figure 1 The process further includes removing the non-permeable layer (step 116) and removing residual components of the second permeable photosensitive layer, thereby forming a metal-containing layer on the surface of the substrate (step 118). In one aspect, the non-permeable layer can be removed in step 114 by selecting an etchant for removing the second permeable photosensitive layer. In another aspect, the non-permeable layer can be removed by step 118, i.e., the process for removing residual components of the second permeable photosensitive layer can also remove the non-permeable layer.

[0079] According to examples of this disclosure, removing residual components from the second permeated photosensitive layer may include contacting the second permeated photosensitive layer with a plasma generated by an oxygen-containing gas. In some embodiments, a plasma containing oxygen, nitrogen, hydrogen, or a mixture thereof may be used to remove residual components from the second permeated photosensitive layer. For example, a plasma generator may be used to excite an oxygen substance to effectively remove residual components. The plasma generator may be supplied with oxygen (O2) or hydrogen (H2), or alternatively, a mixture of hydrogen (H2) or oxygen (O2) and nitrogen (N2). In various embodiments, the plasma generator may be supplied with ammonia (NH3). In various embodiments, the plasma generator may be supplied with carbon dioxide (CO2). In a particular example, the plasma etchant used to remove residual components from the second permeated photosensitive layer may include at least one of an oxygen-excited substance or a nitrogen-excited substance.

[0080] Figure 7 Structure 700 is shown, which includes structure 600 after removing residual components of the first permeable photosensitive layer, the non-permeable layer, and the second permeable photosensitive layer. Figure 6 According to the examples in this disclosure, remove ( Figure 6The remaining components of layers 612, 614, and 616 form a metal-containing layer 718 on substrate 202. In some embodiments, the metal-containing layer may comprise one or more of a metal, a metal oxide, a metal nitride, and a metal carbide. In some embodiments, the metal-containing layer may comprise an elemental metal comprising one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, and molybdenum. In some embodiments, the metal-containing layer may comprise a half-metal comprising one or more of silicon and germanium. In some embodiments, the metal-containing layer comprises a metal oxide comprising one or more of aluminum oxide, hafnium oxide, titanium oxide, niobium oxide, tungsten oxide, cobalt oxide, ruthenium oxide, and molybdenum oxide. In some embodiments, the metal-containing layer may comprise a half-metal oxide comprising one or more of silicon oxide and germanium oxide. In some embodiments, the metal-containing layer comprises a metal nitride comprising one or more of aluminum nitride, hafnium nitride, titanium nitride, niobium nitride, tungsten nitride, cobalt nitride, ruthenium nitride, and molybdenum nitride. In some embodiments, the metal-containing layer may comprise a half-metal nitride comprising one or more of silicon nitride and germanium nitride. In some embodiments, the metal-containing layer comprises a metal carbide, including one or more of aluminum carbide, hafnium carbide, titanium carbide, niobium carbide, tungsten carbide, cobalt carbide, ruthenium carbide, and molybdenum carbide. In some embodiments, the metal-containing layer may comprise a half-metal carbide, including one or more of silicon carbide and germanium carbide. As a non-limiting example, the metal-containing layer may include at least one of molybdenum, aluminum oxide, silicon dioxide, and hafnium oxide.

[0081] Various other embodiments of this disclosure provide methods for filling recessed features on a substrate. These methods may include a bottom-up, lithography-free gap-filling process for the recessed features on the substrate. Such alternative methods may employ irradiation of a selected area of ​​a photosensitive layer and a sequential permeation synthesis process, as described above, but may also additionally include electromagnetic radiation using a selected wavelength. In such examples, the selected wavelength may not penetrate to the lower surface of the recessed feature, as described in detail below.

[0082] Turning back to the attached image, Figure 8 An exemplary method 800 for filling recessed features on a substrate is illustrated. The various steps (and related sub-steps) of method 800 have been described in detail above; therefore, the following detailed description will describe the steps of method 800 in detail, including embodiments different from those previously described.

[0083] According to an example embodiment, method 800 ( Figure 8 This includes providing a substrate and / or, at the substrate, including a recessed feature and a photosensitive layer disposed above the recessed feature (step 802). According to examples of this disclosure, the substrate may include a non-planar substrate that includes one (or more) recessed features.

[0084] Figure 9An exemplary non-planar substrate 902 including a recessed feature 904 is shown. According to an example of this disclosure, the recessed feature 904 includes an upper dimension 906 defining an opening size for an upper portion of the recessed feature. As a non-limiting example, the upper dimension 906 may define the diameter of the upper portion of the recessed feature 904. In some embodiments, the upper dimension is less than 1000 nm, less than 750 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 100 nm, less than 50 nm, less than 25 nm, less than 15 nm, less than 12 nm, less than 8 nm, or between 8 nm and 1000 nm.

[0085] Although the non-planar substrate 902 is Figure 9 The illustration depicts a single recessed feature 904, but it should be understood that the provided methods are not limited to this, and substrates comprising multiple recessed features can be filled using the methods disclosed herein. It should also be noted that the cross-sectional profile of the recessed feature 904 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 904 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 may have an aspect ratio (e.g., height to width ratio) 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.

[0086] According to examples of this disclosure, a photosensitive layer is disposed above a substrate. In some embodiments, the photosensitive layer includes a conformal photosensitive layer disposed on a non-planar substrate, particularly above a recessed feature within the non-planar substrate. In various embodiments, the photosensitive layer is formed and comprises the materials described above. In some embodiments, the photosensitive layer may include an organic layer, such as an organic photosensitive layer.

[0087] Figure 10 Structure 1000 is shown, which includes a non-planar substrate 902 and a photosensitive layer 1004 disposed above the recessed feature 904 and the non-planar substrate 902. Figure 10 As shown, the photosensitive layer 1004 is disposed on the upper surface 908 and the lower surface 910 of the recessed feature 904 and above the sidewall of the recessed feature.

[0088] In an alternative embodiment, the photosensitive layer may be a non-conformal layer (not shown). In such an embodiment, the non-conformal photosensitive layer may fill or substantially fill the recessed feature.

[0089] In various embodiments, method 800 ( Figure 8The process may further include irradiating the photosensitive layer with electromagnetic radiation of a wavelength equal to or less than the upper dimension of the recessed feature (step 804), thereby forming a first region in the photosensitive layer having a first -OH group concentration and a second region in the photosensitive layer having a second -OH group concentration, wherein the first -OH group concentration is greater than the second -OH group concentration. According to an example of this disclosure, irradiating the photosensitive layer with electromagnetic radiation of a wavelength equal to or less than the upper dimension may include blanket exposure of a substrate on which the photosensitive layer is disposed. According to another example of this disclosure, the wavelength of the electromagnetic radiation may be selected to be less than the upper dimension of the recessed feature, such that the electromagnetic radiation is prevented or substantially prevented from penetrating the lower surface of the recessed feature (e.g., the lower surface 910 of the recessed feature 904, such as...). Figure 9 (As shown). In such an example, the upper surface 908 (and the corresponding portion of the photosensitive layer thereon) receives electromagnetic radiation with a higher illuminance (E) compared to the lower surface 910 (and the corresponding portion of the photosensitive layer thereon). In such an example, the portion of the photosensitive layer on the upper surface of the recessed feature may have a higher concentration of hydroxyl groups compared to the portion of the photosensitive layer on the lower surface of the recessed feature (which is not irradiated or exposed to electromagnetic radiation with a lower illuminance compared to the portion of the photosensitive layer on the upper surface). According to examples of this disclosure, the wavelength of the electromagnetic radiation is smaller than the upper dimension of the recessed feature. In such examples, the wavelength of the electromagnetic radiation may be less than 1000 nm, less than 750 nm, less than 500 nm, less than 400 nm, less than 300 nm, less than 200 nm, less than 100 nm, less than 50 nm, less than 25 nm, less than 15 nm, or equal to or less than 13.5 nm. In various embodiments, the photosensitive layer may be irradiated with electromagnetic radiation with wavelengths between 13.5 nm and 1000 nm.

[0090] Figure 11 Structure 1100 is shown, which includes irradiating the photosensitive layer with electromagnetic radiation having a wavelength equal to or smaller than the upper dimension of the recessed feature (i.e., after completing method 800). Figure 8 After step 804, the structure 1000 ( Figure 10 ).like Figure 11 As shown, electromagnetic radiation 1106 can be a blanket wave of electromagnetic (EM) radiation, which is consistent with... Figure 4 The selective electromagnetic radiation 406 forms a contrast. Furthermore, structure 1100 includes a first region 1108 of a photosensitive layer having a first -OH group concentration and a second region 1110 of a photosensitive layer having a second -OH group concentration disposed on the upper surface of the recessed feature, wherein the first -OH group concentration is greater than the second -OH group concentration.

[0091] In various embodiments, method 800 ( Figure 8The method may further include performing a sequential permeation synthesis process to form a first permeated photosensitive layer in a first region, a non-permeable layer disposed below the first permeated photosensitive layer, and a second permeated photosensitive layer in a second region (step 806 and associated substeps 808 and 810, and loop 814). In some embodiments, performing the sequential permeation synthesis process (step 806) includes performing one or more repeated permeation cycles, each permeation cycle including at least introducing a first reactant comprising a metal precursor (substep 808) into the reaction chamber, the metal precursor comprising a metallic substance. In some embodiments, the metallic substance is selected from one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum. In some embodiments, each permeation cycle further includes introducing a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, or a carbon reactant (substep 812). The SIS process of method 800 (step 806) has been previously described with respect to method 100, particularly with respect to step 106 (and substeps 108 and 110), and therefore will not be repeated here.

[0092] Figure 12 Structure 1200 is shown, which includes structure 1200 after the completion of the sequential permeation synthesis process (i.e., after completing step 806 of method 800). Figure 12 As shown, structure 1200 includes a first permeable photosensitive layer 1214 (i.e., the surface corresponding to the first region disposed above the upper surface 908) and a second permeable photosensitive layer 1216 (i.e., the second region disposed above the lower surface 910). In some embodiments, a non-permeable layer 1212 may be disposed below the first permeable photosensitive layer 1214.

[0093] In various embodiments, method 800 may further include removing the first permeable photosensitive layer (step 818), as described in step 114 of previously referred method 100.

[0094] In various embodiments, method 800 may further include removing the non-permeable layer 612 (step 820), as described in step 116 of previously referred to method 100.

[0095] In various embodiments, method 800 may further include removing residual components from the second permeated photosensitive layer to form a metal-containing layer disposed on the lower surface of the recessed feature. In some embodiments, the residual components include residual organic components (e.g., when the photosensitive layer comprises an organic photosensitive layer), and removing the residual organic components includes contacting the residual organic components with a plasma generated by an oxygen-containing gas or other gas, as described in step 118 of previously referred to method 100. According to an example of this disclosure, removing residual components from the second permeated photosensitive layer forms a metal-containing layer disposed on the lower surface of the recessed feature. In such an example, the metal-containing layer comprises one or more of a metal, a metal oxide, a metal nitride, and a metal carbide, as described above and including all the materials previously described. In some embodiments, the metal-containing layer may be used as formed. In alternative embodiments, the metal-containing layer may have sufficient thickness to fill the recessed feature. In alternative embodiments, the metal-containing layer may include a seed layer, and the seed layer may serve as a nucleation layer for depositing a host layer that fills or at least partially fills the recessed feature, as described in detail below.

[0096] Figure 13 Structure 1300 is shown, which includes structure 1200 after removing residual components of the first permeable photosensitive layer 1214, the non-permeable layer 1212, and the second permeable photosensitive layer 1216. Figure 12 According to the examples in this disclosure, remove ( Figure 12 The layers 1212, 1214 of the second permeated photosensitive layer 1216 and residual components can form a metal-containing layer 1318 on the non-planar substrate 902. In such an example, the metal-containing layer 1318 may be formed at the lower surface 910 of the recessed feature 904. In another example, the metal-containing layer 1318 may fill or substantially fill the recessed feature 904 (not shown). In some embodiments, the metal-containing layer 1318 may include one or more of a metal, a metal oxide, a metal nitride, and a metal carbide.

[0097] In various embodiments, a metal-containing layer has been formed at the lower surface of the recessed feature, and the method of this disclosure can be continued by depositing a host layer directly on the metal-containing layer, wherein the host layer fills the recessed feature. In some embodiments, the host layer is deposited using a cyclic deposition process, wherein the host layer fills the recessed feature without forming seams. In some embodiments, the host layer is deposited via a cyclic deposition process. In some embodiments, the host layer is deposited via a selective cyclic deposition process.

[0098] In various embodiments, method 800 ( Figure 8Therefore, the formation of a host layer may be further included. The host layer can be deposited via a cyclic deposition process (step 822 and associated substeps 824 and 826, and deposition loop 828). 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), wherein the host 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 or facilitated by the inherent surface properties of the host layer deposition on the metal-containing layer (i.e., the seed layer) relative to other surfaces in and near the recessed feature. In some embodiments, the selectivity of the host layer formed on the metal-containing layer (i.e., the lower 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 some embodiments, the selectivity may vary within the duration or thickness of the deposition. It should be noted that partially selective processes can produce fully selective structures through post-deposition etching, which removes all deposited material from above the second material without removing the entire deposited material from within the recessed feature.

[0099] Based on the examples in this disclosure, and referring again to Figure 8 The step of depositing the host layer may include at least one deposition cycle (step 822) of performing a cyclic deposition process, wherein each deposition cycle includes introducing a first host metal precursor into a reaction chamber to form an absorbed metal material on the metal-containing layer (sub-step 824), and introducing a second host metal precursor into the reaction chamber to react with the absorbed material to form a host layer on the metal-containing layer (sub-step 826). Sub-steps 824 and 826 may be repeated as shown in deposition cycle loop 828. In a particular example, the deposition cycle (e.g., sub-steps 824 and 826) includes an intermediate purge cycle. In another example, the deposition cycle is repeated until a host layer of sufficient thickness has been 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-containing layer), and by doing so, the host layer disposed within the recessed feature is seamless. In another embodiment, sub-steps 824 and 826 may be started and / or terminated in any order. Furthermore, the cyclic deposition process (step 822) may include one or more (e.g., 1-10 or 1-5) sub-steps 824 and / or 826 preceding another of sub-steps 824 or 826. In some embodiments, each deposition cycle may also include one or more additional sub-steps that may be performed during each deposition cycle or during selected deposition cycles in a sequence.

[0100] According to examples of this disclosure, the host layer may include one or more of a metal, a metal oxide, a metal nitride, a metal carbide, etc. In some embodiments, the host metal layer may include one or more of the materials previously described with reference to the metal-containing layer. In a particular example, the host layer includes at least one of titanium, aluminum, niobium, tungsten, tantalum, cobalt, ruthenium, and molybdenum. In such an example, the first host metal precursor may include at least one of a titanium precursor, an aluminum precursor, a niobium precursor, a tungsten precursor, a cobalt precursor, a ruthenium precursor, and a molybdenum precursor. In some embodiments, the first host metal precursor may contain the same metallic substance as the metallic substance introduced in the SIS process (806). For example, in a particular example, the first host metal precursor includes at least one of a metal halide (e.g., a metal chloride or a metal chloride oxide) and an organometallic compound. As a non-limiting example, the host layer may include titanium, and the first host metal precursor may include at least one of TiCl4, TiI4, TiF4, and a titanium organometallic precursor. As a further non-limiting example, the host layer may include molybdenum, and the first host metal precursor may include at least one of MoCl5, MoF6, MoO2Cl2, MoOCl4, and a molybdenum metal organic precursor.

[0101] According to examples of this disclosure, the second host metal precursor (e.g., an additional precursor or co-reactant) includes one or more of oxygen reactants, nitrogen reactants, carbon reactants, or reducing agents, as previously described above with reference to the formation of the metal layer.

[0102] As described above, the metal layer can be used as a nucleation layer (or a series of nucleation sites) of the host layer.

[0103] In some embodiments, the metal-containing layer may comprise a first metal, and the host layer may also comprise a first metal (i.e., both the metal-containing layer and the host layer comprise the same metallic substance). In a particular example, the metal-containing layer is a titanium seed layer, and the host layer is also a host titanium layer. In another example, the metal-containing layer is a molybdenum seed layer, and the host layer is also a molybdenum layer, i.e., a host molybdenum layer. In yet another example, the metal-containing layer includes a ruthenium-containing layer (e.g., ruthenium tantalum nitride), and the host layer is also a ruthenium-containing layer.

[0104] In some embodiments, the metal-containing layer is a first metal, and the host layer is a different second metal (i.e., the metal-containing layer and the host layer are composed of different metals). In a particular example, the metal-containing layer is a titanium layer, and the host layer is also a molybdenum layer. In another example, the metal-containing layer includes a ruthenium-containing layer (e.g., ruthenium tantalum nitride), and the host layer is a non-ruthenium-containing layer.

[0105] As mentioned above, you can refer to Figure 14 The formation of the host layer through a cyclic deposition process is further illustrated (step 822). According to examples of this disclosure, Figure 14Structure 1400 is shown, which includes (after the formation of the main body layer) Figure 13 The structure 1300. For example... Figure 14 As shown, structure 1400 includes a body layer 1420 disposed above (e.g., on top of) the metal layer 1318. Furthermore, the body layer 1420 is shown to completely fill the recessed feature 904 without forming a seam within the recessed feature 904.

[0106] 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.

[0107] 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 forming a structure on a substrate, the method comprising: At the substrate, the substrate includes a photosensitive layer on the surface of the substrate; A selected area of ​​the photosensitive layer is irradiated with electromagnetic radiation to form a first region with a first -OH group concentration and a second region with a second -OH group concentration, wherein the first -OH group concentration is greater than the second -OH group concentration. A sequential permeation synthesis process is performed to form a first permeation photosensitive layer in a first region, a non-permeation layer disposed below the first permeation photosensitive layer, and a second permeation photosensitive layer in a second region. Remove the first permeated photosensitive layer; Remove the non-penetrating layer; as well as The residual components of the second permeated photosensitive layer are removed, thereby forming a metal-containing layer on the surface of the substrate.

2. The method according to claim 1, wherein, Performing the sequential percolation synthesis process includes performing one or more repeated percolation cycles, each percolation cycle including the introduction of a first reactant containing a metallic substance into the reaction chamber.

3. The method according to claim 2, wherein, Each permeation cycle also includes the introduction of a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, a carbon reactant, or a reducing agent.

4. The method according to claim 2, wherein, The metallic substance includes one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum.

5. The method according to claim 1, wherein, Removing the first permeable photosensitive layer includes contacting the first permeable photosensitive layer with an etchant to expose the non-permeable layer.

6. The method according to claim 1, wherein, Removing the non-permeable layer and residual components from the second permeable photosensitive layer includes contacting the non-permeable layer and the second permeable photosensitive layer with plasma generated by oxygen-containing gas.

7. A method for filling a recessed feature, the method comprising: At the substrate, the substrate includes a recessed feature and a photosensitive layer disposed above the recessed feature; The photosensitive layer is irradiated with electromagnetic radiation of wavelength equal to or less than the upper dimension of the recessed feature, thereby forming a first region with a first -OH group concentration and a second region with a second -OH group concentration in the photosensitive layer, wherein the first -OH group concentration is greater than the second -OH group concentration. A sequential permeation synthesis process is performed to form a first permeation photosensitive layer in a first region, a non-permeation layer disposed below the first permeation photosensitive layer, and a second permeation photosensitive layer in a second region. Remove the first permeated photosensitive layer; Remove the non-penetrating layer; Remove residual components from the second permeable photosensitive layer to form a metal-containing layer disposed on the lower surface of the recessed feature; as well as The host layer is formed directly on the metal-containing layer, wherein the host layer fills the recessed features.

8. The method according to claim 7, wherein, Performing the sequential percolation synthesis process includes performing one or more repeated percolation cycles, each percolation cycle including the introduction of at least a first reactant containing a metal precursor into the reaction chamber, the metal precursor containing a metallic substance.

9. The method according to claim 8, wherein, Each permeation cycle also includes the introduction of a second reactant into the reaction chamber, the second reactant comprising one or more of an oxygen reactant, a nitrogen reactant, or a carbon reactant entering the reaction chamber.

10. The method according to claim 8, wherein, The metallic substance includes one or more of aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum.

11. The method according to claim 1, wherein, The photosensitive layer includes an organic layer.

12. The method according to claim 7, wherein, The residual components include residual organic components, and removing the residual organic components includes contacting the residual organic components with plasma generated by oxygen-containing gas.

13. The method according to claim 8, wherein, Forming the host layer directly on the metal-containing layer includes depositing the host layer through a cyclic deposition process.

14. The method according to claim 13, wherein, The main body layer comprises one or more of metals, metal oxides, metal nitrides, and metal carbides.

15. The method according to claim 13, wherein, Both the main body layer and the metal-containing layer contain the metallic material.

16. The method according to claim 13, wherein, The main body layer is different from the metal-containing layer.

17. The method of claim 7, further comprising heat-treating the photosensitive layer in an ammonia (NH3) environment prior to performing the sequential permeation synthesis process.

18. A photolithography-free method for bottom-up gap filling of recessed features, the method comprising: At the substrate, the substrate includes an organic photosensitive layer disposed on the recessed feature, wherein the recessed feature includes an upper dimension, a lower surface and an upper surface; An organic photosensitive layer is irradiated with electromagnetic radiation of a wavelength equal to or less than the upper dimension of the recessed feature, thereby forming a first region with a first -OH group concentration and a second region with a second -OH group concentration in the organic photosensitive layer, wherein the first -OH group concentration is greater than the second -OH group concentration. The organic photosensitive layer was heat-treated in an ammonia (NH3) environment; Perform at least one permeation cycle of a sequential permeation synthesis (SIS) sequence to introduce a metallic material into an organic photosensitive layer, thereby forming a first metal permeation layer in a first region, a second metal permeation region in a second region, and a non-permeation layer, wherein the metallic material is selected from one or more metallic materials including aluminum, hafnium, titanium, niobium, tungsten, cobalt, ruthenium, silicon, germanium, and molybdenum; The first metal penetration layer is brought into contact with the etchant to remove the first metal penetration layer; The residual organic components in the non-permeable layer and the second metal-permeable region are brought into contact with plasma generated by oxygen reactants, thereby filling the depression feature at least partially with a metal-containing layer.

19. The method according to claim 18, wherein, The metal-containing layer fills the recessed feature into the upper surface without forming a seam.

20. The method according to claim 18, wherein, The metal-containing layer partially fills the recessed feature, and the main layer is deposited on the metal-containing layer to fill the recessed feature onto the upper surface without forming a seam.

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