Gap filling method, system and device

Abstract

Methods, systems, and apparatus are disclosed for depositing an oxide in a recess of a substrate, including: providing a substrate in a chamber, the substrate including at least one opening to the recess, where the at least one opening is defined by a perimeter adjacent the recess and in a surface region external to the recess, where the recess includes an inner surface; pulsing an inhibitor into the chamber to preferentially deposit the inhibitor in a portion of the recess adjacent the at least one opening and on at least a portion of the surface area; pulsing a precursor into the chamber for chemisorption to the inner surface within the recess; pulse an oxygen species into the chamber to form an oxide within the recess upon contact with the chemisorbed precursor; and repeating the above steps to deposit oxide within the recess to a desired thickness level.

Description

Technical Field

[0001] The present disclosure generally relates to methods and systems suitable for forming electronic devices. More specifically, the present disclosure relates to methods and systems that can be used to deposit materials in gaps, trenches, and the like. Background Art

[0002] The reduction in size of semiconductor devices has led to significant increases in the speed and density of integrated circuits. However, as wiring pitches in large-scale integrated devices are miniaturized, void-free filling of high aspect ratio gaps or trenches (e.g., trenches with an aspect ratio of 3 or more) has become increasingly difficult due to limitations of existing deposition processes. Therefore, there is a need for processes that effectively fill high aspect ratio features, such as gaps such as trenches on semiconductor substrates, such as in the case of logic and / or memory devices. In particular, there is a need for processes that effectively fill high aspect ratio features with conductive materials to minimize the formation of seams and gaps.

[0003] Any discussion set forth in this section, including discussion of problems and solutions, has been included in the present disclosure merely to provide context for the present disclosure. Such discussion should not be construed as an admission that any or all information was known at the time the present invention was made, or constitutes prior art. Summary of the invention

[0004] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to necessarily identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] In one aspect, a method for depositing an oxide in a recess of a substrate comprises: providing a substrate in a chamber, the substrate comprising at least one opening leading to the recess, wherein the at least one opening is defined by a perimeter in a surface area adjacent to the recess and outside the recess, wherein the recess comprises an interior surface; pulsing an inhibitor into the chamber to preferentially deposit the inhibitor in a portion of the recess adjacent to the at least one opening and on at least a portion of the surface area; pulsing a precursor into the chamber to chemically adsorb to the interior surface within the recess; pulsing an oxygen species into the chamber to form an oxide within the recess when in contact with the chemically adsorbed precursor; and repeating the above steps to deposit the oxide within the recess to a desired thickness level.

[0006] The method may also include wherein the inhibitor is at least one of an alkyl alcohol, a ketone, a carboxylic acid, or a beta-diketone, or a combination thereof.

[0007] The method may also include wherein the precursor is a metal precursor.

[0008] The method may further include pulsing an inert gas into the chamber to purge the chamber after one or more of the above steps.

[0009] The method may also include where pulsing the inhibitor to preferentially deposit the inhibitor at openings of the recesses further includes pulsing the inhibitor for a first time period and pulsing the precursor for a second time period, wherein the first time period is shorter than the second time period.

[0010] The method can also include where pulsing the inhibitor to preferentially deposit the inhibitor further includes selecting the inhibitor to have a first partial pressure lower than a second partial pressure of the precursor.

[0011] The method can also include where pulsing the inhibitor to preferentially deposit the inhibitor further includes selecting the inhibitor to have a first molecular mass greater than a second molecular mass of the precursor.

[0012] The method can also include where pulsing the inhibitor to preferentially deposit the inhibitor further includes pulsing the inhibitor at a first concentration and pulsing the precursor at a second concentration, wherein the first concentration is less than the second concentration.

[0013] The method may also include simultaneously pulsing the inhibitor and the oxygen species. Simultaneously pulsing the inhibitor and the oxygen species may further include selecting the inhibitor to have a first partial pressure less than a second partial pressure of the oxygen species. The method may also include wherein simultaneously pulsing the inhibitor and the oxygen species further includes selecting the inhibitor to have a first partial pressure less than the second partial pressure of the oxygen species. The method may also include wherein simultaneously pulsing the inhibitor and the oxygen species further includes selecting the inhibitor to have a first molecular mass greater than the second molecular mass of the oxygen species.

[0014] The method may also include wherein at least one opening has a first width leading to a recess, the recess extending to the depth of the substrate, and the inner surface of the recess includes a bottom surface and opposing sidewalls separated by a second width. The method may also include wherein the first width is less than the second width. The method may also include wherein the opposing sidewalls form an inverted taper from the second width to the first width at the opening. The method may also include wherein the second width is the widest portion of the recess measured between the opposing sidewalls.

[0015] The method may also include wherein the recess comprises a through hole having two openings, wherein the recess extends into the depth of the substrate, and an inner surface of the recess comprises opposing sidewalls.

[0016] The method may also include wherein the oxide is a metal oxide.

[0017] The method may also include wherein the inhibitor is an alkyl alcohol.

[0018] The method may also include where simultaneously pulsing the inhibitor and the oxygen species further includes pulsing the inhibitor at a first concentration and pulsing the oxygen species at a second concentration, wherein the first concentration is less than the second concentration.

[0019] The method may also include depositing a higher flux of suppressant proximate the opening on at least a portion of the perimeter surface area as compared to the bottom surface or the opposing sidewall or a combination thereof.

[0020] The method may also include depositing the inhibitor at a higher flux in the region near the opening to produce a concentration gradient of the inhibitor from a perimeter in the surface region to a depth within the recess, wherein a maximum concentration of the inhibitor is located at the surface region, wherein the concentration decreases with increasing depth of the recess.

[0021] In order to summarize the present disclosure and the advantages achieved relative to the prior art, certain objects and advantages of the present disclosure have been described above. Of course, it should be understood that all of these objects or advantages may not be achieved according to any specific embodiment or example of the present disclosure. Thus, for example, those skilled in the art will recognize that the examples disclosed herein can be implemented in a manner that achieves or optimizes one advantage or a group of advantages taught or suggested herein, without necessarily achieving other objects or advantages taught or suggested herein.

[0022] All of these examples are within the scope of the present disclosure.These and other embodiments will become apparent to those skilled in the art through the following detailed description of certain examples with reference to the accompanying drawings, the present disclosure not being limited to any particular examples discussed. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Although the specification concludes with claims that particularly point out and distinctly claim what are considered to be embodiments or examples of the present disclosure, advantages of examples of the present disclosure may be more readily ascertained from the description of certain examples of the present disclosure when read in conjunction with the accompanying drawings. Elements having the same element number are identical in all drawings.

[0024] Figure 1 A schematic diagram of a reactor system according to an example of the present technology is shown.

[0025] Figure 2 A schematic diagram of a reactor system having multiple reaction chambers according to an example of the present technology is shown.

[0026] Figure 3 A device structure according to an example of the present technology is shown.

[0027] Figure 4 A device structure according to an example of the present technology is shown.

[0028] Figure 5 A device structure according to an example of the present technology is shown.

[0029] Figure 6 A processing method according to an example of the present technology is shown.

[0030] Figure 7 A processing method according to an example of the present technology is shown.

[0031] Figure 8 A processing method according to an example of the present technology is shown.

[0032] Fig.9A A device structure according to an example of the present technology is shown.

[0033] Fig. 9B A processing method according to an example of the present technology is shown. DETAILED DESCRIPTION

[0034] The detailed description of each example herein refers to the accompanying drawings, which illustrate exemplary examples by way of illustration. Although these exemplary examples are described in sufficient detail to enable those skilled in the art to practice the present disclosure, it should be understood that other examples may be implemented without departing from the spirit and scope of the present disclosure, and logical, chemical and / or mechanical changes may be made. Therefore, the detailed description here is only for the purpose of illustration, not for limitation. For example, the steps described in any method or process description may be performed in any combination and / or order, and are not limited to the presented combination and / or order. In addition, one or more steps from one of the disclosed methods or processes may be combined with one or more steps from another disclosed method or process in any suitable combination and / or order. In addition, any function or step may be outsourced to one or more third parties or performed by a third party. In addition, any reference to the singular includes plural examples, and any reference to more than one component may include a singular example.

[0035] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the disclosure extends beyond the specifically disclosed examples and / or uses of the disclosure and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosure should not be limited by the specific examples described herein.

[0036] The illustrations presented herein are not meant to be actual views of any particular material, apparatus, structure, or device, but are merely representations of examples used to describe the present disclosure.

[0037] As used herein, the term "substrate" may refer to any underlying material or materials that may be used or upon which a device, circuit, or film / layer may be formed.

[0038] As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle, preferably a plurality of consecutive deposition cycles, is performed in a processing chamber. Typically, during each cycle, a precursor is chemically adsorbed to a deposition surface (e.g., a substrate surface or a previously deposited underlying surface, such as material from a previous ALD cycle) to form a monolayer or sub-monolayer that is not easily reacted with additional precursors (i.e., a self-limiting reaction). Thereafter, if desired, a reactant (e.g., another precursor or a reactive gas) may be subsequently introduced into the processing chamber for converting the chemically adsorbed precursor into the desired material on the deposition surface. Typically, the reactant is capable of further reacting with the precursor. In addition, a purge step may also be utilized during each cycle to remove excess precursor from the processing chamber and / or excess reactant and / or reaction byproducts from the processing chamber after the chemically adsorbed precursor is converted. In addition, the term "atomic layer deposition" as used herein is also meant to include processes designated by related terms, such as "chemical vapor atomic layer deposition", "atomic layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of a precursor composition, a reactive gas, and a purge gas (e.g., an inert carrier gas).

[0039] As used herein, the term "chemical vapor deposition" (CVD) may refer to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposit.

[0040] As used herein, the terms "layer", "film" and / or "thin film" may refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. For example, a "layer", "film" and / or "thin film" may include 2D materials, nanorods, nanotubes or nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters. A "layer", "film" and / or "thin film" may include a material or layer having pinholes, but still being at least partially continuous.

[0041] In addition, in the present disclosure, any two numbers of a variable may constitute a feasible range for the variable, and any range indicated may include or exclude endpoints. In addition, any values ​​of the variables indicated (regardless of whether they are expressed as "about") may refer to exact values ​​or approximate values, and include equivalents, and may refer to average values, median values, representative values, majority values, etc. In addition, in the present disclosure, the terms "including", "consisting of" and "having" may independently refer to "generally or broadly including", "comprising", "essentially consisting of" or "consisting of" in some examples. In the present disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some examples.

[0042] Reference now Figure 1 In various examples, the reactor system 150 may include a reaction chamber 104, a pedestal 106 that holds a substrate 130 (including at least one recess 31) during processing, a fluid distribution system 108 (e.g., a showerhead) that distributes one or more reactants to the surface of the substrate 130, one or more reactant sources 110, 112, and / or 113, and / or a carrier gas and / or purge gas source 114 fluidly coupled to the reaction chamber 104 via corresponding lines 116, 118, 119, and 120, and corresponding valves or controllers 122, 123, 125, and 126. Reactant gases (e.g., precursors 115, oxygen species 117, and inhibitors 121) or other materials from corresponding sources 110, 112, and / or 113 may be applied to the substrate 130 in the reaction chamber 104. A purge gas 123 from a gas source 114 can flow to and through the reaction chamber 104 to remove any excess reactants or other undesirable materials from the reaction chamber 104. The system 150 can also include a vacuum source 128 fluidly coupled to the reaction chamber 104, which can be configured to evacuate the reactants, purge gas, or other materials from the reaction chamber 104.

[0043] Controller 152 may be configured to perform various functions and / or steps as described herein. Controller 152 may include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although illustrated as a single unit, controller 152 may alternatively include multiple devices. For example, controller 152 may be used to control airflow (e.g., by monitoring flow and controlling valves 122, 123, 125, and / or 126), motors, heaters, cooling devices, and / or vacuum source 128 to perform various processes (e.g., at each Figure 6 , 7 , 8 and / or 9). In addition, when the system includes two or more reaction chambers, as described in more detail below, the two or more reaction chambers can be coupled to the same / shared controller.

[0044] In one example, a gap fill process may be performed to deposit an oxide within the recess 31 of the substrate 130. The process may include pulsing a precursor 115 from a reactant source 110 to the reaction chamber 104 through a showerhead 108. An oxygen species 117 may be pulsed to the reaction chamber 104 through the showerhead 108 together with or independently of the precursor 115 from the reactant source 112. As the precursor 115 and the oxygen species 117 contact the substrate 130, an oxide may be formed on the substrate 130 within the recess 31. To inhibit the deposition of metal oxides on the top and / or outside of the recess, an inhibitor 121 may also be pulsed from the reactant source 113 into the chamber 104. The inhibitor 121 may flow into the chamber 104 separately from the precursor 115 and / or the oxygen species 117 or simultaneously with one or more of the precursors 115 and / or the oxygen species. In one example, the inhibitor 121 may flow into the chamber 104 after the oxygen species 117 flows into the chamber 104. In another example, the inhibitor 121 may flow into the chamber 104 simultaneously with the flow of the oxygen species 117 into the chamber 104 .

[0045] Inhibitor 121 may be selected to preferentially deposit at the openings of recesses 31 to prevent oxide from forming to a greater extent at the openings to recesses 31 than within recesses 31. Reduction in deposition at the openings of recesses 31 may reduce the formation of gaps or seams in oxide deposited therein.

[0046] In an example, oxide materials such as precursor 115 and oxygen species 117 may be deposited in the same chamber as inhibitor 121 or may be deposited in a different chamber.

[0047] The oxide gap fill layer may be formed by any of a variety of methods, including various deposition cycles, including pulsing the precursor 115, the inhibitor 121, and / or the oxygen species 117 into the chamber, and purging the chamber with a purge gas 124 between one or more pulses and / or between one or more deposition cycles. Such deposition cycles (or portions thereof) may be repeated until a desired thickness of oxide is deposited within the recess 31. The precursor 115, the inhibitor 121, and / or the oxygen species 117 may be pulsed into the chamber in various sequences, and / or one or more may be pulsed simultaneously. For example, a deposition cycle for forming an oxide within the recess 31 may include pulsing the precursor 115 into the chamber 104, purging the chamber 104 with the purge gas 124, then pulsing the inhibitor 121 and the oxygen species 117 into the chamber 104 simultaneously, and purging the chamber 104 with the purge gas 124 at various intervals. In another example, a deposition cycle for forming an oxide within the recess 31 may include pulsing the inhibitor 121 into the chamber 104 to inhibit deposition of the metal oxide at various regions on the outside or top of the recess 31, then pulsing the precursor 115 into the chamber 104, purging the chamber 104 with the purge gas 124, then pulsing the inhibitor 121, then purging the chamber 104 with the purge gas 124, and finally simultaneously pulsing the oxygen species 117 into the chamber 104. The chamber 104 may be purged with the purge gas 124 at various intervals (e.g., between pulses or deposition cycles).

[0048] In some examples, a reactor system (e.g., reactor system 150) can include multiple reaction chambers. Figure 2 In the reactor system 200 shown, a plurality of reaction chambers 204 (each reaction chamber can be Figure 1 The load lock chamber 212 and the reaction chamber 204 may be disposed around and / or coupled to a transfer chamber 280 that includes a transfer tool 285 for transferring substrates between the reaction chambers 204. The substrate may be transferred between the load lock chamber 212 and the reaction chamber 204 (e.g., via the transfer chamber 280). For example, the substrate 130 may be disposed in different chambers for different steps of a semiconductor manufacturing process (e.g., etching, oxidation, passivation, and / or deposition steps may each be performed in the same or different chambers).

[0049] Figure 3 A structure 300 according to an example of the present disclosure is shown. The device structure 300 can be any of a variety of semiconductor structures. In various examples, substrate 310 features can be formed in or on a surface 330 of substrate 310, for example, a three-dimensional structure such as a recess 312 can form a portion of a FinFET or a full gate (GAA) FET and / or a storage element. In some examples, the structure 300 can have a high aspect ratio (e.g., an aspect ratio of about 4 or more) or a complex morphology.

[0050] In an example, structure 300 includes substrate 310 having recess 312. Recess 312 may have top 334 and bottom 336. Recess 312 may extend depth 322 from opening 328 to bottom surface 318 and may be filled with oxide layer 314. Recess 312 may be defined by perimeter 360 in surface area 332 around opening 328. Recess 312 may also include inner surface 320 including sidewall surface 316 and bottom surface 318. Opposing sidewall surfaces 316 may be substantially parallel. Structure 300 may be formed according to the examples described herein.

[0051] Figure 4 A structure 400 according to an example of the present disclosure is shown. The device structure 400 can be any of a variety of semiconductor structures. In various examples, substrate 410 features can be formed in or on a surface 430 of the substrate 410, such as a three-dimensional structure, such as a depression, a cavity, or a groove or a combination thereof. Such a patterned substrate 410 can include partially fabricated semiconductor device structures, such as transistors (e.g., such as FinFETs or full gate (GAA) FETs) and / or storage elements. In some examples, the structure can have a high aspect ratio (e.g., an aspect ratio of about 4 or more) or a complex morphology.

[0052] In an example, structure 400 includes substrate 410 having recess 412. Recess 412 may have top 434 and lower portion 436. Recess 412 may be filled with oxide 414. Recess 412 may be defined by perimeter 460 in surface region 432 near opening 428. Recess 412 may also include inner surface 420 including sidewall surface 416 and bottom surface 418. Recess 412 may extend depth 422 into recess 412. Opposing sidewalls 416 may be inclined such that recess 412 is an inverted cone extending from opening 428 to bottom surface 418. In such an example, width 424 of bottom surface 418 is greater than width 426 of opening 428. Structure 400 may be formed according to the examples described herein.

[0053] Figure 5 A structure 500 according to an example of the present disclosure is shown. The device structure 500 can be any of a variety of semiconductor structures (e.g., a full gate (GAA) structure). In various examples, substrate 510 features can be formed in or on a surface 531 and / or 535 of the substrate 510 (e.g., a three-dimensional structure, such as a hole or a via). Such a patterned substrate 510 may include partially fabricated semiconductor device structures, such as transistors (e.g., such as FinFETs or full gate (GAA) FETs) and / or storage elements. In some examples, the structure may have a high aspect ratio (e.g., an aspect ratio of about 4 or more) or a complex morphology.

[0054] In an example, structure 500 includes substrate 510 having recess 512. Recess 512 may have outer portions 534 and 538 and inner portion 536. Recess 512 may be filled with oxide 514. Recess 512 may be bounded by perimeter 560 in surface region 532 on a first side 550, and on an opposite side 552, recess 512 may be bounded by perimeter 562 in surface region 533. Surface region 532 may be disposed in a plane around perimeter 560 of recess 512 near opening 528. Surface region 533 may be disposed in a plane around perimeter 562 of recess 512 near opening 5530. Recess 512 may also include inner surface 520 including sidewall surface 516. Recess 512 may extend from opening 528 through to opening 530 to form a hole or via in substrate 510. Opposing sidewall surfaces 516 may be parallel or have different geometries. Structure 500 may be formed according to the examples described herein.

[0055] Figure 6 (refer to Figure 1-5 ) shows a method for depositing oxide in a recess of a substrate to form a semiconductor structure (e.g., in a corresponding Figure 3 , 4 5 and 300, 400 and / or 500). In one example, process 600 can begin at operation 602, in a chamber (e.g., Figure 1 A substrate is provided in a chamber 104 (shown in FIG. Figure 1 , 3 , 4 and / or 5). The substrate may be disposed on a base (e.g. Figure 1 The substrate may include a recess (e.g., in a corresponding Figure 1 , 3 , 4 and / or 5) of the recess 31, 328, 428 and / or 528) shown in at least one opening (for example in the corresponding Figure 3 , 4 and / or openings 328, 428, 528, and / or 530 shown in FIG. 5 ). A recess may include at least one opening formed by a surface area adjacent to and outside of the recess (e.g., in a corresponding Figure 3 , 4 and / or the perimeter of the surface area 332, 432, 532 and / or 533 shown in FIG. 5 (e.g., in the corresponding Figure 3 , 4 and / or 5) are defined by the perimeter 360, 460, 560 and / or 562 shown in FIG. 5, wherein the recess includes an inner surface (e.g., at the corresponding Figure 3 , 4and / or the inner surfaces 320, 420 and / or 520 shown in FIG. 5 ).

[0056] Process 600 may move to deposition cycle 612, which includes (and may or may not begin with) operation 604, where inhibitor 121 may be pulsed into the chamber. Thus, inhibitor 121 may contact the substrate, preferentially depositing inhibitor 121 on portions of the recesses adjacent to at least one opening of the recess (e.g., at the corresponding Figure 3 , 4 and / or the top 334 or 434 and / or the outer 534 and / or 538 shown in 5) and on at least a portion of the surface area.

[0057] In some examples, inhibitor 121 is a growth inhibitor and includes a gas phase reactant. Inhibitor 121 can be a non-consumable reagent that is not incorporated into the deposited film during the deposition process and helps to improve the properties of the deposited film. In some examples, the growth inhibitor can include one or more organic molecules. In some embodiments, inhibitor 121 can include alkyl alcohols, ketones, carboxylic acids and / or β-diketones or combinations thereof. For example, inhibitor 121 can include methanol (MeOH), ethanol (EtOH), isopropanol (iPrOH), n-propanol (n-PrOH), butanol (t-BuOH, n-BuOH), acetone ((CH3)2CO), acetic acid (CH3COOH), acetylacetone (hacac) and / or acetonitrile (CH3CN), dimethylaminotrimethylsilane (TMSDMA), or bis (N, N-dimethylamino) dimethylsilane or a combination thereof, or any other suitable inhibitory substance.

[0058] In one example, (without being bound by any particular theory) the inhibitor 121 can occupy or replace surface hydroxyl active sites, thereby reducing the growth rate of the metal oxide (e.g., in CVD and / or ALD processes). In one example, the exposure time required to saturate the high aspect ratio structure is given by the following equation:

[0059] t(seconds)~(m^0.5*g*(L / D)^2) / p

[0060] Where m = molecular mass of reactant or inhibitor, g = active site density, (L / D) = aspect ratio, and p = partial pressure of reactant or inhibitor.

[0061] In one example, by adjusting the inhibitor 121 exposure to low (step 605), the bottom of the depression (e.g., at the corresponding Figure 3 and 4 The bottom 336, 436 shown in FIG. 1 ) or the interior of the depression (e.g., in FIG. Figure 5 Compared to the interior 536 shown in FIG. Figure 3 ,4 and / or the surface areas 332, 432, 532 and / or 533 shown in FIG. 5 ) and the surface areas near the openings (e.g., in the corresponding Figure 3 , 4 5 and / or the top 334 or 434 and / or the outer portion 534 and / or 538 shown in FIG. 5 can receive a higher flux of inhibitor 121. The term "flux" herein refers to the number of collisions of molecules (e.g., inhibitor 121) with a surface (e.g., surface area 332) per unit area per unit time (e.g., seconds). Thus, for example, a higher flux of inhibitor 121 on surface area 332 compared to bottom surface 318 may result in greater inhibition at surface area 332 compared to bottom surface 318. This may also result in a greater inhibitory effect at and / or adjacent to or near the opening to the recess, such that at the bottom surface (e.g., at the corresponding Figure 3 and Figure 4 bottom surface 318 or 418 shown in FIG. 1 ) and / or the bottom (e.g., at the corresponding Figure 3 and Figure 4 Similarly, with respect to structure 500, adjusting the inhibitor 121 exposure to low can produce a greater inhibitory effect at the opening leading to the opening, such that the growth rate of the oxide is higher at the inner 536 (as compared to the outer 534 and 538). Figure 5 The oxide growth rate is higher at ).

[0062] In one example, adjusting the inhibitor 121 exposure to low (at step 605) can include selecting the inhibitor 121 to have a higher concentration of reactants than other reactants used during the deposition cycle 612 (e.g., Figure 1 The precursor 115 and / or oxygen species 117 shown have a molecular mass that is higher than a molecular mass.

[0063] In one example, adjusting the inhibitor 121 exposure low (at step 605 ) can include selecting the inhibitor 121 to have a lower partial pressure than the partial pressures of other reactants (eg, precursor 115 and / or oxygen species 117 ) used during the deposition cycle 612 .

[0064] In one example, adjusting the inhibitor 121 exposure down (at step 605) may include selecting or adjusting a dilution of the inhibitor 121 (e.g., diluting the inhibitor 121 with an inert substance (e.g., purge gas 124)) greater than a dilution of other reactants (e.g., precursor 115 and / or oxygen species 117) used in the deposition cycle 612 to reduce the exposure of the inhibitor 121 relative to the other reactants. In other words, adjusting the inhibitor 121 exposure down may include pulsing the inhibitor 121 at a first concentration and pulsing the precursor 115 and / or oxygen species 117 at a second concentration, wherein the first concentration is less than the second concentration.

[0065] In one example, adjusting the inhibitor 121 exposure down (at step 605) can include selecting and / or adjusting the inhibitor 121 exposure time to be less than the exposure time of other reactants (e.g., precursor 115 and / or oxygen species 117) used during the deposition cycle 612. The methods described for adjusting the inhibitor 121 exposure down can be used in various combinations and / or alone. In addition, the methods described for adjusting the inhibitor 121 exposure can be used during the deposition cycle 612 when the inhibitor 121 is pulsed separately from other reactants and / or when the inhibitor 121 is pulsed simultaneously with other reactants.

[0066] In one example, by adjusting the inhibitor 121 exposure to low (at step 605), the area adjacent to the recess opening (e.g., at the corresponding portion 318, 418 and / or lower portion 336, 436 and / or inner portion 536) receives a lower flux of inhibitor 121 than the lower portion or inner portion or bottom surface of the recess (e.g., bottom surface 318, 418 and / or lower portion 336, 436 and / or inner portion 536). Figure 3 , 4 5 and 5) can receive a higher flux of inhibitor 121. This creates a greater inhibitory effect in those regions receiving a higher flux of inhibitor 121, thereby enabling a higher growth rate of oxide in those regions receiving a lower flux of inhibitor 121 when the substrate is exposed to precursor 115 and / or oxygen species 117 during deposition cycle 612 (as described in more detail below).

[0067] It will be appreciated that the application of the inhibitor 121 results in a depression (e.g., in the corresponding Figure 1 , 3 , 4 and / or 5. The proximal region of the recess is the region where the recess and opening are more exposed to the inhibitor 121 during the deposition cycle 612 (e.g., the surface region 332, 432 and / or 532, 533, the top 334, 434 and / or the outer portion 534, 538). The distal region of the recess is the region where the recess is less exposed to the inhibitor 121 during the deposition cycle 612 (e.g., including the bottom surface 318, 418 and / or the lower portion 336, 436 and / or the inner portion 536).

[0068] In one example, the distal region may be substantially unaffected, or at least less affected than the proximal region. In other words, the proximal region may be suitably rendered less reactive to the precursor 115 that may subsequently be provided to the reaction chamber. In addition, contacting the substrate with the inhibitor 121 may result in an inhibition gradient in the recessed feature. This gradual change in inhibition strength may be obtained from the surface area surrounding the opening to the recess (e.g., corresponding to the region at Figure 3 ,4 and / or the surface areas 332, 432, 532 and / or 533 shown in FIG. 5) to the bottom of the depression (e.g., in the corresponding Figure 3 and 4 The lower portion 336, 436 shown in FIG. 1 ) or the interior of the recess (e.g., in FIG. Figure 5 The inner portion 536 shown in FIG. 1 is reduced. Therefore, the inhibition in the proximal region of the depression is stronger than the inhibition in the distal region of the depression. As the exposure of the inhibitor 121 decreases, the adsorption of the inhibitor 121 decreases, and thus the inhibition gradually decreases. Therefore, an inhibition gradient is generated from stronger inhibition in the proximal region of the depression to weaker inhibition in the distal region of the depression.

[0069] Without being bound by any particular theory or mode of operation, it is believed that inhibition in the proximal region is caused by depletion of reactive surface groups near the substrate surface in the proximal region, while reactive surface groups deeper in the recess in the distal region are believed to be less exposed to inhibitor 121 due to the exposure of inhibitor 121 being tuned to preferentially contact and adsorb to the substrate surface in the proximal region (e.g., surface regions 332, 432 and / or 532, 533, top 334, 434 and / or exterior).

[0070] In one example, the inhibitor 121 may be pulsed into the reaction chamber for any suitable duration (e.g., a pulse time between 0.05 and 200 seconds). The pressure within the reaction chamber during the provision of the inhibitor 121 may be any suitable pressure, such as between 1 and 10 Torr. The temperature during the pulse of the inhibitor 121 may be between about 100° C. and 500° C., or about 450° C., or between about 100° C. and 400° C., or about 350° C., or between about 100° C. and 300° C., or about 250° C., or between about 100° C. and 200° C., or about 150° C. (“about” herein means ±50° C.), or any sufficient temperature.

[0071] In one example, the deposition cycle 612 of the process 600 can move to operation 606, where the precursor 115 can be pulsed into the chamber, where the precursor 115 can be chemisorbed onto the interior surface within the recess (e.g., at the corresponding Figure 3 , 4 and / or the inner surfaces 320, 420 and / or 520 shown in FIG. 5 ).

[0072] In one example, the precursor 115 may be applied through a showerhead (e.g. Figure 1The precursor 115 may be provided to the substrate by a showerhead 108 shown in Figure 1, or by a cross-flow fluid distribution system. In one example, the precursor 115 may be a metal-containing precursor for forming a metal or metal oxide, including but not limited to magnesium oxide (MgO), aluminum oxide (Al2O3), zirconium oxide (ZrO2), hafnium oxide (HfO2), hafnium silicon oxide (HfSiO), tantalum oxide (Ta2O5), tantalum silicon oxide (TaSiO), titanium dioxide (TiO2), zinc oxide (ZnO), barium strontium titanate (BST), and strontium bismuth tantalate (SBT). Such precursors may include, for example, trimethylaluminum (TMA), dimethylaluminum hydride (DMAH), dimethylaluminum isopropoxide (DMAI), dimethylethylaluminum (DMEAA), trimethylaluminum amide (TEAA), N-methylpyrrolidinoaluminum (MPA), aluminum triisopropoxide, triisobutylaluminum (TIBA) and tri-tert-butylaluminum (TTBA), diethylzinc (DEZ), tetraisopropylorthotitanate (TTIP), titanium tetrachloride (TiCl4), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(dimethylamino)zirconium (IV) (TDMAZ), magnesium olefin (Mg-(Cp)2), dimethylzinc (ZnMe2), diethylzinc (ZnEt2), methylisopropoxyzinc (ZnMe(OPr)) or zinc acetate (Zn(CH3CO2)2, hafnium chloride (HfCl4) and / or zirconium (IV) chloride (ZrCl4), or the like or a combination thereof, or any other suitable precursor.

[0073] In other examples, precursor 115 can be a lanthanide-containing precursor for forming lanthanide oxides (i.e., oxides of physically stable "rare earth" metal elements), such as scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu), as well as silicon nitride (SiN). Such precursors may include, for example, 2,2,6,6-tetramethyl-3,5-heptanediolato(III) lanthanum (La(thd)3), tri(cyclopentadienyl)lanthanum (III) (La(Cp)3), tri(isopropylcyclopentadienyl)lanthanum (III) (La(iPrCp)3) and / or tri(N,N'-diisopropylacetamidine) scandium (Sc(amd)3), or the like or a combination thereof, or any other suitable precursor.

[0074] In one example, before placing a substrate (e.g., Figure 1 , 3, 4 and / or 5) is exposed to the inhibitor 121, exposing the substrate to the precursor 115 (e.g., a metal precursor) can cause the density of the chemisorbed precursor per unit area to gradually change from greater chemisorption in the distal region to weaker (or less) chemisorption in the proximal region. The substrate is then exposed to an oxygen reactant and the oxygen-containing species is then allowed to react with the chemisorbed precursor to form an oxide. Because more precursor 115 can be chemisorbed in the distal region than in the proximal region, the oxide can be more easily formed and grow faster in the distal region than in the proximal region in one or more deposition cycles 612. As a result, the oxide layer (e.g., in the corresponding Figure 3 and Figure 4 The oxide layer 314 and / or 414 shown in FIG. 1 may be grown in a bottom-up manner and / or may be grown from a side surface (e.g., at Figure 5 The side surface 516 shown in FIG. 5 grows inwardly.

[0075] In one example, the precursor 115 can be pulsed into the reaction chamber for any suitable duration (e.g., a pulse time between 0.05 and 200 seconds). During the provision of the precursor 115, the pressure within the reaction chamber can be any suitable pressure, such as between 1 and 10 Torr. The temperature during the pulse of the precursor 115 can be between about 100° C. and 500° C., or about 450° C., or between about 100° C. and 400° C., or about 350° C., or between about 100° C. and 300° C., or about 250° C., or between about 100° C. and 200° C., or about 150° C. (“about” herein means ±50° C.), or any sufficient temperature.

[0076] In one example, the deposition cycle 612 of the process 600 may proceed to operation 608, where the oxygen species 117 may be pulsed into the chamber to deposit the oxygen species 117 within the recess (e.g., at the corresponding Figure 3 , 4 An oxide layer (eg, oxide layer 314, 414, and / or 514) is formed in a recess (eg, recess 312, 412, and / or 512) on the inner surface 320, 420, and / or 520 shown in FIGS. 5A and 5B.

[0077] Operation 608 may be performed in the same or different chamber as operation 604 and / or operation 606. Figure 3 , 4 The oxide layer 314, 414, and / or 514 shown in FIG. 5 may be formed in response to the oxygen species 117 contacting the chemisorbed precursor 115 deposited on the inner surface of the substrate (i.e., when in contact with the chemisorbed precursor). After multiple repetitions of the deposition cycle 612, the oxide layer may fill the recess (e.g., at the corresponding Figure 3 ,4 5). The inhibitor 121 will not substantially participate in the film growth of the oxide layer and will not be incorporated into the growing film. As previously described, because more precursor 115 may be chemically adsorbed in the distal region of the recess than in the proximal region, the oxide layer may be more easily formed and grow faster in the distal region than in the proximal region in one or more deposition cycles 612. Thus, the oxide layer (e.g., in the corresponding Figure 3 and Figure 4 The oxide layer 314 and / or 414 shown in FIG. 1 may be grown in a bottom-up manner and / or may be grown from a side surface (eg, Figure 5 The side surface 516 shown in FIG. 5 grows inwardly.

[0078] Various inhibitors 121 may have some reactivity with the surfaces within the recesses. For example, an alkyl alcohol may have surface reactivity. In this case, the inhibitor 121 may be selected to be less reactive and produce a lower growth rate than the oxygen species 117, and / or the inhibitor 121 exposure may be tuned low to saturate only the proximal regions of the structures (e.g., structures 300, 400, and 500) at a low growth rate, while the more reactive oxidant, oxygen species 117, may be pulsed at a fully saturated exposure to produce a (higher) growth rate of oxide (e.g., oxide layers 314, 414, and / or 514) at the distal portions of the recesses.

[0079] In some examples, oxygen species 117 and inhibitor 121 may be pulsed simultaneously during one or more deposition cycles 612. In the case of a mixed oxygen species 117 (e.g., H2O) and inhibitor 121 (e.g., an alkyl alcohol), where the inhibitor 121 is less reactive and / or produces a lower growth rate than the oxygen species 117, the inhibitor 121 exposure may be adjusted to tune the exposure low, thereby saturating only the proximal regions of the structures (e.g., structures 300, 400, and 500) at a low growth rate, while the more reactive oxidant, oxygen species 117, may be pulsed at a fully saturated exposure, producing a (higher) growth rate.

[0080] In an example, when pulsing the inhibitor 121 and the oxygen species 117 simultaneously, exposing the inhibitor 121 to a low setting (at step 605 ) may include selecting the inhibitor to have a first partial pressure that is lower than a second partial pressure of the oxygen species 117 .

[0081] In one example, when simultaneously pulsing the inhibitor 121 and the oxygen species 117 , adjusting the inhibitor 121 exposure low (at step 605 ) may include selecting the inhibitor 121 to have a first molecular mass greater than a second molecular mass of the oxygen species 117 .

[0082] In one example, when pulsing the inhibitor 121 and the oxygen species 117 simultaneously, adjusting the inhibitor 121 exposure down (at step 605 ) may include pulsing the inhibitor 121 at a first concentration and pulsing the oxygen species 117 at a second concentration, wherein the first concentration is less than the second concentration.

[0083] When pulsing the inhibitor 121 and the oxygen species 117 simultaneously, the methods described for adjusting the inhibitor 121 exposure to low at step 605 may be used in various combinations and / or alone.

[0084] In one example, the oxygen species 117 may include any suitable compound including oxygen and / or an oxidizing compound, such as water (H2O), ozone (O3), hydrogen peroxide (H2O2), deuterium oxide (D2O), nitrous oxide (N2O), nitrogen dioxide (NO2) and / or an alcohol (e.g., tert-butyl alcohol), etc., or a combination thereof.

[0085] The temperature during the pulse of oxygen species 117 may be between about 100°C and 500°C, or about 450°C, or between about 100°C and 400°C, or about 350°C, or between about 100°C and 300°C, or about 250°C, or between about 100°C and 200°C, or about 150°C (where "about" herein means ±50°C), or any sufficient temperature.

[0086] In one example, the oxide layer may be formed to a thickness sufficient to fill the recess.

[0087] The steps of pulsing the precursor 115, oxygen species 117, and inhibitor 121 in respective operations 604, 606, and 608 may be performed in any suitable order. In various examples, the steps of providing the precursor 115, oxygen species 117, and inhibitor 121 may each be separated by a purge gas 124 (operation 610) to remove excess precursor, byproducts, or other unwanted materials. In various examples, the purge gas may be provided after each operation (e.g., after pulsing the precursor 115, oxygen species 117, and / or inhibitor 121, regardless of order) and / or after depositing an oxide layer (e.g., oxide layer 314, 414, and / or 514).

[0088] In various examples, the steps of providing the precursor 115, the oxygen species 117, and the inhibitor 121 can be performed in any suitable order. For example, one or more of the steps of pulsing the precursor 115, the oxygen species 117, and the inhibitor 121 can be performed sequentially and / or simultaneously. One or more steps of pulsing the precursor 115, the oxygen species 117, and / or the inhibitor 121 into the chamber can be separated by a purge gas 124 to remove excess precursor, byproducts, or other unwanted materials. In various examples, the purge gas 124 can be provided after each step (e.g., after providing the precursor 115 and providing the oxygen species 117, regardless of order) and / or after each deposition cycle 612 and / or after oxide deposition or after inhibitor deposition.

[0089] In some embodiments, contacting the substrate 130 with the oxygen species 117 may include pulsing the oxygen species 117 into the reaction chamber and subsequently contacting the substrate 130 for a time period between about 0.01 seconds and about 200 seconds, or between about 0.01 seconds and about 180 seconds, or between about 0.01 seconds and about 160 seconds, or between about 0.01 seconds and about 140 seconds, or between about 0.01 seconds and about 120 seconds, or between about 0.01 seconds and about 100 seconds, or between about 0.01 seconds and about 80 seconds, or between about 0.01 seconds and about 60 seconds, or between about 0.01 seconds and about 50 seconds, or between about 0.01 seconds and about 20 seconds, or between about 0.01 seconds and about 10 seconds, or between about 0.01 seconds and about 5.0 seconds ("about" herein means ±10 seconds).

[0090] The pulses of the precursor 115, the oxygen species 117, and the inhibitor 121 may be alternating, sequential, and / or simultaneous. One or more of the precursor 115, the oxygen species 117, and the inhibitor 121 may be pulsed from about 1 cycle to about 200 cycles, or from about 1 cycle to about 180 cycles, or from about 1 cycle to about 160 cycles, or from about 1 cycle to about 140 cycles, or from about 1 cycle to about 120 cycles, or from about 1 cycle to about 100 cycles, or from about 1 cycle to about 80 cycles, or from about 1 cycle to about 60 cycles, or from about 1 cycle to about 40 cycles, or from about 1 cycle to about 20 cycles, or from about 1 cycle to about 5 cycles ("about" herein means ±20 cycles) or any suitable number of cycles.

[0091] Figure 7 An example process 700 for forming a semiconductor structure according to an example of the present disclosure is shown. In one example, the process 700 may begin at operation 702, in a chamber (e.g. Figure 1 A substrate 710 is provided within chamber 104 as shown.

[0092] The substrate 710 may be disposed on a base (eg Figure 1The substrate 710 may include at least one opening 728 leading to the recess 712. In one example, the opening 728 is defined by a perimeter in the surface area 732. The recess 712 includes an inner surface 720.

[0093] Process 700 may move to operation 704, where the metal oxide deposition cycle 612 (see Figure 6 ) can include pulsing an inhibitor 121 into a chamber where the inhibitor 121 can contact the substrate 710. In some examples, the inhibitor 121 is a growth inhibitor as described in more detail above. In one example, the exposure of the inhibitor 121 is adjusted to provide a higher level of inhibitor 121 exposure to an area near an opening 728 of the recess 712 including the surface area 732 and the top 734 to promote a higher flux of inhibitor 121 compared to the bottom 736 of the recess 712. This can produce a greater inhibitory effect on the recess and / or near the opening 728 at the opening 728, resulting in a higher growth rate of the oxide at the bottom surface 718 and / or the bottom 736. In one example, adjusting the inhibitor 121 exposure low can gradually reduce the exposure of the substrate 710 to the inhibitor during the process 700.

[0094] In one example, the suppressant 121 may be pulsed into the reaction chamber for any suitable duration (eg, a pulse time between 0.05 and 200 seconds).

[0095] Operation 704 may continue by pulsing the precursor 115 into the chamber, where the precursor 115 may chemisorb to the interior surface 720 within the recess 712 .

[0096] In one example, the precursor 115 can be passed through a showerhead (e.g. Figure 1 The precursor 115 may be provided to the substrate by a showerhead 108 shown in FIG. 1 or by a cross-flow fluid distribution system. In one example, the precursor 115 may be a precursor as described above.

[0097] In one example, exposing the substrate to the precursor 115 can cause the density of the chemisorbed precursor 115 per unit area to gradually change from a larger chemisorption in the distal region 750 to a weaker (or smaller) chemisorption in the proximal region 752. The substrate is then exposed to an oxygen reactant, and the oxygen-containing species are then allowed to react with the chemisorbed precursor to form a metal oxide. Because more precursor 115 can be chemisorbed in the distal region 750 than in the proximal region 752, more metal oxide can be formed in the distal region than in the proximal region. In other words, the metal oxide can grow in a bottom-up manner.

[0098] In an example, operation 704 can continue by pulsing the oxygen species 117 into the chamber to contact the substrate surface 720 .

[0099] The oxide layer 714 may begin to form in response to the oxygen species 117 contacting the chemisorbed precursor 115 deposited on the inner surface of the substrate.

[0100] Process 700 may continue with operations 706 - 710 , where deposition cycle 612 may be repeated a number of times sufficient to allow oxide layer 714 to fill recess 712 substantially without gaps or seams.

[0101] Figure 8 An example process 800 for forming a semiconductor structure according to an example of the present disclosure is shown. In one example, the process 800 may begin at operation 802, in a chamber (e.g. Figure 1 A substrate 810 is provided within chamber 104 as shown.

[0102] The substrate 810 may be disposed on a base (eg Figure 1 The substrate 810 may include at least one opening 828 leading to the recess 812. In one example, the opening 828 is defined by a perimeter in the surface area 832. The recess 812 includes an inner surface 820. The recess 812 may be in the shape of an inverted cone.

[0103] Process 800 may move to operation 804, where the metal oxide deposition cycle 612 (see Figure 6 ) can include pulsing an inhibitor 121 into a chamber where the inhibitor 121 can contact the substrate 810. In some embodiments, the inhibitor 121 is a growth inhibitor as described in more detail above. In one example, the exposure of the inhibitor 121 is adjusted to provide a higher level of inhibitor 121 exposure to an area near an opening 828 to the recess 812 including the perimeter region 832 and the top 834 to promote a higher flux of inhibitor 121 than the bottom 836 of the recess 812. This can produce a greater inhibitory effect on the recess and / or near the opening 828 at the opening 828, resulting in a higher growth rate of the oxide at the bottom surface 818 and / or the bottom 836. In one example, adjusting the inhibitor 121 exposure low can gradually reduce the exposure of the substrate 810 to the inhibitor during the process 800.

[0104] In one example, the suppressant 121 may be pulsed into the reaction chamber for any suitable duration (eg, a pulse time between 0.05 and 200 seconds).

[0105] Operation 804 may continue by pulsing the precursor 115 into the chamber, wherein the precursor 115 may chemisorb to the interior surface within the recess.

[0106] In one example, the precursor 115 can be passed through a showerhead (e.g. Figure 1The precursor 115 may be provided to the substrate by a showerhead 108 shown in FIG. 1 or by a cross-flow fluid distribution system. In one example, the precursor 115 may be a precursor as described above.

[0107] In one example, exposing the substrate 810 to the precursor 115 after exposing the substrate 810 to the inhibitor 121 can cause the density of the chemisorbed precursor 115 per unit area to gradually change from greater chemisorption in the distal region 850 to weaker (or smaller) chemisorption in the proximal region 852. The substrate is then exposed to an oxygen reactant, and the oxygen-containing species are then allowed to react with the chemisorbed precursor to form a metal oxide. Because more precursor 115 can be chemisorbed in the distal region 850 than in the proximal region 852, more metal oxide can be formed in the distal region than in the proximal region. In other words, the metal oxide can grow in a bottom-up manner.

[0108] In an example, operation 804 can continue by pulsing the oxygen species 117 into the chamber to contact the substrate surface 820 .

[0109] The oxide layer 814 may begin to form in response to the oxygen species 117 contacting the chemisorbed precursor 115 deposited on the inner surface of the substrate.

[0110] Process 800 may continue with operations 806 - 810 , where deposition cycle 612 may be repeated a number of times sufficient to allow oxide layer 814 to fill recess 812 substantially without gaps or seams.

[0111] Fig.9A A structure 901 according to an example of the present disclosure is shown. The device structure 901 can be any of a variety of semiconductor structures (e.g., a full gate (GAA) structure). In various examples, various features can be formed in or on the surface of a substrate 910 (e.g., a three-dimensional structure, such as a hole or a via). Such a patterned substrate 910 may include partially fabricated semiconductor device structures, such as transistors (e.g., such as a FinFET or a full gate (GAA) FET) and / or storage elements. In some examples, the structure may have a high aspect ratio (e.g., an aspect ratio of about 4 or more) or a complex morphology.

[0112] Fig. 9B An example process 900 for forming a semiconductor structure 901 according to an example of the present disclosure is shown. Fig.9A Cross-sectional view AB.

[0113] In one example, process 900 may begin at operation 902 by providing a Figure 1A substrate 910 is provided within the chamber 104 shown. In one example, the structure 901 includes a recess 912. The recess 912 can have outer portions 934 and 938 and an inner portion 936.

[0114] At least one opening 928 leads to the recess 812. In one example, the opening 828 is defined by a perimeter in the surface area 832. The recess 812 includes an inner surface 820. The recess 812 can be in the shape of an inverted cone.

[0115] The substrate 910 may include an opening defined on a first side 950 by a perimeter 960 in a surface area 932. On the opposite side 952, a recess 912 may be defined by a perimeter 963 in a surface area 933. The surface area 932 may be disposed in a plane around the perimeter 960 of the recess 912 near the opening 928. The surface area 933 may be disposed in a plane around the perimeter 963 of the recess 912 near the opening 930. The recess 912 may also include an inner sidewall surface 920 including a sidewall surface. The recess 912 may extend from the opening 928 through to the opening 930 to form a hole or via in the substrate 910. The opposing sidewall surfaces 920 may be parallel or have different geometries. The structure 901 may be formed according to the examples described herein.

[0116] Process 900 may move to operation 904, where oxide deposition cycle 612 (see Figure 6 ) can include pulsing an inhibitor 121 into a chamber where the inhibitor 121 can contact the substrate 910. In some examples, the inhibitor 121 is a growth inhibitor as described in more detail above. In one embodiment, the exposure of the inhibitor 121 is adjusted to provide a higher level of inhibitor 121 exposure to the area near the opening 928 and 930 of the recess 912 including the surface region 932 and the outer portions 934 and 938 to promote a higher flux of the inhibitor 121 compared to the inner portion 936 of the recess 912. This can produce a greater inhibitory effect on the recess and / or near the opening at the openings 928 and 930, enabling a higher growth rate of the oxide at the inner sidewall surface 920 at the inner portion 936.

[0117] In one example, the suppressant 121 may be pulsed into the reaction chamber for any suitable duration (eg, a pulse time between 0.05 and 200 seconds).

[0118] Operation 804 may continue by pulsing the precursor 115 into the chamber, wherein the precursor 115 may chemisorb to the interior surface within the recess.

[0119] In one example, the precursor 115 can be passed through a showerhead (e.g. Figure 1The precursor 115 may be provided to the substrate by a showerhead 108 shown in FIG. 1 or by a cross-flow fluid distribution system. In one example, the precursor 115 may be a precursor as described above.

[0120] In one example, exposing the substrate 910 to the precursor 115 after exposing the substrate 910 to the inhibitor 121 can cause the density of the chemisorbed precursor 115 per unit area to gradually change from greater chemisorption in the distal region 961 to weaker (or smaller) chemisorption in the proximal region 962. The substrate is then exposed to the oxygen species 117, and the oxygen-containing species are then allowed to react with the chemisorbed precursor to form an oxide. Because more precursor 115 can be chemisorbed in the distal region 961 than in the proximal region 962, more oxide can be formed in the distal region 961 per deposition cycle 612 compared to the proximal region 962. As a result, the oxide can grow inward from the inner sidewall surface 920 with substantially no seams or gaps.

[0121] In an example, operation 904 can continue by pulsing oxygen species 117 into the chamber to contact the sidewall surface 920. An oxide layer 914 can begin to form in response to the oxygen species 117 contacting the chemisorbed precursor 115 deposited on the inner surface of the substrate.

[0122] Process 900 may continue with operations 906 - 908 , where deposition cycle 612 may be repeated a number of times sufficient to allow oxide layer 914 to fill recess 912 substantially without gaps or seams.

[0123] Although exemplary examples of the present disclosure are described herein, it should be understood that the present disclosure is not limited thereto. Various modifications, changes and enhancements may be made to the systems and methods described herein without departing from the spirit and scope of the present disclosure.

[0124] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various systems, components and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for depositing an oxide in a recess of a substrate, comprising: a) providing a substrate in a chamber, the substrate comprising at least one opening leading to a recess, wherein the at least one opening is defined by a perimeter in a surface area adjacent to and external to the recess, wherein the recess comprises an inner surface; b) pulsing an inhibitor into the chamber to preferentially deposit the inhibitor in a portion of the recess adjacent to the at least one opening and on at least a portion of the surface area; c) pulsing a precursor into the chamber to chemically adsorb onto the interior surface within the recess; d) pulsing an oxygen species into the chamber to form an oxide within the recess upon contact with the chemisorbed precursor; as well as e) Repeating steps b)-d) to deposit oxide within the recess to a desired thickness level.

2. The method according to claim 1, wherein: The inhibitor is at least one of an alkyl alcohol, a ketone, a carboxylic acid, or a β-diketone, or a combination thereof.

3. The method according to claim 1, wherein: The precursor is a metal precursor.

4. The method according to claim 3, wherein: The oxide is a metal oxide.

5. The method of claim 1, further comprising pulsing an inert gas into the chamber to purge the chamber after one or more of steps b)-d).

6. The method according to claim 1, wherein: Pulsing the inhibitor to preferentially deposit the inhibitor at the at least one opening further comprises pulsing the inhibitor for a first time period and pulsing the precursor for a second time period, wherein the first time period is shorter than the second time period.

7. The method according to claim 1, wherein: Pulsing the inhibitor to preferentially deposit the inhibitor also includes selecting the inhibitor to have a first partial pressure that is lower than a second partial pressure of the precursor.

8. The method according to claim 1, wherein: Pulsing the inhibitor to preferentially deposit the inhibitor also includes selecting the inhibitor to have a first molecular mass greater than a second molecular mass of the precursor.

9. The method according to claim 1, wherein: Pulsing the inhibitor to preferentially deposit the inhibitor further comprises pulsing the inhibitor at a first concentration and pulsing the precursor at a second concentration, wherein the first concentration is less than the second concentration.

10. The method of claim 1, further comprising pulsing the inhibitor and oxygen species simultaneously.

11. The method according to claim 10, wherein: The inhibitor is an alkyl alcohol.

12. The method according to claim 10, wherein: Pulsing the inhibitor and the oxygen species simultaneously further includes selecting the inhibitor to have a first partial pressure that is less than a second partial pressure of the oxygen species.

13. The method according to claim 10, wherein: Pulsing the inhibitor and the oxygen species simultaneously further includes selecting the inhibitor to have a first molecular mass greater than a second molecular mass of the oxygen species.

14. The method according to claim 10, wherein: Simultaneously pulsing the inhibitor and the oxygen species further comprises pulsing the inhibitor at a first concentration and pulsing the oxygen species at a second concentration, wherein the first concentration is less than the second concentration.

15. The method according to claim 1, wherein: The at least one opening has a first width leading into the recess, wherein the recess extends into the depth of the substrate, and an inner surface of the recess includes a bottom surface and opposing sidewalls separated by a second width.

16. The method of claim 15, further comprising depositing a higher flux of suppressant proximate the at least one opening on at least a portion of the perimeter surface area as compared to the bottom surface or the opposing sidewall, or a combination thereof.

17. The method according to claim 16, wherein: The deposition of the inhibitor at the higher flux in the region near the at least one opening produces an inhibitor concentration gradient from a perimeter in the surface region to a depth within the recess, wherein a maximum concentration of the inhibitor is located at the surface region, wherein the concentration decreases with increasing recess depth.

18. The method according to claim 15, wherein: The first width is smaller than the second width.

19. The method according to claim 15, wherein: The opposing side walls form an inverse taper from the second width to the first width at the at least one opening.

20. The method according to claim 16, wherein: The second width is the widest portion of the recess measured between the opposing sidewalls.

21. The method according to claim 1, wherein: The recess comprises a through hole having two openings, wherein the recess extends into the depth of the substrate and an inner surface of the recess comprises opposing sidewalls.

22. The method according to claim 1, wherein: The inhibitor includes methanol (MeOH), ethanol (EtOH), isopropanol (iPrOH), n-propanol (n-PrOH), butanol (t-BuOH, n-BuOH), acetone ((CH3)2CO), acetic acid (CH3COOH), acetylacetone (hacac) and / or acetonitrile (CH3CN), dimethylaminotrimethylsilane (TMSDMA) or bis(N,N-dimethylamino)dimethylsilane or a combination thereof.

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