Method and system for in-situ etching and depositing materials

Abstract

A method for forming material on a surface of a substrate is provided. The method includes the steps of providing a substrate within a reaction chamber, the substrate including a second material; conformally depositing a layer of a first material onto the substrate; selectively etching at least a portion of the first material; and conformally depositing a second layer of the first material. The step of depositing the first material and the step of selectively etching the first material are performed in the same reaction chamber.

Description

Technical Field

[0001] This disclosure relates to semiconductor manufacturing technology, and more particularly to methods for enhancing etch selectivity and gap filling quality during thin film deposition processes. Background Technology

[0002] In semiconductor manufacturing, processes for producing precise and reliable microstructures are crucial. Techniques for depositing thin films with high uniformity and conformal properties are widely used. However, achieving selective material removal between the deposited film and the underlying material presents challenges that can impact the quality and performance of the final product. Existing methods often struggle with selectivity, leading to undesirable effects such as over-removal or damage to the underlying layer. These limitations necessitate innovative approaches to enhance selectivity and improve the overall process.

[0003] Furthermore, the formation of seams during material deposition presents significant challenges in maintaining the integrity of the microstructure through subsequent processing steps. Current solutions may not adequately address seam formation, leading to compromised quality and potential defects in the final product. A streamlined approach is urgently needed to generate layers capable of withstanding demanding processing conditions, thereby ensuring the reliability and performance of semiconductor devices. Summary of the Invention

[0004] Various embodiments of this disclosure relate to methods for depositing material onto the surface of a substrate (e.g., depositing material over features on the surface of the substrate), methods suitable for filling gaps on the substrate surface. While various embodiments of this disclosure address the shortcomings of existing methods and systems in more detail below, in general, various embodiments of this disclosure provide improved methods suitable for filling gaps on surfaces.

[0005] Other embodiments of this disclosure relate to methods of etching material from the surface of a substrate including gaps. In one embodiment, this disclosure includes a method for etching material, the method comprising providing a substrate containing a deposited first material into a reaction chamber; providing a reactive substance generated by plasma into the reaction chamber to etch the first material, the plasma being generated by an etching reactant gas. The plasma is a pulsed plasma, selected from at least one of high-density plasma, microwave plasma, or inductively coupled plasma. In some embodiments, the etching is spontaneous etching, and the etching reactant is selected from NF3, CF4, C2F6, SF6, NH2F, C3F8, F2, XeF2, HF, CHF3, CH3F, CH2F2, C4F8, C4F6, Cl2, SiCl4, BCl3, C4F6, NH3, N2H2, and any combination thereof.

[0006] In another embodiment, this disclosure includes a method for depositing material on a substrate. The method includes: providing a substrate into a reaction chamber, the substrate comprising a second material; conformally depositing a first material onto the substrate; selectively etching at least a portion of the first material; and conformally depositing a third or second material onto the substrate, wherein the steps of depositing the first and third materials and the step of selectively etching the first material are performed in the same reaction chamber. In some embodiments, the selective etching step includes removing the first material and not removing or substantially not removing any second material. The selective etching step is performed by a method according to the etching method described above.

[0007] In some embodiments, the substrate includes at least one gap having a proximal surface, sidewalls and a distal surface, and a first material is conformally deposited into the at least one gap to fill the gap, such that the deposited first material covers the proximal surface, sidewalls and distal surface.

[0008] In some embodiments, during the step of selectively etching at least a portion of the first material, the first material is etched such that the gaps are partially filled. In some embodiments, the second material comprises silicon oxide, and the first material comprises boron nitride. In some embodiments, the third material comprises silicon nitride.

[0009] In another embodiment, the method includes etching a third or first material such that the proximal surface of the gap is substantially free of material covering it.

[0010] In another embodiment, a first material is conformally deposited by performing at least one deposition cycle, wherein the at least one deposition cycle includes providing a silicon precursor in the gas phase into a reaction chamber; and providing a reactive material generated by plasma into the reaction chamber, the plasma being generated by a nitrogen-containing gas. The boron precursor includes one or more of boron halides, boranes, cycloboranes, and organoboranes. In some embodiments, the boron precursor comprises a boron halide selected from boron triiodide, boron tribromide, boron trichloride, diboron tetrachloride, boron monofluoride, boron trifluoride, and diboron tetrafluoride. In some embodiments, the boron precursor comprises a borane selected from boranes, diboranes, tetraboranes, pentaboranes, decaboranes, and borane-amine complexes. In some embodiments, the boron precursor comprises cycloboranes or substituted cycloboranes. In some embodiments, the boron precursor comprises an organoborane selected from trimethylborane, triethylborane, 3-tri-(dimethylamino)borane, dimethylamineborane, and triethylamineborane. In some embodiments, the nitrogen-containing gas includes one or more of nitrogen (N2), N2O, and NO.

[0011] In a third aspect, this disclosure includes a system for depositing material on the surface of a substrate, the system comprising: a reaction chamber for receiving a substrate including a gap and a second material; a boron precursor source fluidly connected to the reaction chamber via a first valve; a nitrogen reactant source fluidly connected to the reaction chamber via a second valve; an etchant reactant source fluidly connected to the reaction chamber via a third valve; and a controller operatively connected to the first, second, and third valves and configured and programmed to control: supplying the boron precursor to the reaction chamber; supplying the nitrogen reactant to the reaction chamber; supplying the etchant to the reaction chamber; and depositing the material on the surface of the substrate using the method for depositing material on a substrate as described above. These and other features will become more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims.

[0012] This synopsis is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the following detailed description of exemplary embodiments of this disclosure. This synopsis is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Attached Figure Description

[0013] Figure 1 A method according to at least one embodiment of the present disclosure is shown.

[0014] Figure 2 A system according to at least one embodiment of the present disclosure is shown.

[0015] Figure 3 A method according to at least one embodiment of the present disclosure is shown.

[0016] 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 aid in understanding the embodiments shown in this disclosure. Detailed Implementation

[0017] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific embodiments described below.

[0018] As used herein, the term "substrate" can refer to any one or more underlying materials, including any one or more underlying materials that can be modified or on which devices, circuits, or films can be formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. 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 semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0019] As an example, the substrate in powder form can have applications for pharmaceutical manufacturing. Porous substrates can contain polymers. Examples of workpieces may include medical devices (e.g., stents and syringes), jewelry, tooling devices, components for battery manufacturing (e.g., anodes, cathodes, or separators), or components for photovoltaic cells, etc.

[0020] The continuous substrate can extend beyond the boundary of the processing chamber where the deposition process takes place. In some processes, the continuous substrate can move through the processing chamber, allowing the process to continue until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate supply system to allow the continuous substrate to be manufactured and output in any suitable form.

[0021] Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, fiber webs, flexible materials, bundles of continuous filaments or fibers (e.g., ceramic fibers or polymer fibers). Continuous substrates may also include carriers or sheets on which non-continuous substrates are mounted.

[0022] According to the present disclosure, the vapor deposition method refers to the process in which material is deposited from the vapor phase onto a substrate.

[0023] Typically, in a cyclic deposition process according to this disclosure, such as atomic layer deposition (ALD) and molecular layer deposition (MLD), during each cycle, a precursor is introduced into a reaction chamber and chemisorbed onto a substrate surface (e.g., the substrate surface may include previously deposited material or other material from a previous deposition cycle). In some embodiments, the precursor on the substrate surface does not readily react with another precursor (i.e., the deposition of the precursor may be a partially or completely self-limiting reaction). Thereafter, a reactant may be introduced into the reaction chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more cycles, e.g., during each step of each cycle, a purging step may be utilized to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber. Therefore, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor to it. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor to it. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the reactant precursor to it. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor into the reaction chamber and after providing the reactant into the reaction chamber. Without limiting this disclosure to any particular theory, ALD and MLD can be similar processes to CVD in terms of self-limiting reactions and slower, more controllable layer growth rates. Typically, ALD is used to deposit inorganic materials, while in MLD, the precursor can be a completely organic molecule.

[0024] The method may include one or more cyclic phases. In some embodiments, the method includes one or more acyclic (i.e., continuous) phases. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In such embodiments, the method includes a continuous flow of a precursor or reactant. In some embodiments, one or more precursors / reactants are continuously provided in a reaction chamber.

[0025] In some embodiments, at least one of the precursor and reactant is provided to the reaction chamber in a pulsed manner. In some embodiments, the precursor is supplied in a pulsed manner and the reactant is supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses of the precursor and reactant. The duration for which the precursor and / or reactant is provided to the reaction chamber (i.e., the silicon precursor pulse time and the nitrogen-containing reactant pulse time, respectively) can be, for example, from about 0.01 s to about 60 s, for example, from about 0.01 s to about 5 s, or from about 1 s to about 20 s, or from about 0.5 s to about 10 s, or from about 5 s to about 15 s, or from about 10 s to about 30 s, or from about 10 s to about 60 s, or from about 20 s to about 60 s. The duration of the first precursor or second precursor pulse can be, for example, 0.03 s, 0.1 s, 0.5 s, 1 s, 1.5 s, 2 s, 2.5 s, 3 s, 4 s, 5 s, 8 s, 10 s, 12 s, 15 s, 25 s, 30 s, 40 s, 50 s, or 60 s. In some embodiments, the first precursor pulse duration may be at least 5 seconds or at least 10 seconds. In some embodiments, the first precursor pulse duration may be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds. In some embodiments, the second precursor pulse duration may be at least 5 seconds, at least 10 seconds, or at least 20 seconds. In some embodiments, the second precursor pulse duration may be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds.

[0026] The pulse times for precursors and reactants vary independently depending on the process under discussion. The appropriate pulse time may depend on the substrate topology. For higher aspect ratio structures, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Furthermore, the chosen precursor and reactant chemicals can influence the appropriate pulse time. For process optimization purposes, shorter pulse times may be preferred, provided that suitable layer properties are achieved. In some embodiments, the precursor pulse time is longer than the reactant pulse time. In some embodiments, the reactant pulse time is longer than the precursor pulse time. In some embodiments, the precursor pulse time is the same as the reactant pulse time.

[0027] In some embodiments, the precursor and / or reactant are provided to the reaction chamber comprising pulsed precursors and reactants on a substrate. In some embodiments, pulse durations in the range of several minutes may be used for the precursor and / or reactant. In some embodiments, the precursor may be pulsed more than once, e.g., two, three, four, or five times, before the reactant is pulsed into the reaction chamber. Similarly, the reactant may be present with more than one pulse, e.g., two, three, or four pulses, before the precursor is pulsed (i.e., provided) into the reaction chamber.

[0028] As used herein, the term "purge" refers to the process of removing gaseous precursors and / or gaseous byproducts from a substrate surface, for example by evacuating the reaction chamber with a vacuum pump and / or replacing the gas in the reaction chamber with an inert or substantially inert gas (e.g., argon or nitrogen). Purge can be performed between two gas pulses that react with each other. However, purging can also be performed between two gas pulses that do not react with each other. For example, purging can be provided between pulses of two precursors or between a precursor and a reactant. Purge can avoid or at least reduce gaseous interactions between two gases that react with each other. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, the purging step can be used, for example, in the temporal sequence of providing a first precursor to the reaction chamber, providing a purge gas to the reaction chamber, and providing a second precursor to the reaction chamber, wherein the substrate on which the deposited layer is deposited does not move. For example, in the case of spatial purging, the purging step can take the form of moving the substrate from a first position where the first precursor is continuously supplied by means of a purge gas curtain or another means of separating two spaces to a second position where the second precursor is continuously supplied. The purging time can be, for example, about 0.01 seconds to about 20 seconds, about 0.05 seconds to about 20 seconds, or about 1 second to about 20 seconds, or about 0.5 seconds to about 10 seconds, or about 1 second to about 7 seconds, such as 5 seconds, 6 seconds, or 8 seconds. However, other purging times can be used if desired, for example, in cases where a high conformal stepped coverage is required on structures with extremely high aspect ratios or other structures with complex surface morphologies, or in specific reactor types, such as batch reactors.

[0029] As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous material, such as materials deposited by the methods disclosed herein. For example, layers and / or films can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers or partially or entirely atomic layers or atomic and / or molecular clusters. Films or layers can include materials or layers with pinholes, which may be at least partially continuous. In some embodiments, layers according to this disclosure are substantially continuous.

[0030] In this disclosure, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may consist of a single gas or a mixture of gases, depending on the circumstances. The term "inert gas" can refer to a gas that does not participate in a chemical reaction and / or does not become part of the layer to a perceptible degree. Exemplary inert gases include He and Ar and any combination thereof. In some cases, molecular nitrogen and / or hydrogen may be inert gases. Gases other than process gases, i.e., gases not introduced through a precursor injector system, other gas dispensing devices, etc., may be used, for example, to seal the reaction space, and may include sealing gases.

[0031] The terms "precursor" and "reactant" can refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction to produce another compound or element. A precursor typically contains a portion at least partially bound to the compound or element produced by the chemical reaction in question. The resulting compound or element can then be deposited on a substrate. In some cases, the reactant is the precursor. In other cases, the compound or element produced by the chemical reaction does not contain a portion of the reactant (an element or group within the reactant), and therefore the reactant is not a precursor.

[0032] In some embodiments, the precursor or reactant is provided as a mixture of two or more compounds. In the mixture, the compounds other than the precursor may be inert compounds or elements. In some embodiments, the precursor or reactant is provided in the composition. The composition may be a solution or a gas under standard conditions.

[0033] The method for depositing materials according to this disclosure includes providing a substrate in a reaction chamber. In other words, the substrate is situated in a space where deposition conditions can be controlled. The reaction chamber may be a single-wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a vapor-phase processing assembly for fabricating semiconductor devices. The processing assembly may include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations in a multi-station processing chamber. The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. The various stages of the method may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a cluster tool or the deposition station of a multi-station processing chamber.

[0034] In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a spray-head reactor. In some embodiments, the reaction chamber may be a hot-wall reactor. In some embodiments, the reaction chamber may be a spatially partitioned reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a high-capacity manufacturing single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates.

[0035] The reaction chamber can be part of an atomic layer deposition (ALD) assembly. The reaction chamber can also be part of a chemical vapor deposition (CVD) assembly.

[0036] As used herein, the term "comprising" means including certain features, but does not exclude the presence of other features, provided they do not render the claim unfeasible. In some embodiments, the term "comprising" includes "consisting of".

[0037] As used herein, the term "composed of" indicates that no other features exist in the apparatus / method / product besides the features following the wording. When the term "composed of" is used to refer to a compound, substance, or composition of substances, it indicates that the compound, substance, or composition of substances contains only the listed components. Similarly, when the term "essentially composed of" is used to refer to a compound, substance, or composition of substances, it indicates that the compound, substance, or composition of substances contains the listed components, but may also contain trace elements and / or impurities that do not materially affect the properties of the compound, substrate, or composition of substances. Nevertheless, in some embodiments, in addition to the listed components, the chemical compound, substrate, or composition of substances may also contain other components as trace elements or impurities.

[0038] Furthermore, in this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any indicated range 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 may refer to an average, median, representative value, multi-value, etc. Furthermore, in this disclosure, the terms “comprising,” “consisting of,” and “having” independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of” in some embodiments. The meaning of any definition in this disclosure does not necessarily exclude the common and customary meaning in some embodiments.

[0039] In this specification, it will be understood that the terms "on" or "above" may 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 between them, 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 will be understood that the terms "below," "under," or "beneath" will be interpreted as relative concepts.

[0040] The term "basic" applied to film-forming compositions, methods, systems, or structures generally refers to a proportion of a value, property, characteristic, etc., or conversely, to its absence, i.e., at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or more, or any proportion between about 70% and about 100%. In some embodiments, the term "basic" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0041] The term "basic" when applied to compositions, methods, or systems generally means that the addition of components does not substantially alter the properties and / or function of the composition, method, or system.

[0042] The terms "at least one," "one or more," and "and / or" are open-ended expressions that are both conjunction and disjunctive in operation. For example, each of the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," "one or more of A, B, or C," and "A, B, and / or C" represents a single A, a single B, a single C, A and B together, A and C together, B and C together, or A, B, and C together. When each of A, B, and C in the above expressions refers to an element (e.g., X, Y, and Z) or an element category (e.g., X1-X), the meaning is different. n Y1-Y m and Z1-Z o When used, this phrase is intended to refer to a single element selected from X, Y, and Z; a combination of elements selected from the same category (e.g., X1 and X2); and a combination of elements selected from two or more categories (e.g., Y1 and Z). o ).

[0043] Now turn to the attached image. Figure 1 A method 100 according to an exemplary embodiment of the present disclosure is shown. In the illustrated example, method 100 includes the steps of: providing a substrate 102 in a reaction chamber, depositing a first material 104, etching a portion of the first material 105 and depositing a first or third material 106, and ending the process 107.

[0044] In step 102, a substrate is provided into a reaction chamber. The reaction chamber used during step 102 may be or include the reaction chamber of a chemical vapor deposition reactor system configured to perform a deposition process. The deposition process may be a chemical vapor deposition process and / or a circulating deposition process. The reaction chamber may be a standalone reaction chamber or part of a cluster tool. The reaction chamber may be a batch processing tool. In some embodiments, a flow reactor may be used. In some embodiments, a spray head reactor may be used. In some embodiments, a spatially partitioned reactor may be used. In some embodiments, a single-wafer reactor capable of high-volume manufacturing may be used. In other embodiments, a batch reactor comprising multiple substrates may be used. For embodiments in which a batch reactor is used, the number of substrates may range from 10 to 200, or 50 to 150, or even 100 to 130. The reactor may be configured as a thermal reactor—without a plasma excitation device. Alternatively, the reactor may include direct and / or remote plasma devices.

[0045] In some embodiments, the exposed surfaces of the substrate may be pretreated to provide reactive sites, if desired. In some embodiments, a separate pretreatment step is not required. In some embodiments, the substrate is pretreated, for example, by exposing the substrate surface to a pretreatment plasma to provide the desired surface termination.

[0046] In some embodiments of this disclosure, the substrate disposed within the reaction chamber can be heated to a desired deposition temperature for subsequent deposition. For example, the substrate can be heated to temperatures less than about 600°C, less than about 500°C, less than about 450°C, less than about 400°C, less than about 350°C, less than about 300°C, less than about 250°C, or even less than about 200°C. In some embodiments of this disclosure, the substrate temperature during step 102 can be greater than room temperature, between about 300°C and about 600°C, or between about 350°C and about 550°C, or between about 200°C and about 400°C. Lower temperatures may be preferred for plasma-assisted processes, while higher temperatures may be desirable for thermal deposition processes. Temperatures during steps 104, 105, and / or 106 can also be within these ranges.

[0047] In addition to controlling the substrate temperature, the pressure in the reaction chamber can be adjusted to allow for the deposition of the desired boron nitride. In some embodiments, the boron nitride comprises hexagonal boron nitride. In some embodiments, the boron nitride comprises amorphous boron nitride. In some embodiments, the pressure can be controlled between about 0.5 Torr and about 50 Torr (e.g., for heat treatment) or between about 1 Torr and about 10 Torr (e.g., for plasma-enhanced processes). The pressure during steps 104, 105, and / or 106 can also be within these ranges.

[0048] Once the substrate temperature has been set to the desired deposition temperature and the pressure in the reaction chamber has been adjusted as needed, method 100 can proceed to step 104. During step 104, a first material is deposited onto the substrate. Step 104 can be divided into two sub-steps: a first sub-step is to provide a boron precursor into the reaction chamber, and a second sub-step is to contact the substrate with a reactive material generated by a plasma, which is produced by a nitrogen-containing gas. When step 104 includes a cyclic process, the first and second sub-steps can be performed sequentially, with interspersed purging steps. When step 104 includes a CVD process, the first and second sub-steps can overlap. In the first sub-set, the boron precursor is provided to the reaction chamber in the gas phase. In the case of cyclic deposition, the boron precursor can be pulsed into the reaction chamber. According to some embodiments, the boron precursor can be supplied to the reaction chamber along with some carrier gas flow. In some embodiments, the boron precursor may comprise a volatile silicon material that reacts with the surface of the substrate. The boron precursor pulse can self-saturate the substrate surface, such that excess components of the boron precursor pulse do not further react with the molecular layer formed by this process.

[0049] The boron precursor pulse is preferably supplied as a gaseous reactant. For the purposes of this disclosure, the boron precursor gas may be considered "volatile" if the substance exhibits sufficient vapor pressure under processing conditions to deliver the substance to the substrate surface at a sufficient concentration to saturate the exposed surface.

[0050] In some embodiments, the gaseous boron precursor includes one or more of boron halides, boranes, cycloboranes, and organoboranes. In some embodiments, the boron precursor comprises boron halides selected from boron triiodide, boron tribromide, boron trichloride, diboron tetrachloride, boron monofluoride, boron trifluoride, and diboron tetrafluoride.

[0051] In some embodiments, the boron precursor comprises a borane selected from the group consisting of borane, diborane, tetraborane, pentaborane, decaborane, and borane-ammonia complexes. In some embodiments, the gaseous boron precursor comprises boron and hydrogen. In some embodiments, the boron precursor comprises borane, diborane, tetraborane, pentaborane, decaborane, and borane-ammonia complexes.

[0052] In some specific embodiments, as disclosed herein, the boron precursor may be specified as being represented by the following general formula (I):

[0053] (I)

[0054] Among them, R 1 R 2 R 3 R 4 R 5 R 6 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, and alkoxy.

[0055] The term "halogenated" or "halogen" as a group or part of a group is generally used for fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0056] The term "alkyl" as a group or part of a group refers to the formula C n H 2n+1 The alkyl group is a hydrocarbon group, where n is a number greater than or equal to 1. The alkyl group can be straight-chain or branched and can be substituted as shown herein. Typically, the alkyl groups disclosed herein contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When a subscript is used herein following a carbon atom, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C1-20 alkyl," as a group or part of a group, refers to the formula C1-20 alkyl. n H 2n+1The alkyl group, where n is a number from 1 to 20. Therefore, for example, "C1-8 alkyl" includes all straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and thus includes methyl, ethyl, n-propyl, isopropyl, butyl and their isomers (e.g., n-butyl, isobutyl, and tert-butyl); pentyl and its isomers, hexyl and its isomers, etc. "Substituted alkyl" refers to an alkyl group that is substituted at any available junction with one or more substituents (e.g., 1 to 3 substituents, such as 1, 2, or 3 substituents).

[0057] When the suffix "alkylene" is used in conjunction with alkyl, it is called "alkylenetriene," which is intended to indicate that an alkyl group, as defined herein, has two single bonds as points of attachment to other groups. As used herein, the term "alkylenetriene" itself, or as part of another substituent, is also called "alkyldiyl," referring to a divalent alkyl group, i.e., having two single bonds for attachment to two other groups. Alkylenetrienes can be straight-chain or branched and can be substituted as shown herein. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methyl-ethylene (-CH(CH3)-CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3-methylpropylene (-CH2-CH2-CH(CH3)-), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH(CH3)-CH2-CH2-), 4-methylbutylene (-CH2-CH2-CH2-CH(CH3)-), pentylene and its chain isomers, and hexylene and its chain isomers.

[0058] The term "alkenyl" as a group or part of a group refers to an unsaturated hydrocarbon group, which may be straight-chain or branched and contains one or more carbon-carbon double bonds. Typically, the alkenyl groups disclosed herein contain 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. When a subscript is used herein following a carbon atom, the subscript indicates the number of carbon atoms that the named group may contain. Examples of C3-20 alkenyl groups are vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl, etc.

[0059] The term "alkoxy" or "alkyloxy", as a group or part of a group, refers to a group having the formula -OR b The group, wherein R b It is an alkyl group as defined above. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, and hexoxy.

[0060] In the presence of alkylene groups, the linkages to the molecular structure forming part of them can be through common carbon atoms or different carbon atoms. To illustrate this, using the asterisk nomenclature of this disclosure, the C3 alkylene group can be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-*, or *-CH2CH(-CH3)-*.

[0061] In some embodiments, as specified in the methods disclosed herein, for one or more boron precursors represented by general formula (I), the alkyl group is a C1-8 alkyl group, more particularly a C1-4 alkyl group. More specifically, the alkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 alkyl group.

[0062] In some embodiments, as specified in the methods disclosed herein, for one or more boron precursors represented by general formula (I), the alkenyl group is a C2-8 alkenyl group, more particularly a C2-4 alkenyl group. More specifically, the alkenyl group is a C2, C3, C4, C5, C6, C7, and / or C8 alkenyl group.

[0063] In some embodiments, as specified in the methods disclosed herein, for one or more boron precursors represented by general formula (I), the alkoxy group is a C1-8 alkoxy group, more particularly a C1-4 alkoxy group. More specifically, the alkoxy group is a C1, C2, C3, C4, C5, C6, C7, and / or C8 alkoxy group.

[0064] In some embodiments, this disclosure specifies that R 1 R 2 R 3 R 4 R 5 R 6 Each is independently selected from hydrogen, halogen, C1-8 alkyl, C2-8 alkenyl and C1-8 alkoxy.

[0065] In some embodiments, this disclosure specifies that R 1 R 2 R 3 R 4 R 5 R 6 Each is independently selected from hydrogen, halogen, C1-4 alkyl, C2-4 alkenyl and C1-4 alkoxy.

[0066] In certain embodiments, as specified in the methods disclosed herein, one or more boron precursors may include cycloborazane or substituted cycloborazane.

[0067] In some embodiments, the boron precursor comprises an organoborane, including alkylboranes or alkylaminoboranes. The boron precursor may comprise molecules selected from: trimethylborane, triethylborane, 3-tris-(dimethylamino)borane, dimethylamineborane, and triethylamineborane.

[0068] In some embodiments of this disclosure, the boron precursor can be pulsed into the reaction chamber for a duration of about 0.05 seconds to about 5.0 seconds, or about 0.1 seconds to about 3 seconds, or even about 0.2 seconds to about 1.0 seconds. Furthermore, during the contact between the substrate and the boron precursor, the flow rate of the boron precursor can be less than 20 slm, or less than 10 slm, or less than 7 slm, or less than 5 slm, or even less than 3 slm. Additionally, during the contact between the substrate and the boron precursor, the flow rate of the boron precursor can be in the range of about 0.05 to 10 slm, about 0.1 to 7 slm, or about 0.1 to about 5 slm.

[0069] In some embodiments, excess boron precursor can be purged by stopping the flow of the gaseous boron precursor while continuing to flow the carrier gas, purge gas, or gas mixture for a sufficient time to diffuse from the reaction chamber or to purge excess reactants and reactant byproducts (if any). In some embodiments, excess boron precursor can be purged by means of one or more inert gases (e.g., nitrogen, helium, or argon) that can flow throughout the cyclic deposition sub-step.

[0070] In some embodiments, the boron precursor may be purged from the reaction chamber for a period of about 0.1 seconds to about 10 seconds, or about 0.3 seconds to about 5 seconds, or even about 0.3 seconds to about 1 second. The supply and removal of the boron precursor may be considered as the first sub-step of step 104.

[0071] After the excess boron precursor and any reaction byproducts in the reaction chamber have been purged, the cyclic deposition stage 104 of the exemplary PEALD process 100 can proceed to a second sub-step, which includes contacting the substrate with a reactive material generated by a plasma, the plasma being produced by a nitrogen-containing gas.

[0072] In some embodiments, the nitrogen-containing gas includes one or more of nitrogen (N2), N2O, NO, N2H2, and NH3.

[0073] In the second sub-step, nitrogen-containing plasma can be generated by applying RF power of about 100W to 10000W, or about 10W to about 2000W, or about 50W to about 1500W, or about 100W to about 1200W. In some embodiments, the plasma can be generated in situ, while in other embodiments, the plasma can be generated remotely. In some embodiments, a spray head reactor can be used, and plasma can be generated between a base (with a substrate on top) and a spray head plate.

[0074] In some embodiments, the reactive material generated from the plasma can contact the substrate for a period of time between about 0.1 seconds and about 20 seconds, or about 0.5 seconds and about 10 seconds, or even between about 0.5 seconds and about 5 seconds. In some embodiments, the reactive material generated from the plasma can contact the substrate for a period of time between about 2 seconds and 10 seconds.

[0075] After a sufficient period of time to fully saturate the previously absorbed molecular layer and react with the nitrogen-based plasma pulse, any excess reactants and reaction byproducts can be removed from the reaction chamber. Similar to the removal of the first reactant (i.e., the gaseous boron precursor), this step may involve stopping the production of reactive substances and continuing the flow of an inert gas (e.g., a gas containing nitrogen, helium, and, in some embodiments, argon). The inert gas flow can be sufficient to allow excess reactive substances and volatile reaction byproducts to diffuse out of and be purged from the reaction chamber. For example, the purging process may utilize a time period between about 0.1 seconds and about 10 seconds, or about 0.1 seconds and about 4.0 seconds, or even between about 0.1 seconds and about 0.5 seconds. The supply and removal of nitrogen plasma together represent... Figure 1 The second sub-step of step 104 in the exemplary PEALD process 100.

[0076] A method in which the substrate is alternately and sequentially contacted with a gaseous boron precursor and with a reactive substance generated from a gas containing a nitrogen precursor can constitute a unit deposition cycle. In some embodiments of this disclosure, exemplary PEALD process step 104 may include repeating a unit deposition cycle once or more. For example, cyclic deposition may continue regardless of whether the desired thickness is achieved, for example, if the thickness of the deposited film is insufficient for the desired device structure, the process of a first sub-step contacting the substrate with the boron precursor and a second sub-step contacting the substrate with the reactant may be repeated once or more. For example, if the thickness of the deposited material is less than the thickness required for a particular application, the first and second sub-steps may be repeated once or more. In some embodiments, the method includes at least 1 cycle to at most 500 cycles, or at least 2 cycles to at most 450 cycles, or at least 3 cycles to at most 400 cycles, or at least 4 cycles to at most 350 cycles, or at least 5 cycles to at most 300 cycles, or at least 10 cycles to at most 290 cycles, or at least 20 cycles to at most 280 cycles. In some embodiments, the method includes up to 400 cycles, or up to 350 cycles, or up to 320 cycles, or up to 300 cycles, or up to 280 cycles, or up to 100 cycles, or up to 80 cycles, or up to 30 cycles, or up to 20 cycles, or up to 10 cycles, or up to 5 cycles, or up to 4 cycles, or up to 3 cycles, or up to 2 cycles, or a single cycle.

[0077] Although PEALD cycles are generally referred to herein as beginning with a boron precursor stage, it is conceivable that in other embodiments, the cycle may begin with a reactive material stage. Those skilled in the art will recognize that the first precursor phase typically reacts with the end phase left by the last phase in the previous cycle. Therefore, while if the reactive material is the first stage in a PEALD cycle, no reactant may have previously been absorbed onto the substrate surface or present in the reaction chamber, the reactive material stage will effectively follow the boron precursor stage in subsequent cycles. In some embodiments, one or more different PEALD cycles are provided during the deposition process.

[0078] In some embodiments, the deposited first material comprises boron nitride. In some embodiments of this disclosure, boron nitride may be deposited on a three-dimensional structure, such as a non-planar substrate containing high aspect ratio features. In some embodiments, in structures with an aspect ratio (height / width) greater than about 2, greater than about 5, greater than about 10, greater than about 25, greater than about 50, or even greater than about 100, the step coverage of the boron nitride film may be equal to or greater than about 50%, or greater than about 60%, or greater than about 70%, or greater than about 80%, or greater than about 90%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or greater.

[0079] In some embodiments, boron nitride is deposited on a substrate containing gaps. In some embodiments, the substrate comprises a silicon oxide material. In some embodiments, the substrate comprises silicon nitride, silicide, amorphous silicon, or metal. Boron nitride is conformally deposited into the gaps to at least partially fill them.

[0080] Next, in step 105 of method 100, a portion of the first material is etched. In step 105, the etching is selective. In other words, the etchant removes only the desired first material, such as boron nitride, but does not etch the substrate beneath the first material, such as silicon oxide. The selective etching step 105 can be performed, for example, by providing an etching reactant and providing etching plasma power to form an activating material from the etching reactant.

[0081] In step 105, only a portion of the first material is removed from the surface of the substrate. In some embodiments, the substrate includes gaps, and in step 104, the first material is conformally deposited to at least partially fill the gaps. In these embodiments, the first material is removed near the top of the gaps, still leaving gaps at least partially filled with the first material.

[0082] In step 105, the plasma may be provided as pulsed plasma. According to an example, the plasma pulse period is between approximately 0.01 milliseconds and 0.2 milliseconds. The total plasma pulse period may be approximately 1 second to approximately 20 (e.g., 10) seconds, approximately 0.3 seconds to approximately 10 (e.g., 5) seconds, approximately 8 seconds to approximately 12 seconds, or approximately 3 seconds to approximately 7 seconds, for a total plasma on-time. Additionally, during the contact between the substrate and the etching reactant, the flow rate of the etching reactant may be less than 20 slm, or less than 10 slm, or less than 7 slm, or less than 5 slm, or even less than 3 slm. Furthermore, during the contact between the substrate and the etching reactant, the flow rate of the etching reactant may be in the range of approximately 0.05 to 10 slm, approximately 0.1 to 7 slm, or approximately 0.1 to approximately 5 slm.

[0083] According to another example, the plasma power on-time duty cycle is greater than 0 and less than 99%, or between about 5% and 95%. The plasma power during step 105 can range from about 100W to about 10,000W, or from about 150W to about 1,000W, or from about 100W to about 1,000W, or from about 100W to about 400W.

[0084] The frequency of the pulsed plasma power can vary between approximately 400 kHz and 100 GHz, depending on the plasma source. The plasma source in step 104 is selected from at least one of high-density plasma, microwave plasma, or inductively coupled plasma. In inductively coupled plasma, the RF is between 25 and 45 MHz, for example, 27 to 41 MHz. In high-density plasma, the RF is up to 100 MHz, for example, 50 to 90 MHz, or 55 to 70 MHz. In microwave plasma, microwave radiation is applied at an RF of 0.3-100 GHz, for example, 0.5-100 GHz, such as 1-20 GHz or 2-5 GHz. In some embodiments, the plasma source in step 104 is selected from two of high-density plasma, microwave plasma, or inductively coupled plasma.

[0085] In embodiments using high-density plasma, the thermal conductivity of the deposited film may increase. High-density plasma alters the crystallinity of the film when it reacts with free radicals. In some embodiments, the thermal conductivity of films deposited using high-density plasma is approximately twice as high as that of films deposited using other types of plasma.

[0086] In some embodiments, the etchant reactant comprises fluorine. In some embodiments, the etchant reactant is selected from NF3, CF4, C2F6, SF6, NH2F, C3F8, F2, XeF2, HF, CHF3, CH3F, CH2F2, C4F8, C4F6, Cl2, SiCl4, BCl3, C4F6, NH3, N2H2, and any combination thereof. When the etchant reactant is treated with the plasma described above, the etchant reactant decomposes into reactive substances, such as more reactive ions and free radicals. These reactive substances are then capable of etching the first material deposited on the substrate. The plasma enhances the etching process by providing the necessary energy to activate the etchant reactant, thereby facilitating the removal of the desired material from the substrate surface. This process is particularly useful for achieving selective etching, where only specific materials are removed without affecting the underlying layers.

[0087] In some embodiments, the etching process is spontaneous etching. In spontaneous etching, the reactive material generated by the etchant reactant gas is sufficiently reactive to interact with the first material on the substrate surface, thereby causing its removal. This type of etching relies on the inherent chemical reactivity of the etchant material with the first material to be etched. The amount of first material etched depends on the amount of etchant reactant provided to the reaction chamber. The more etchant reactant provided to the reaction chamber, in other words, the longer the etchant reactant pulse time, the more first material is etched.

[0088] Once the required amount of the first material has been etched, method 100 proceeds to step 106 to deposit the first material. In step 106, the first material is deposited similarly to that in step 104. In some embodiments, instead of depositing the first material, a third material is deposited in step 106. The third material may include silicon nitride. Examples of depositing the third material are described below.

[0089] Step 106 can be divided into two sub-steps: the first sub-step is to provide a silicon precursor into the reaction chamber, and the second sub-step is to contact the substrate with a reactive material generated by a plasma, which is produced by a nitrogen-containing gas. When step 104 includes a cyclic process, the first and second sub-steps can be performed sequentially, with an interspersed purging step between them. When step 104 includes a CVD process, the first and second sub-steps can overlap. In the first sub-group, the silicon precursor is provided to the reaction chamber in the gas phase. In the case of cyclic deposition, the silicon precursor can be pulsed into the reaction chamber. According to some embodiments, the silicon precursor can be supplied to the reaction chamber using a carrier gas flow. In some embodiments, the silicon precursor may contain a volatile silicon material that reacts with the substrate surface. The silicon precursor pulse can cause the substrate surface to self-saturate, so that the excess components of the silicon precursor pulse will not further react with the molecular layer formed by the process.

[0090] The silicon precursor pulse is preferably supplied as a gaseous reactant. For the purposes of this disclosure, the silicon precursor gas may be considered "volatile" if the material exhibits sufficient vapor pressure under processing conditions to deliver the material at a sufficient concentration to the substrate surface to saturate the exposed surface.

[0091] In some embodiments, the fumed silicon precursor comprises a silane, a halosilane, or an organosilane. In some embodiments, the silicon precursor comprises a halosilane, and the halosilane comprises one or more of dichlorosilane, diiodosilane, hexachloroethylsilane, octachloropropane, dibromosilane, tribromosilane, trichlorosilane (HSiCl3), chlorosilane (H3SiCl), silicon tetrachloride (SiCl4), bromosilane (H3SiBr), triiodosilane (HSiI3), iodosilane (H3SiI), diiodosilane (H2Si2I4), H4Si2I2, and H5Si2I.

[0092] In some embodiments, the silicon precursor comprises an organosilane, and the organosilane comprises one or more of aminosilanes and heterosilanes.

[0093] In some embodiments, the silicon precursor is selected from tris(dimethylamino)silane, bis(tert-butylamino)silane, bis(sec-butylamino)silane, trimethylsilylamine, neopentylsilane, bis(dimethylamino)silane (DMAS), bis(diethylamino)silane (BDEAS), bis(ethylmethylamino)silane (BEMAS), tetra(dimethylamino)silane (TKDMAS), trimethylsilane (SiH(CH3)3), tetramethylsilane (Si(CH3)4), silane, tetra(ethoxy)silane (TEOS, Si(OC2H5)4), tri(tert-butoxy)silanol (TBOS), tri(tert-pentoxy)silanol (TPSOL), and dimethyldichlorosilane (Si(OC2H5)4, Si(CH3)2(OCH3)2).

[0094] In some embodiments of this disclosure, the silicon precursor can be pulsed into the reaction chamber for a period of about 0.05 seconds to about 5.0 seconds, or about 0.1 seconds to about 3 seconds, or even about 0.2 seconds to about 1.0 seconds. Additionally, during the contact between the substrate and the silicon precursor, the silicon precursor flow rate can be less than 20 slm, or less than 10 slm, or less than 7 slm, or less than 5 slm, or even less than 3 slm. Furthermore, during the contact between the substrate and the silicon precursor, the silicon precursor flow rate can be in the range of about 0.05 to 10 slm, about 0.1 to 7 slm, or about 0.1 to about 5 slm.

[0095] In some embodiments, excess silicon precursor can be purged by stopping the flow of the gaseous silicon precursor while continuing to allow the carrier gas, purge gas, or gas mixture to flow for a sufficient time to diffuse from the reaction chamber or to purge excess reactants and reactant byproducts (if any). In some embodiments, excess silicon precursor can be purged by means of one or more inert gases (e.g., nitrogen, helium, or argon) that can flow throughout the cyclic deposition sub-step.

[0096] In some embodiments, the silicon precursor may be purged from the reaction chamber for a period of about 0.1 seconds to about 10 seconds, or about 0.3 seconds to about 5 seconds, or even about 0.3 seconds to about 1 second. The provision and removal of the silicon precursor may be considered as the first sub-step of step 106.

[0097] After the excess silicon precursor and any reaction byproducts in the reaction chamber have been purged, the cyclic deposition stage 106 of the exemplary PEALD process 100 can proceed to a second sub-step, which includes contacting the substrate with a reactive material generated by a plasma, the plasma being generated by a nitrogen-containing gas.

[0098] In some embodiments, the nitrogen-containing gas includes one or more of nitrogen (N2), N2O, and NO.

[0099] In the second sub-step, nitrogen-containing plasma can be generated by applying RF power of about 10W to about 2000W, or about 50W to about 1500W, or about 100W to about 1200W. In some embodiments, the plasma can be generated in situ, while in other embodiments, the plasma can be generated remotely. In some embodiments, a spray head reactor can be used, and plasma can be generated between a base (with a substrate on top) and a spray head plate.

[0100] In some embodiments, the reactive material generated from the plasma can contact the substrate for a period of time between about 0.1 seconds and about 20 seconds, or about 0.5 seconds and about 10 seconds, or even between about 0.5 seconds and about 5 seconds. In some embodiments, the reactive material generated from the plasma can contact the substrate for a period of time between about 2 seconds and 10 seconds.

[0101] After a sufficient period of time to fully saturate the previously absorbed molecular layer and react with the nitrogen-based plasma pulse, any excess reactants and reaction byproducts can be removed from the reaction chamber. Similar to the removal of the first reactant, i.e., the gaseous silicon precursor, this step may include stopping the production of reactive material and continuing the flow of an inert gas (e.g., a gas containing nitrogen, helium, and in some embodiments, argon). The inert gas flow can be sufficient to allow excess reactive material and volatile reaction byproducts to diffuse out of and be purged from the reaction chamber. For example, a purging process of about 0.1 seconds to about 10 seconds, or about 0.1 seconds to about 4.0 seconds, or even a period between about 0.1 seconds and about 0.5 seconds can be utilized. The supply and removal of nitrogen plasma together represent... Figure 1 The second sub-step of step 106 in the exemplary PEALD process 100.

[0102] A method in which the substrate is alternately and sequentially contacted with a vapor-phase silicon precursor and with a reactive substance generated from a gas containing a nitrogen precursor can constitute a unit deposition cycle. In some embodiments of this disclosure, exemplary PEALD process step 106 may include repeating a unit deposition cycle once or more. For example, cyclic deposition may continue regardless of whether the desired thickness is achieved, for example, if the thickness of the deposited film is insufficient for the desired device structure, the process of a first sub-step contacting the substrate with the silicon precursor and a second sub-step contacting the substrate with the reactants may be repeated once or more. For example, if the thickness of the deposited material is less than the thickness required for a particular application, the first and second sub-steps may be repeated once or more. In some embodiments, the method includes at least 1 cycle to at most 1000 cycles, or at least 2 cycles to at most 850 cycles, or at least 3 cycles to at most 800 cycles, or at least 4 cycles to at most 750 cycles, or at least 5 cycles to at most 700 cycles, or at least 10 cycles to at most 590 cycles, or at least 20 cycles to at most 480 cycles. In some embodiments, the method includes up to 1,500 cycles, or up to 1,000 cycles, or up to 800 cycles, or up to 320 cycles, or up to 300 cycles, or up to 280 cycles, or up to 100 cycles, or up to 80 cycles, or up to 30 cycles, or up to 20 cycles, or up to 10 cycles, or up to 5 cycles, or up to 4 cycles, or up to 3 cycles, or up to 2 cycles, or a single cycle.

[0103] Although PEALD cycles are generally referred to herein as beginning with a silicon precursor stage, it is conceivable that in other embodiments, the cycle may begin with a reactive material stage. Those skilled in the art will recognize that the first precursor phase typically reacts with the end phase left by the last phase in the previous cycle. Therefore, while no reactant may be pre-absorbed on the substrate surface or present in the reaction chamber if the reactive material is the first stage in a PEALD cycle, the reactive material phase will effectively follow the silicon precursor phase in subsequent cycles. In some embodiments, one or more different PEALD cycles are provided during the deposition process.

[0104] In embodiments involving gap filling, the gap is completely filled in step 106. Once the first or third material has been deposited in step 106, method 100 ends 107.

[0105] Now go to Figure 2 The present invention illustrates a reactor system 200 according to exemplary embodiments thereof. The reactor system 200 may be used to perform one or more steps or sub-steps as described herein and / or to form one or more structures or portions thereof as described herein.

[0106] The reactor system 200 includes a pair of parallel, facing conductive plate electrodes 4, 2 within the interior 11 (reaction zone) of the reaction chamber 3. Plasma can be excited within the reaction chamber 3 by applying HRF power (e.g., 100 kHz, 13.56 MHz, 27 MHz, 2.45 GHz, or any value between) from a power source 25 to one electrode (e.g., electrode 4) and electrically grounding the other electrode (e.g., electrode 2). A temperature regulator is located in the lower platform 2 (lower electrode), and the temperature of the substrate 1 placed thereon can be maintained at a desired temperature, such as the substrate temperature described above. Electrode 4 can serve as a gas distribution device, such as a spray plate or spray head. Precursor gas, nitrogen reactant gas, etching reactant gas, and dilution gas / carrier gas (if any) can be introduced into the reaction chamber 3 from sources 21, 22, and 20 and through the spray plate 4 using one or more of gas lines 23, 24, and 25, respectively. Although four gas lines 23, 24, 25, and 26 are shown, reactor system 200 may include any suitable number of gas lines. For example, source 21 may correspond to a boron precursor source, source 22 may correspond to a nitrogen reactant source, and source 20 may correspond to an etching reactant source.

[0107] In the reaction chamber 3, a circular pipe 13 with an exhaust line 7 is provided, through which gases in the interior 11 of the reaction chamber 3 can be discharged. Additionally, a transfer chamber 5 located below the reaction chamber 3 is provided with a sealing gas line 24 to introduce sealing gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5. A separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve is omitted from the figure; the substrate is transferred in and out of the transfer chamber 5 through this gate valve). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition and / or etching steps are performed in the same reaction space, allowing two or more (e.g., all) steps to be performed consecutively without exposing the substrate to air or other oxygen-containing atmospheres.

[0108] In some embodiments, a flow-through system (FPS) can be used to achieve continuous flow of carrier gas to reaction chamber 3, wherein the carrier gas line is provided with a bypass line having a precursor reservoir (bottle), and the main line and the bypass line are switched, wherein the bypass line is closed when only carrier gas is intended to be delivered to the reaction chamber, and the main line is closed when both carrier gas and precursor gas are intended to be delivered to the reaction chamber, and the carrier gas flows through the bypass line and flows out of the bottle together with the precursor gas. In this way, the carrier gas can flow continuously into the reaction chamber, and the precursor gas can be carried in pulses by switching between the main line and the bypass line, without substantially causing pressure fluctuations in the reaction chamber.

[0109] Reactor system 200 may include one or more controllers 26, which are programmed or otherwise configured to cause one or more method steps as described herein to be performed. As those skilled in the art will understand, controller 26 is coupled to various power supplies, heating systems, pumps, robots, and gas flow controllers or valves of the reactor. For example, controller 26 may be configured to control the gas flow of silicon precursors, nitrogen reactants, and etching reactants into at least one of one or more reaction chambers.

[0110] In some embodiments, the reactor system 200 may include a remote plasma unit, a microwave plasma unit, or a high-density plasma unit (not shown). At least one of these plasma units may be activated when etching reactants are provided to the reaction chamber to provide reactive material. In these embodiments, such as Figure 1 The deposition steps shown in method 100, namely steps 104 and 106, can be performed in the same reactor system as the etching step 105.

[0111] In some embodiments, a dual-chamber reactor (for processing two portions or compartments of a substrate disposed close to each other) may be used, wherein reactant gases and rare gases may be supplied via a common line, while precursor gases may be supplied via a non-common line.

[0112] Now go to Figure 3This illustrates a method 300 according to an exemplary embodiment of the present disclosure. Method 300 involves filling a gap in a substrate. The substrate 302 includes a second material, such as silicon oxide, and includes at least one gap, such as... Figure 3 As shown. The gap includes a proximal surface, sidewalls, and a distal surface. The proximal surface is the surface at the top of the gap, and the distal surface is the surface at the bottom of the gap.

[0113] First, the initial deposition is performed. Deposition can be similar to... Figure 1 Step 104 is described. A first deposition conformally deposits a first material 301, such as boron nitride, onto the surface of the substrate 302 to fill gaps. The first material is deposited on the proximal and distal surfaces and the sidewalls. The thickness of the deposited first material is substantially the same on each of the proximal and distal surfaces and the sidewalls. In some embodiments, the first deposition leaves seams or voids in the gaps.

[0114] Second, selectively etch a portion of the first material from the gaps. Etching can be similar to... Figure 1 Step 105 is described. Selective etching is performed on a portion of the first material 301 deposited through the gaps, but without etching or substantially without etching the substrate 302 material. The etching is performed in situ in the same reaction chamber as the first and second deposition steps.

[0115] Third, once the required amount of the first material has been etched, a second deposition is performed. The second deposition can be similar to... Figure 1 Step 106 is described. A second deposition conformally deposits a first material (e.g., boron nitride) or a third material (e.g., silicon nitride) 303 onto the portions of the surface of the underlying first material 301 and substrate 302 that are not covered by the first material 301 to fill the gap. The first or third material 303 is deposited on the proximal and distal surfaces and sidewalls. The thickness of the deposited first or third material is substantially the same on each of the proximal and distal surfaces and sidewalls. In some embodiments, the second deposition leaves a seam or void in the gap. When the first or third material 303 is conformally deposited onto the seam or void of the first deposition, a seam stop layer 304 is formed in the gap. The seam stop layer 304 improves the gap filling quality and allows the seam stop layer 304 to withstand subsequent process flow steps (not described herein).

[0116] In some embodiments (not shown), the first or third material 303 is eventually etched back so that it substantially does not cover the proximal surface, and the gap is filled only to the level of the proximal surface.

[0117] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0118] The specific embodiments shown and described are illustrative of the invention and its best mode, and are not intended to limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, fabrication, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0119] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples herein should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted.

[0120] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of various processes, systems and configurations, as well as other features, functions, actions and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method for forming a structure, comprising: A substrate containing the deposited first material is provided into the reaction chamber; as well as Reactive materials generated by plasma are supplied to the reaction chamber to etch the first material; the plasma is generated by the etching reactant gas. The plasma is pulsed plasma, and The plasma is selected from at least one of high-density plasma, microwave plasma, and inductively coupled plasma.

2. The method according to claim 1, wherein, The etching is spontaneous etching.

3. The method according to claim 1, wherein, The etching reactants are selected from NF3, CF4, C2F6, SF6, NH2F, C3F8 and F2, XeF2, HF, CHF3, CH3F, CH2F2, C4F8, C4F6, Cl2, SiCl4, BCl3, C4F6, NH3, N2H2 and any combination thereof.

4. A method for forming a structure, comprising: The step of providing a substrate into the reaction chamber, the substrate comprising a second material; The step of conformally depositing the first material onto the substrate; The step of selectively etching at least a portion of the first material; as well as The step of conformally depositing the third or first material onto the substrate. All of the steps described herein are performed in the same reaction chamber.

5. The method according to claim 4, wherein, The substrate includes at least one gap having a proximal surface, sidewalls, and a distal surface.

6. The method according to claim 4, wherein, The second material is conformally deposited into the at least one gap to fill the gap, such that the deposited first material covers the proximal surface, the sidewall, and the distal surface.

7. The method according to claim 5 or 6, wherein, During the step of selectively etching at least a portion of the first material, the etching of the first material causes the gap to be partially filled.

8. The method of claim 5, further comprising etching the third or first material such that substantially no material covers the proximal surface.

9. The method according to any one of claims 4 to 8, wherein, The second material includes silicon oxide.

10. The method according to any one of claims 4 to 8, wherein, The first material includes boron nitride.

11. The method according to any one of claims 4 to 10, wherein, The third material includes silicon nitride.

12. The method according to any one of claims 4 to 11, wherein, The selective etching step includes removing the first material and not removing or substantially not removing any of the second material.

13. The method according to claim 4, wherein, The selective etching step is performed by the method according to any one of claims 1 to 3.

14. The method according to claim 4, wherein, The first material is conformally deposited by performing at least one deposition cycle, wherein the at least one deposition cycle includes: The boron precursor is provided to the reaction chamber in the gas phase; and Reactive substances generated by plasma are supplied to the reaction chamber; the plasma is generated by nitrogen-containing gas.

15. The method according to claim 14, wherein, The boron precursors include one or more of boron halides, boranes, cycloboranes, and organoboranes.

16. The method of claim 14, wherein, The boron precursors include boron halides selected from the following: boron triiodide, boron tribromide, boron trichloride, diboron tetrachloride, boron monofluoride, boron trifluoride, and diboron tetrafluoride.

17. The method of claim 14, wherein, The boron precursor includes boranes selected from the following: borane, diborane, tetraborane, pentaborane, decaborane, and borane-ammonia complexes.

18. The method according to claim 14, wherein, The boron precursor comprises a cycloborane represented by formula (I): (I) Among them, R 1 R 2 R 3 R 4 R 5 R 6 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, and alkoxy.

19. The method of claim 14, wherein, The boron precursor includes organoboranes selected from the following: trimethylborane, triethylborane, 3-tri-(dimethylamino)borane, dimethylamineborane, and triethylamineborane.

20. The method of claim 14, wherein, The nitrogen-containing gas includes one or more of nitrogen (N2), N2O, and NO.

21. A system for depositing material on the surface of a substrate, the system comprising: The reaction chamber is used to contain a substrate including gaps and a second material; A silicon precursor source is fluidly connected to the reaction chamber via a first valve; The nitrogen reactant source is in fluid communication with the reaction chamber via a second valve; An etching reactant source, which is in fluid communication with the reaction chamber via a third valve; and A controller, operably connected to the first, second, and third valves, and configured and programmed to control: The boron precursor is supplied to the reaction chamber; Nitrogen reactants are supplied to the reaction chamber; The etchant is supplied to the reaction chamber; as well as The material is deposited on the surface of the substrate using the method according to claim 4.

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