Novel oxidizing agents and strained ring precursors

Abstract

Novel cyclic silicon precursors and oxidizers are described. Methods for depositing silicon-containing films on substrates are described. The substrate is exposed to the silicon precursors and reactants to form silicon-containing films (e.g., elemental silicon, silicon oxide, silicon nitride). The exposures can be sequential or simultaneous.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] Embodiments of the present disclosure relate to silicon precursors, oxidizers, and methods for depositing silicon-containing films. More particularly, embodiments of the present disclosure relate to strained-ring silicon precursors, oxaziridine oxidizers, P / S / N oxides, and methods of using them. [Background technology]

[0002]

[0002] The semiconductor processing industry continues to strive for higher production yields while increasing the uniformity of layers deposited on substrates with larger surface areas. These same factors, combined with new materials, also increase the density of circuits per unit area of ​​the substrate. As circuit density increases, the need for uniformity and process control over layer thickness increases. As a result, various techniques have been developed for depositing layers on substrates in a cost-effective manner while maintaining control over the layer's properties.

[0003] Chemical vapor deposition (CVD) is one of the most common deposition processes used to deposit layers on substrates. CVD is a flux-dependent deposition technique that requires precise control of the substrate temperature and precursors introduced into the processing chamber to produce a desired layer of uniform thickness. These requirements become more important as substrate size increases, necessitating more complex chamber designs and gas flow techniques to maintain adequate uniformity.

[0004]

[0004] One type of CVD that exhibits excellent step coverage is cyclic deposition, or atomic layer deposition (ALD). Cyclic deposition is based on atomic layer epitaxy (ALE) and uses chemisorption techniques to deliver precursor molecules onto a substrate surface in sequential cycles. The cycles expose the substrate surface to a first precursor, a purge gas, a second precursor, and a purge gas. The first and second precursors react to form a product compound as a film on the substrate surface. This cycle is repeated to form a layer to a desired thickness.

[0005]

[0005] The increasing complexity of advanced microelectronic devices places stringent demands on currently used deposition techniques. Unfortunately, there are a limited number of viable chemical precursors available that possess the necessary properties, such as robust thermal stability, high reactivity, and suitable vapor pressure for film growth to occur. In addition, precursors that meet these requirements often suffer from long-term stability issues and result in thin films that contain high concentrations of contaminants, such as oxygen, nitrogen, and halides, that are often detrimental to the target film application.

[0006]

[0006] Silicon-containing films are often contaminated with halogens due to the use of halogen-containing precursors. These halogen contaminants often adversely affect device performance and require separate removal procedures, which may not be completely effective.

[0007] Additionally, lower temperature deposition processes are required because many substrate materials often already contain temperature-sensitive materials and structures (e.g., logic devices), and plasma- and / or ozone-free deposition procedures may reduce hardware demands and improve selectivity.

[0008]

[0008] Therefore, there is a need in the art for new silicon precursors and oxidizers that are halogen-free, have low activation energy requirements, and / or are capable of depositing silicon-containing films without the use of plasma. Summary of the Invention

[0009]

[0009] One or more embodiments of the present disclosure relate to a method for depositing a silicon-containing material, the method comprising exposing a substrate to a cyclic silicon precursor and a reactant, the cyclic silicon precursor comprising a silicon-containing three- or four-membered ring.

[0010] A further embodiment of the present disclosure relates to a method for depositing silicon oxide, the method comprising exposing a substrate to a silicon precursor and an oxidizing agent comprising an oxaziridine.

[0011] A further embodiment of the present disclosure relates to a method for depositing silicon oxide, the method comprising exposing a substrate to an oxidizing agent comprising a silicon precursor and a P / S / N oxide.

[0012]

[0012] So that the above-mentioned features of the present disclosure can be understood in detail, a more particular description of the present disclosure briefly summarized above can be made by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered as limiting its scope. [Brief explanation of the drawings]

[0013] [Figure 1] 1 illustrates a process flow diagram of a method according to one or more embodiments of the present disclosure. [Figure 2]

[0014] FIG. 1 illustrates an exemplary silicon precursor according to one or more embodiments of the present disclosure. [Figure 3]

[0015] FIG. 1 shows an exemplary oxaziridine according to one or more embodiments of the present disclosure. [Figure 4]

[0016] FIG. 4 illustrates an exemplary P / S / N oxide according to one or more embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014]

[0017] Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or carried out in various ways.

[0015]

[0018] Embodiments of the present disclosure provide precursors, reactants, and processes for depositing silicon-containing films. Some embodiments of the present disclosure provide cyclic silicon precursors. In some embodiments, the cyclic silicon precursors are substantially halogen-free. In some embodiments, the cyclic silicon precursors include a 3- or 4-membered silicon-containing ring. In some embodiments, the cyclic silicon precursors can be used under ALD and CVD conditions to deposit silicon-containing films.

[0016]

[0019] As noted above, the cyclic silicon precursor of one or more embodiments is substantially free of halogen. As used herein, the term "substantially free" means that the cyclic silicon precursor has less than about 5% halogen, including less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5%, on an atomic basis.

[0017]

[0020] Some embodiments of the present disclosure provide an oxidizing agent. In some embodiments, the oxidizing agent comprises an oxaziridine. In some embodiments, the oxidizing agent comprises a P / S / N oxide. In some embodiments, the oxidizing agent can be used under ALD and CVD conditions to deposit silicon-containing films.

[0018]

[0021] The process of various embodiments provides silicon-containing films using vapor deposition techniques such as atomic layer deposition (ALD) or chemical vapor deposition (CVD). The cyclic silicon precursors and / or oxidizers of one or more embodiments are volatile and thermally stable, and therefore suitable for vapor deposition. In some embodiments, the cyclic silicon precursors and / or oxidizers have a relatively low activation barrier for forming silicon-containing films. In some embodiments, the cyclic silicon precursors and / or oxidizers can be used to form silicon-containing films at relatively low temperatures. In some embodiments, the cyclic silicon precursors and / or oxidizers can be used to form silicon-containing films without the use of a plasma.

[0019]

[0022] As used herein, "substrate" refers to any substrate or material surface formed on a substrate upon which film processing is performed during a manufacturing process. For example, substrate surfaces upon which processing can be performed include, depending on the application, materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials. Substrates include, but are not limited to, semiconductor wafers. Substrates can be subjected to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to film processing directly on the surface of the substrate itself, any of the disclosed film processing steps can be performed on an underlying layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include the underlying layer as the context indicates. Thus, for example, when a film / layer or partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0020]

[0023] As used herein, "substrate surface" refers to any substrate surface upon which a layer may be formed. The substrate surface may have one or more features formed therein, one or more layers formed thereon, and combinations thereof. The substrate (or substrate surface) may be pretreated prior to deposition of the molybdenum-containing layer, for example, by polishing, etching, reducing, oxidizing, halogenating, hydroxylating, annealing, baking, etc.

[0021]

[0024] The substrate may be any substrate on which a material can be deposited, such as a silicon substrate, a III-V compound substrate, a silicon germanium (SiGe) substrate, an epitaxial substrate, a silicon-on-insulator (SOI) substrate, a display substrate such as a liquid crystal display (LCD), a plasma display, or an electroluminescent (EL) lamp display, a solar cell array, a solar panel, a light-emitting diode (LED) substrate, a semiconductor wafer, or the like. In some embodiments, one or more additional layers may be disposed on the substrate such that a molybdenum-containing layer is at least partially formed thereon. For example, in some embodiments, a layer comprising a metal, a nitride, an oxide, or a combination thereof may be disposed on the substrate, and a silicon-containing layer may be formed on such a layer.

[0022]

[0025] According to one or more embodiments, the method uses an atomic layer deposition (ALD) process. In such embodiments, the substrate surface is exposed to precursors (also called reactants or reactive gases) in a sequential or substantially sequential manner. As used throughout this specification, "substantially sequential" means that the majority of the precursor exposure periods do not overlap with exposure to co-reagents, although there may be some overlap.

[0023]

[0026] As used herein and in the appended claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gas species capable of reacting with the substrate surface.

[0024]

[0027] As used herein, "atomic layer deposition" or "cyclic deposition" refers to the sequential exposure of two or more reactive compounds to deposit layers of material on a substrate surface. As used in this specification and the appended claims, Terms such as “reactive compound,” “reactive gas,” “reactive species,” “precursor,” and “process gas” are used interchangeably to refer to substances having species capable of reacting with a substrate surface or materials on the substrate surface in a surface reaction (e.g., chemisorption, oxidation, reduction). A substrate or a portion of a substrate is sequentially exposed to two or more reactive compounds introduced into a reaction zone of a processing chamber. In a time-domain ALD process, exposure to each reactive compound is separated by a time delay to allow each compound to adhere to and / or react with the substrate surface. In a spatial ALD process, different portions of the substrate surface, or materials on the substrate surface, are exposed to two or more reactive compounds simultaneously, so that no point on the substrate is substantially exposed to multiple reactive compounds at the same time. As used in this specification and the appended claims, the term “substantially” as used in this context means that, as will be understood by those skilled in the art, a small portion of the substrate may be exposed to multiple reactive gases simultaneously due to diffusion, and is not intended to be simultaneously exposed.

[0025]

[0028] In one aspect of a time-domain ALD process, a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction zone, followed by a first time delay. Then, a second precursor or compound B is pulsed into the reaction zone, followed by a second delay. During each delay, a purge gas, such as argon, is introduced into the process chamber to purge the reaction zone or remove residual reactive compounds or by-products from the reaction zone. Alternatively, the purge gas may flow sequentially throughout the deposition process, with only the purge gas flowing during the time delay between pulses of reactive compounds. The reactive compounds are alternately pulsed until the desired film or film thickness is formed on the substrate surface. In either scenario, the ALD process of pulsing compound A, purge gas, compound B, and purge gas constitutes one cycle. The cycle begins with either compound A or compound B, and continues in each order until the desired film thickness is achieved.

[0026]

[0029] In one embodiment of a spatial ALD process, a first reactive gas and a second reactive gas (e.g., hydrogen radicals) are simultaneously supplied to a reaction zone but separated by an inert gas curtain and / or a vacuum curtain, and the substrate is moved relative to the gas supply system so that any point on the substrate is exposed to both the first reactive gas and the second reactive gas.

[0027]

[0030] Without intending to be bound by theory, it is believed that the presence of halogens in the structure of silicon precursors can pose a problem, as halogen contamination can affect device performance and may require additional removal steps.

[0028]

[0031] Silicon-containing films can be grown by atomic layer deposition or chemical vapor deposition for many applications. One or more embodiments of the present disclosure advantageously provide an atomic layer deposition or chemical vapor deposition process for forming silicon-containing films. As used in this specification and the appended claims, the term "silicon-containing film" refers to a film containing silicon atoms, and has about 1 atomic % or more silicon, about 2 atomic % or more silicon, about 3 atomic % or more silicon, about 4 atomic % or more silicon, about 5 atomic % or more silicon, about 10 atomic % or more silicon, about 15 atomic % or more silicon, about 20 atomic % or more silicon, about 25 atomic % or more silicon, about 30 atomic % or more silicon, about 35 atomic % or more silicon, about 40 atomic % or more silicon, about 45 atomic % or more silicon, about 50 atomic % or more silicon, or about 60 atomic % or more silicon. In some embodiments, the silicon-containing film comprises one or more of elemental silicon (e.g., amorphous silicon, polycrystalline, crystalline), silicon oxide (SiO), silicon nitride (SiN), silicon carbide (SiC), or combinations thereof. Those skilled in the art will recognize that the use of a molecular formula such as SiO does not imply a particular stoichiometric relationship between elements, but simply refers to the identity of the film's major components. For example, SiO refers to a film whose major components are silicon and oxygen atoms. In some embodiments, the major composition of a particular film (i.e., the sum of the atomic percentages of the particular atoms) is greater than or equal to about 95%, 98%, 99%, or 99.5% of the film on an atomic basis.

[0029]

[0032] 1, one or more embodiments of the present disclosure are directed to a method 100 of depositing a film. The method shown in FIG. 1 represents an atomic layer deposition (ALD) process in which a substrate or substrate surface is sequentially exposed to reactive gases in a manner that prevents or minimizes gas-phase reaction of the reactive gases. In some embodiments, the method includes a chemical vapor deposition (CVD) process in which reactive gases are mixed in a processing chamber to enable gas-phase reaction of the reactive gases and deposition of a thin film.

[0030]

[0033] In some embodiments, the method 100 includes a pretreatment operation 105. The pretreatment may be any suitable pretreatment known to those skilled in the art. Suitable pretreatments include, but are not limited to, preheating, cleaning, soaking, removing native oxides, or depositing an adhesion layer (e.g., titanium nitride (TiN)).

[0031]

[0034] In deposition 110, a process is performed to deposit a silicon-containing film on a substrate (or substrate surface). The deposition process can include one or more operations to form a film on the substrate. In operation 112, the substrate (or substrate surface) is exposed to a silicon precursor to deposit a film on the substrate (or substrate surface). The silicon precursor can be any suitable silicon-containing compound that can react with (i.e., adsorb or chemisorb) the substrate surface to leave a silicon-containing species on the substrate surface.

[0032]

[0035] In some embodiments, the silicon precursor comprises a silane, polysilane, or cyclosilane, and may comprise one or more halogen atoms. In some embodiments, the silicon precursor comprises one or more of silane, disilane, trisilane, tetrasilane, cyclopentasilane, cyclohexasilane, chlorosilane, dichlorosilane, or hexachlorodisilane.

[0033]

[0036] Unless otherwise noted, the terms "lower alkyl," "alkyl," or "alk," as used herein alone or as part of another group, include both linear and branched hydrocarbon groups typically containing 1 to 20 carbons, 1 to 10 carbons, 1 to 8 carbons, 1 to 6 carbons, 1 to 4 carbons, or 1 to 2 carbons in the chain, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and various branched isomers thereof. Such groups may optionally contain up to 1 to 4 substituents. Alkyl may be substituted or unsubstituted.

[0034]

[0037] In one or more embodiments, the cyclic silicon precursor comprises a three- or four-membered ring containing silicon. In some embodiments, the cyclic silicon precursor has the general formula:

[0038] TIFF0007730931000001.tif19170,

[0039] wherein X and Y are independently selected from CH2, SiH2, NH, S, or Se, and R1 and R2 are each independently H or alkyl. In some embodiments, at least one or both of X or Y is S. In some embodiments, R1 and R2 are each independently C1-C8 alkyl, C1-C6 alkyl, C1-4 alkyl, C1-C2 alkyl, or together form a C3-C8 cycloalkyl.

[0035]

[0040] In some embodiments, the cyclic silicon precursor has the general formula:

[0041] TIFF0007730931000002.tif20170

[0042] wherein X and Y are independently selected from CH2, SiH2, NH, S, or Se, and R1-R4 are each independently H or alkyl. In some embodiments, R1-R4 are each independently C1-C8 alkyl, C1-C6 alkyl, C1-4 alkyl, or C1-C2 alkyl. In some embodiments, the cyclic silicon precursor comprises:

[0043] TIFF0007730931000003.tif15170.

[0036]

[0044] FIG. 2 shows a non-limiting collection of exemplary cyclic silicon precursors.

[0037]

[0045] Without being bound by theory, it is believed that the cyclic silicon precursors disclosed herein react via a thermodynamically favorable ring-opening mechanism. In some embodiments, the ring-opening reaction of the cyclic silicon precursor has a more negative reaction energy than the silicon halide bond.

[0038]

[0046] In operation 114, the processing chamber is optionally purged to remove unreacted silicon precursor, reaction products, and by-products. As used in this manner, the term "processing chamber" does not encompass the entire interior volume of the processing chamber, but also includes a portion of the processing chamber adjacent to the substrate surface. For example, in spatially separated processing chamber sectors, the portion of the processing chamber adjacent to the substrate surface is purged of molybdenum precursor by any suitable technique, including, but not limited to, moving the substrate through a gas curtain to a portion or sector of the processing chamber that is free of, or substantially free of, silicon precursor. In one or more embodiments, purging the processing chamber includes applying a vacuum. In some embodiments, purging the processing chamber includes flowing a purge gas over the substrate. In some embodiments, the portion of the processing chamber refers to a microvolume or small-volume processing station within the processing chamber. The term "adjacent" with reference to the substrate surface refers to the physical space adjacent to the substrate surface that provides sufficient space for surface reactions (such as precursor adsorption) to occur. In one or more embodiments, the purge gas is selected from one or more of nitrogen (N2), helium (He), and argon (Ar).

[0039]

[0047] In operation 116, the substrate (or substrate surface) is exposed to a reactant to form a silicon-containing film on the substrate. The reactant can react with silicon-containing species on the substrate surface to form a silicon-containing film. In some embodiments, the reactant includes a reducing agent. In one or more embodiments, the reducing agent can include any reducing agent known to those of skill in the art. In other embodiments, the reactant includes an oxidizing agent. In one or more embodiments, the oxidizing agent can include any oxidizing agent known to those of skill in the art. In further embodiments, the reactant includes one or more oxidizing agents and a reducing agent.

[0040]

[0048] In certain embodiments, the reactant is selected from one or more of 1,1-dimethylhydrazine (DMH), alkylamines, hydrazine, alkylhydrazine, arylhydrazine, hydrogen (H), ammonia (NH), alcohol, water (H0), oxygen (O), ozone (O), nitrous oxide (NO), nitrogen dioxide (NO), peroxide, and plasmas thereof. In some embodiments, the alkylamine is selected from one or more of tert-butylamine (tBuNH), isopropylamine (iPrNH), ethylamine (CHCHNH), diethylamine ((CHCH)NH), or butylamine (BuNH). In some embodiments, the reactants include one or more compounds having the formula R'NH, R'NH, R'N, R'SiNH, (R'Si)NH, (R'Si)N, where each R' is independently H or an alkyl group having 1 to 12 carbon atoms. In some embodiments, the alkylamine consists essentially of one or more of tert-butylamine (tBuNH), isopropylamine (iPrNH), ethylamine (CHCHNH), diethylamine ((CHCH)NH), or butylamine (BuNH).

[0041]

[0049] In some embodiments, the oxidizing agent comprises an oxaziridine. In some embodiments, the oxaziridine has the general formula:

[0050] TIFF0007730931000004.tif17170

[0051] wherein R1, R2, and R3 are independently selected from H, SO2NO2, CN, C1-C8 alkyl, C1-C8 perfluoroalkyl, pyridine, aryl, substituted aryl, perfluoroaryl, SO2-NO2 substituted aryl, or R2 and R3 combine to form a carbonyl. In some embodiments, R1, R2, and R3 are each independently selected from C1-C6 alkyl, C1-C6 perfluoroalkyl, C1-C4 alkyl, or C1-C6 perfluoroalkyl. Figure 3 shows a non-limiting collection of exemplary oxaziridines.

[0042]

[0052] In some embodiments, R1 is an electron withdrawing group when R2 and R3 are H. In some embodiments, the electron withdrawing group is -CN or -SO2NO2.

[0043]

[0053] In certain embodiments, the oxaziridine comprises one or more of the following:

[0054] TIFF0007730931000005.tif18170.

[0044]

[0055] In some embodiments, the oxaziridine is bicyclic. In some embodiments, the oxaziridine comprises one or more of the following:

[0056] TIFF0007730931000006.tif32170.

[0045]

[0057] In some embodiments, the oxidizer comprises a P / S / N oxide. As used in this regard, "P / S / N oxide" refers to a class of oxides including P-oxides, S-oxides, and N-oxides. In some embodiments, the P / S / N oxide has the general formula:

[0058] TIFF0007730931000007.tif21170

[0059] wherein R4, R5, and R6 are independently selected from H, alkyl, or aryl, and R4 and R5 can be joined to form a 3- to 6-membered ring containing at least one P, S, or N heteroatom. In some embodiments, R4, R5, and R6 are independently selected from C1-C6 alkyl, or C1-C4 alkyl. Figure 4 shows a non-limiting collection of exemplary P / S / N oxides.

[0046]

[0060] In some embodiments, the P / S / N oxide comprises a P-oxide, in some embodiments, the P-oxide comprises one or more of HPO, (CH)PO, (CH)PO, MPPO (3-methyl-1-phenyl-2-phospholene 1-oxide), 3-methyl-1-phenyl-2-phospholene 1-oxide, neopentylene phosphite (5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide), HASPO-1 (4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide), 2-methyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-one, or diphenylphosphine oxide.

[0047]

[0061] In some embodiments, the P / S / N oxides include S-oxides. In some embodiments, the S-oxides include one or more of HSO, or MPSO (methyl phenyl sulfoxide).

[0048]

[0062] In some embodiments, the P / S / N oxide comprises an N-oxide, in some embodiments, the N-oxide comprises one or more of HN→O, trimethylamine n-oxide, pyridine-n-oxide, TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl), N-hydroxyphthalimide, or 4-methylmorpholine n-oxide.

[0049]

[0063] In operation 118, the processing chamber is optionally purged after exposure to the reactants. Purging the processing chamber in operation 118 may be the same process as purging in operation 114, or may be a different process. The processing chamber, a portion of the processing chamber, an area adjacent to the substrate surface, etc., may be purged to remove unreacted reactants, reaction products, and by-products from the area adjacent to the substrate surface.

[0050]

[0064] The thickness of the deposited film or the number of cycles of silicon precursor and reactant is considered in decision 120. Once the deposited film reaches a predetermined thickness or a predetermined number of process cycles have been performed, method 100 proceeds to optional post-treatment operation 130. If the deposited film thickness or number of process cycles has not reached a predetermined threshold, method 100 returns to operation 110 and continues by again exposing the substrate surface to a molybdenum precursor in operation 112.

[0051]

[0065] The optional post-treatment operation 130 may be, for example, a process that alters film properties (e.g., annealing) or a further film deposition process (e.g., an additional ALD or CVD process) to grow an additional film. In some embodiments, the optional post-treatment operation 130 may be a process that alters the properties of the deposited film. In some embodiments, the optional post-treatment operation 130 includes annealing the as-deposited film. In some embodiments, the annealing is performed at a temperature in the range of about 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, or 1000°C. The annealing environment in some embodiments includes one or more of an inert or reducing gas (e.g., molecular nitrogen (N), argon (Ar)) or an oxidizing agent such as, but not limited to, oxygen (O), ozone (O), or a peroxide. The annealing may be performed for any suitable time. In some embodiments, the film is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the as-deposited film increases the film's density, decreases its resistivity, and / or increases its purity. In one or more embodiments, annealing can also be performed using a gas under a plasma. In one or more embodiments, the annealing temperature can be lower using a plasma.

[0052]

[0066] In one or more embodiments, the plasma includes one or more of nitrogen (N), argon (Ar), helium (He), hydrogen (H), carbon monoxide (CO), carbon dioxide (CO), methane (CH), and ammonia (NH). In some embodiments, the plasma is a remote plasma. In other embodiments, the plasma is a direct plasma.

[0053]

[0067] In one or more embodiments, the plasma can be generated remotely or within the processing chamber. In one or more embodiments, the plasma is an inductively coupled plasma (ICP) or a conductively coupled plasma (CCP). Any suitable power can be used, depending, for example, on the reactants and other process conditions. In some embodiments, the plasma is generated at a plasma power ranging from about 10 W to about 3000 W. In some embodiments, the plasma is generated at a plasma power of about 3000 W or less, about 2000 W or less, about 1000 W or less, about 500 W or less, or about 250 W or less.

[0054]

[0068] Method 100 can be performed at any suitable temperature, depending, for example, on the silicon precursor, reactants, or heat budget of the device. In one or more embodiments, the use of high temperature processing may be undesirable for temperature-sensitive substrates, such as logic devices. In some embodiments, exposure to the silicon precursor (operation 112) and exposure to the reactants (operation 116) occurs at the same temperature. In some embodiments, the substrate is maintained at a temperature ranging from about 20°C to about 400°C, or from about 50°C to about 500°C.

[0055]

[0069] In some embodiments, the exposure to the silicon precursor (operation 112) is performed at a different temperature than the exposure to the reactants (operation 116). In some embodiments, the substrate is maintained at a first temperature in the range of about 20°C to about 400°C, or about 50°C to about 500°C, for the exposure to the silicon precursor, and a second temperature in the range of about 20°C to about 400°C, or about 50°C to about 500°C, for the exposure to the reactants.

[0056]

[0070] In the embodiment shown in Figure 1, a substrate (or substrate surface) is sequentially exposed to a silicon precursor and a reactant in a deposition operation 110. In another embodiment, not shown, a substrate (or substrate surface) is simultaneously exposed to a silicon precursor and a reactant in a CVD reaction. In a CVD reaction, a substrate (or substrate surface) can be exposed to a gas mixture of a silicon precursor and a reactant to deposit a silicon-containing film having a predetermined thickness. In a CVD reaction, a silicon-containing film can be deposited in a single exposure to a reactive gas mixture, or multiple exposures to a reactive gas mixture with intervening purges can be used.

[0057]

[0071] In some embodiments, the silicon-containing film formed comprises elemental silicon. In some embodiments, the film consists essentially of silicon. As used in this manner, the term "consisting essentially of silicon" means that the silicon-containing film is greater than or equal to about 80%, 85%, 90%, 95%, 98%, 99%, or 99.5% silicon on an atomic basis. Measurements of the composition of silicon-containing films refer to the bulk of the film, excluding interfacial regions where diffusion of elements from adjacent films may occur.

[0058]

[0072] In other embodiments, the silicon-containing film is silicon oxide (SiO ) having an oxygen content of about 5%, 7.5%, 10%, 12.5, or 15% or more on an atomic basis. x In some embodiments, the silicon-containing film comprises, on an atomic basis, a silicon content in the range of about 1% to about 50%, or about 2% to about 40%, or about 3% to about 30%, or about 4% to about 25%, or about 5% to about 20%.

[0059]

[0073] In other embodiments, the silicon-containing film is silicon nitride (SiN) having a nitrogen content of about 5%, 7.5%, 10%, 12.5, or 15% or more on an atomic basis. x In some embodiments, the silicon-containing film comprises, on an atomic basis, a nitrogen content in the range of about 1% to about 40%, or in the range of about 2% to about 30%, or in the range of about 3% to about 25%, or in the range of about 4% to about 20%.

[0060]

[0074] In other embodiments, the silicon-containing film is silicon carbide (SiC) having a carbide content of about 5%, 7.5%, 10%, 12.5, or 15% or more on an atomic basis. x In some embodiments, the silicon-containing film comprises, on an atomic basis, a carbon content in the range of about 2% to about 30%, or in the range of about 3% to about 25%, or in the range of about 4% to about 20%.

[0061]

[0075] Deposition operation 110 can be repeated to form one or more of a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbide film, or a combination thereof having a predetermined thickness. In some embodiments, deposition operation 110 is repeated to provide one or more of a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbide film, or a combination thereof having a thickness in the range of about 0.3 nm to about 100 nm, or in the range of about 30 Å to about 3000 Å.

[0062]

[0076] According to one or more embodiments, the substrate is subjected to processing before and / or after forming a layer. This processing can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate second chamber for further processing. The substrate can be moved directly from the first chamber to another processing chamber, or from the first chamber to one or more transfer chambers and then to another processing chamber. Thus, the processing apparatus can include multiple chambers in communication with a transfer station. This type of apparatus is sometimes referred to as a "cluster tool" or "cluster system," among other terms.

[0063]

[0077] Generally, a cluster tool is a modular system with multiple chambers that perform various functions, including substrate center detection and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, a cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber can house a robot capable of shuttling substrates between processing chambers and load lock chambers. The transfer chamber is typically maintained under vacuum and provides an intermediate stage for shuttling substrates from one chamber to another and / or to a load lock chamber located at the front end of the cluster tool. Two well-known cluster tools that can be adapted for the present disclosure are the Centura® and Endura®, both available from Applied Materials, Inc. of Santa Clara, California. However, the exact arrangement and combination of chambers may be varied to perform specific steps of the processes described herein. Other processing chambers that can be used include, but are not limited to, cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitridation, degassing, alignment, hydroxylation, and other substrate processing. Performing processing in a cluster tool chamber avoids contamination of the substrate surface from atmospheric impurities without oxidation prior to depositing the next film.

[0064]

[0078] According to one or more embodiments, the substrate is continuously under reduced pressure or "load-lock" conditions and is not exposed to ambient air as it moves from one chamber to the next. Thus, the transfer chamber is under reduced pressure and is "pumped down" under reduced pressure. An inert gas may be present in the processing or transfer chamber. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants (e.g., reactants). According to one or more embodiments, a purge gas is injected into the outlet of the deposition chamber to prevent reactants (e.g., reactants) from moving from the deposition chamber to the transfer chamber and / or additional processing chambers. Thus, the flow of inert gas forms a curtain at the chamber outlet.

[0065]

[0079] Substrates can be processed in a single-substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed in a continuous manner, where multiple substrates are individually loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber, similar to a conveyor system. The shape of the chamber and associated conveyor system can form a linear or curved path. Additionally, the processing chamber can be a carousel, where multiple substrates move around a central axis and are subjected to processes such as deposition, etching, annealing, cleaning, etc., along the entire carousel path.

[0066]

[0080] During processing, the substrate can be heated or cooled. Such heating or cooling can be achieved by any suitable means, including, but not limited to, altering the temperature of the substrate support and flowing heated or cooled gases over the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas used (either a reactive gas or an inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, a heater / cooler is positioned within the chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0067]

[0081] The substrate can be stationary or rotating during processing. A rotating substrate can be rotated (about the substrate axis) sequentially or in discrete steps. For example, the substrate can be rotated throughout the entire process, or the substrate can be rotated only a small amount between exposures to different reactive or purge gases. Rotating the substrate (continuously or in steps) during processing can help minimize the effects of local variations in gas flow profiles, for example, and produce a more uniform deposition or etch.

[0068] Spatially relative terms such as "beneath," "below," "lower," "above," "upper," and the like may be used herein to describe the relationship of one element or feature to another element or feature shown in the figures for ease of description. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, an element described as "below" or "beneath" another element or feature would therefore be oriented "above" the other element or feature. Thus, the exemplary term "below" can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or in other directions) and the spatially relative descriptors used herein interpreted accordingly.

[0069] The use of the terms "a," "an," and "the" and similar referents in the context of describing the materials and methods discussed herein (particularly in the context of the claims below) should be construed to cover both the singular and the plural unless otherwise stated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each individual value falling within the range, unless otherwise stated herein, and each individual value is incorporated into the specification as if set forth individually herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "etc."), provided herein is intended merely to better clarify the materials and methods and does not impose a limitation on scope unless otherwise specified in the claims. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0070]

[0084] References throughout this specification to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of phrases such as "in one or more embodiments," "a particular embodiment," "in an embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the present disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0071]

[0085] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the present disclosure. Therefore, it is intended that the present disclosure cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. exposing a substrate to a cyclic silicon precursor and a reactant, wherein the cyclic silicon precursor comprises a silicon-containing three- or four-membered ring; The cyclic silicon precursor has the following general formula: or wherein X and Y are independently CH ２ , SiH ２ , NH, S, or Se; R １ , R ２ , R ３ and R ４ are independently selected from H or alkyl, and at least one of X or Y is S.

2. the silicon-containing material is silicon nitride; Hydrazine, alkylhydrazine, arylhydrazine, hydrogen (H ２ ), ammonia (NH ３ ), formula R'NH ２ , R' ２ N.H., R' ３ N, R' ２ SiNH ２ , (R' ３ Si) ２ NH and (R' ３ Si) ３ and a reactant selected from the group consisting of N; 2. The method of claim 1, wherein each R' is independently H or an alkyl group having 1 to 12 carbon atoms.

3. The cyclic silicon precursor is The method of claim 1 , comprising:

4. 10. The method of claim 1, wherein the silicon-containing material comprises silicon oxide and the reactant is selected from the group consisting of P / S / N oxides and oxaziridines.

5. 5. The method of claim 4, wherein the silicon oxide comprises greater than 98 atomic percent silicon and oxygen atoms.

6. The oxaziridine has the following general formula: [In the formula, R １ , R ２ and R ３ are independently H, SO ２ NO ２ , CN, C1-C8 alkyl, C1-C8 perfluoroalkyl, pyridine, aryl, substituted aryl, perfluoroaryl, SO ２ -NO ２ substituted aryl, or R ２ and R ３ in combination to form a carbonyl.

7. The oxaziridine is The method of claim 4, comprising one or more of:

8. 5. The method of claim 4, wherein the oxaziridine is bicyclic.

9. The oxaziridine is The method of claim 4, comprising one or more of:

10. The P / S / N oxide has the following general formula: [In the formula, R ４ , R ５ and R ６ is independently selected from H, alkyl, or aryl; R ４ and R ５ can be linked to form a 3-6 membered ring containing at least one P, S, or N heteroatom.

11. The aforementioned But, H ３ PO, (CH ３ ) ３ PO, (CH ２ H ５ ) ３ PO, MPPO (3-methyl-1-phenyl-2-phospholene 1-oxide), 3-methyl-1-phenyl-2-phospholene 1-oxide, neopentylene phosphite (5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide), HASPO-1 (4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide), 2-methyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-one, or diphenylphosphine oxide.

12. The aforementioned But, H ２ 11. The method of claim 10, comprising one or more of SO or MPSO (methyl phenyl sulfoxide).

13. The aforementioned But, H ３ 11. The method of claim 10, comprising one or more of N→O, trimethylamine n-oxide, pyridine-n-oxide, TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl), N-hydroxyphthalimide, or 4-methylmorpholine n-oxide.

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