Methods and systems for forming a layer comprising silicon

Abstract

Methods and systems for forming a silicon-containing layer on a substrate are disclosed. The methods include performing a plurality of deposition cycles. A deposition cycle includes a first precursor pulse including exposing the substrate to a first precursor. The first precursor includes a molecule including a P-Si bond. The deposition cycle also includes a plasma pulse including exposing the substrate to a plasma treatment. The plasma treatment includes generating a plasma.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefits of U.S. Provisional Application No. 63 / 610,434, filed December 15, 2023; U.S. Provisional Application No. 63 / 560,233, filed March 1, 2024; U.S. Provisional Application No. 63 / 560,276, filed March 1, 2024; and U.S. Provisional Application No. 63 / 560,303, filed March 1, 2024, the entire contents of each of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to the field of semiconductor processing methods and systems, and more specifically to the field of integrated circuit manufacturing. In particular, methods and systems suitable for forming silicon-containing layers are disclosed. Background Technology

[0004] As integrated circuits continue to shrink in size and 3D integration becomes a reality, the demand for silicon-containing materials with excellent conformability and improved material properties, such as dielectric constant, resistivity, and wet etch rate tolerance, is increasing. Additionally, there is a growing need for silicon-containing materials that can be formed using low-temperature processes, such as those operating at temperatures up to 400°C, 300°C, or 200°C. For example, conformal silicon nitride (SiN) low-k spacers are required, exhibiting high conformability, low leakage, low dielectric constant, and excellent wet etch rate tolerance.

[0005] Any discussion presented in this paragraph, including discussions of problems and solutions, is included in this disclosure solely for the purpose of providing background information. Such discussion should not be construed as an admission that any or all information was known at the time of making this invention or otherwise constitutes prior art. Summary of the Invention

[0006] This overview is provided to introduce a set of concepts in a simplified form. These concepts are described in more detail below in the exemplary embodiments of this disclosure. This overview 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.

[0007] Various embodiments of this disclosure relate to methods for depositing silicon-containing materials, to structures and devices formed using such methods, and to apparatus for performing these methods and / or for forming such structures and / or devices. These layers can be used in a variety of applications, including etch stop layers, back-end dielectric materials, capping layers, spacers, etc.

[0008] This article describes a method for depositing an amorphous silicon layer on a substrate in a reaction chamber. The method includes providing a first precursor in gaseous form to the reaction chamber, and providing a nitrogen-containing reactive material to the reaction chamber. The first precursor has the general formula:

[0009] PX n (SiR3) 3-n ,

[0010] Where P is phosphorus;

[0011] Si is silicon bonded to phosphorus through Si-P bonds;

[0012] n is an integer with a value of 0, 1, or 2;

[0013] X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; and

[0014] R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl.

[0015] Each of R and X can be independently selected from the above groups.

[0016] In some implementations, the reactive substance is generated by plasma from the reactants.

[0017] In some implementations, the reactive substances include those selected from nitrogen, nitrogen atoms, nitrogen plasma, nitrogen radicals, etc. , and At least one compound of the group consisting of free radicals.

[0018] In some embodiments, the reactive material is generated directly above the substrate. In some embodiments, the reactive material is generated away from the substrate. In some embodiments, a remote plasma generator is used to generate the reactive material.

[0019] In some embodiments, the first precursor is selected from the group consisting of trimethylsilylphosphine, tri(trimethylsilyl)phosphine, silylphosphine, dimethylsilylphosphine, bis(disyl)phosphine, disylphosphine, tri(trisilyl)phosphine, bis(trisilyl)phosphine, trisilylphosphine, dichlorosilylphosphine, dichlorosilylphosphine, bis(disyl)chlorophosphine, disyldichlorophosphine, trisilyldichlorophosphine, bis(trisilyl)chlorophosphine, dimethylsilylphosphine, dimethylsilylmethylphosphine, bis(disyl)methylphosphine, disyldimethylphosphine, trisilyldimethylphosphine, and bis(trisilyl)methylphosphine.

[0020] In some embodiments, the amorphous silicon layer comprises amorphous silicon and nonmetals. In some embodiments, the amorphous silicon layer is selected from the group consisting of silicon nitride, silicon oxide, silicon carbonitride, silicon oxynitride, and silicon oxycarbonitride.

[0021] In some implementations, the silicon-containing layer is formed on a three-dimensional structure.

[0022] In some embodiments, the method further includes a purging step following one or both of the steps of providing the first precursor into the reaction chamber and providing the reactive substance into the reaction chamber.

[0023] This article further describes a method for depositing a silicon-containing layer on a substrate in a reaction chamber, the method comprising:

[0024] The silicon precursor is provided to the reaction chamber in gaseous form;

[0025] The phosphorus precursor is provided to the reaction chamber in gaseous form; and

[0026] Nitrogen-containing reactive substances are supplied to the reaction chamber.

[0027] In some embodiments, the silicon precursor comprises silicon and substituents selected from the group consisting of hydrogen, halogens, and nitrogen-containing substituents. In some embodiments, the nitrogen-containing substituents are selected from the group consisting of amino, alkylamino, and dialkylamino.

[0028] In some embodiments, the silicon precursor is selected from SiH4, Si2H6, Si3H8, cyclopentylsilane, cyclohexylsilane, neopentylsilane, SiH3Cl, SiH2Cl2, SiHCl3, SiCl4, SiH3Br, SiH2Br2, SiHBr3, SiBr4, SiH3I, SiH2I2, SiHI3, SiI4, Si(NMe2)4, SiH(NMe2)3, SiCl(NMe2)3, Si(NH2)(NMe3)3, SiH2(NEt2)2, SiH2(NHtBu)2, SiH3[N(iPr2)], SiH3[N(sBu2)], N(SiH3)3, N(SiMe3)3, NH(SiH3)2, NH(SiMe3)2 The group consists of Si2(NHEt)6, NH[SiH2N(SiH3)2]2, and SiH2[N(SiH3)2]2.

[0029] In some embodiments, the phosphorus precursor comprises phosphorus and a substituent selected from the group consisting of hydrogen, halogen, and nitrogen-containing substituents. In some embodiments, the nitrogen-containing substituent is selected from the group consisting of amino, alkylamino, and dialkylamino.

[0030] In some embodiments, the phosphorus precursor is selected from PH3, tBuPH2, EtPH2, phenylphosphine, 1,2-diphosphineethane, (2-methylpropyl)phosphine, cyclohexylphosphine, and 1,2-diphosphinebenzene, PCl3, PCl5, PBr3, PBr5, PI3, MePCl2, EtPCl2, PrPCl2, iPrPCl2, BuPCl2, tBuPCl2, tBu2PCl, iPr2PCl, Et2PCl, Me2PCl, sBu The group consisting of 2PCl, tBuMePCl, tBu2PBr, P(NMe2)3, PH(NMe2)2, PH2(NMe2), P(NEt2)3, PCl2(NEt2), PCl[N(iPr)2]2, tris(N-pyrrolyl)phosphine, PCl(NEt2)2, PCl2(NMe2), PCl2[N(iPr)2], P(=NH)(NMe2)3, PCl(NMe2)2 and PMe(NMe2)2.

[0031] In some implementations, nitrogen-containing reactive substances include those selected from nitrogen, nitrogen atoms, nitrogen plasma, nitrogen radicals, etc. , and At least one compound of the group consisting of free radicals.

[0032] In some embodiments, the method is performed via a cyclic deposition process. In some embodiments, the method is performed via a thermal atomic layer deposition process. In some embodiments, the method is performed via a thermochemical vapor deposition process. In some embodiments, the method is performed via a plasma-enhanced atomic layer deposition process. In some embodiments, the method is performed via a plasma-enhanced chemical vapor deposition process.

[0033] This paper further describes the deposition of a non-amorphous silicon and non-metallic layers by depositing a precursor having a structure according to the following general formula:

[0034] PX n (SiR3) 3-n ,

[0035] Where P is phosphorus;

[0036] Si is silicon bonded to phosphorus through Si-P bonds;

[0037] n is an integer with a value of 0, 1, or 2; and

[0038] X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; and

[0039] R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl.

[0040] Each of R and X can be independently selected from the above groups.

[0041] This paper further describes the layers formed by the above method.

[0042] In some implementations, the layer contains less than 4 atomic% of phosphorus impurities.

[0043] In some implementations, the layer has a wet etching rate of less than 1.5 nm / min in 1.5% dilute hydrofluoric acid.

[0044] In some implementations, the layer has a growth rate of 0.3 to 2.0 Å / cycle.

[0045] In some implementations, the layer has a step coverage of more than about 80%.

[0046] In some implementations, the layer has a step coverage of more than about 90%.

[0047] This article further describes a composition constructed for deposition layers, the composition comprising a chemical precursor having a structure according to the following general formula:

[0048] PX n (SiR3) 3-n ,

[0049] Where P is phosphorus;

[0050] Si is silicon bonded to phosphorus through Si-P bonds;

[0051] n is an integer with a value of 0, 1, or 2; and

[0052] X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; and

[0053] R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl.

[0054] Each of R and X can be independently selected from the above groups.

[0055] This article further describes a container that contains a chemical precursor having a structure according to the following general formula:

[0056] PX n (SiR3) 3-n ,

[0057] Where P is phosphorus;

[0058] Si is silicon bonded to phosphorus through Si-P bonds;

[0059] n is an integer with a value of 0, 1, or 2; and

[0060] X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; and

[0061] R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl.

[0062] The container is configured to supply vapors of chemical precursors to the chamber of a semiconductor processing device.

[0063] Each of R and X can be independently selected from the above groups.

[0064] This document further describes a semiconductor processing apparatus. The apparatus includes: a reaction chamber including a substrate support for supporting a substrate; a heater configured and arranged to heat the substrate in the reaction chamber; a plasma module including a radio frequency power supply configured and arranged to generate plasma; a plasma gas source in fluid communication with the plasma module; a first precursor source in fluid connection with the reaction chamber via one or more precursor valves; and a controller configured to cause the semiconductor processing apparatus to perform the methods described above.

[0065] This document further describes a semiconductor processing apparatus. The apparatus includes: a reaction chamber including a substrate support for supporting a substrate; a heater configured and arranged to heat the substrate in the reaction chamber; a plasma module including a radio frequency power supply configured and arranged to generate plasma; a plasma gas source in fluid communication with the plasma module; a silicon precursor source in fluid connection with the reaction chamber via one or more precursor valves; a phosphorus precursor source in fluid connection with the reaction chamber via one or more precursor valves; and a controller configured to cause the semiconductor processing apparatus to perform the methods described above.

[0066] These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0067] A more complete understanding of the embodiments of this disclosure can be obtained by referring to the detailed description and claims, and by considering the following illustrative drawings.

[0068] Figure 1 A schematic diagram of an implementation scheme of the system (100) as described herein is shown.

[0069] Figure 2 A schematic diagram of another embodiment of the system (200) as described herein is shown.

[0070] Figure 3 A schematic diagram of another embodiment of the system (300) as described herein is shown.

[0071] Figure 4 This is a schematic diagram of a plasma-enhanced atomic layer deposition (PEALD) apparatus suitable for depositing structures and / or performing methods according to at least one embodiment of this disclosure.

[0072] Figure 5 A schematic diagram of an implementation scheme as described herein is shown.

[0073] Figure 6 A schematic diagram of an implementation scheme as described herein is shown.

[0074] Figure 7 A schematic diagram of a substrate (700) including a gap (710) is shown.

[0075] It should be understood that the components in the figures are for simplicity and clarity only and are not necessarily drawn to scale. For example, the dimensions of some components in the figures may be enlarged relative to other components to help improve the understanding of the illustrated embodiments of this disclosure. Detailed Implementation

[0076] Although certain embodiments and implementations are disclosed below, those skilled in the art will understand that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, as well as obvious modifications and equivalents thereof. Therefore, it is contemplated that the scope of the invention should not be limited to the specific disclosed embodiments described below.

[0077] The descriptions of exemplary embodiments of the methods, structures, apparatuses, and systems provided below are merely illustrative and intended for purposes of explanation only; the following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having the stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise stated, exemplary embodiments or components thereof may be combined or applied separately from each other.

[0078] In this disclosure, depending on the context, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), vaporized solids, and / or vaporized liquids, and can consist of a single gas or a mixture of gases. Gases other than process gases, i.e., gases introduced without passing through gas distribution components, other gas distribution devices, etc., can be used for, for example, sealing a reaction space, and said gas can include sealing gases, such as rare gases. In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, and particularly to a compound constituting the membrane matrix or main framework of the membrane; the term "reactant" is used interchangeably with the term "precursor." Exemplary gases may contain both precursors and reactants.

[0079] As used herein, the term "comprising" indicates the inclusion of certain features, but does not exclude the presence of other features, provided that the features do not render the claims or embodiments unfeasible. In some embodiments, the term "comprising" includes "consisting of". As used herein, the term "consisting of" indicates that no other features exist in the device / method / product besides the features following the wording. When the term "consisting of" is used to refer to a compound or substance, it indicates that the compound contains only the listed components.

[0080] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films can be formed. A substrate may comprise a bulk material, such as silicon (e.g., single-crystal silicon); other Group IV materials, such as germanium; or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials, and may comprise one or more layers covering or beneath the bulk material. Additionally, a substrate may include various features, such as recesses, protrusions, etc., formed within or on at least a portion of the layers of the substrate. As an example, a substrate may comprise a base semiconductor material and an insulating or dielectric material layer covering at least a portion of the base semiconductor material. Alternatively or additionally, an exemplary substrate may comprise a bulk semiconductor material and a conductive layer covering at least a portion of the bulk semiconductor material.

[0081] As used herein, the terms "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers may comprise two-dimensional materials, three-dimensional materials, nanoparticles, partially or entirely molecular layers, or partially or entirely atomic layers, or clusters of atoms and / or molecules. Films or layers may consist partially or entirely of a plurality of dispersed atoms on a substrate surface and / or embedded in a substrate and / or embedded in a device fabricated on said substrate. Films or layers may comprise materials or layers having pinholes and / or island-like portions. Films or layers may be at least partially continuous. Films or layers may be patterned, e.g., subdivided, and may be included in multiple semiconductor devices.

[0082] As used herein, "structure" can be or includes a substrate as described herein. A structure can include one or more layers covering the substrate, such as one or more layers formed according to the methods described herein. Device portions and interconnects can be or include the structure.

[0083] As used herein, the term "deposition process" can refer to the introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate. "Cyclic deposition process" is an example of "deposition process".

[0084] The term “cyclic deposition process” or “cyclical deposition process” can refer to a process in which a substrate is sequentially exposed to precursors (and / or reactants) in a reaction chamber and exposed to plasma-generated material to deposit a layer on the substrate, and includes processing techniques such as plasma-enhanced atomic layer deposition (PEALD).

[0085] The term "plasma-enhanced atomic layer deposition" can refer to a deposition process in which deposition cycles (usually multiple consecutive deposition cycles) are performed in a processing chamber.

[0086] Typically, for the PEALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., the substrate surface may include previously deposited material from a previous PEALD cycle or other materials) and forms a monolayer or sub-monolayer of material that does not readily react with further precursors (i.e., self-limiting reaction). The substrate is then exposed to plasma-generated material, which can be generated using any plasma, such as direct plasma, indirect plasma, or remote plasma. The plasma can be generated capacitively, inductively, using microwave radiation, or otherwise. The plasma-generated material converts the chemisorbed precursor into the desired material on the deposition surface. A purging step may be utilized during one or more cycles (e.g., after each step or pulse of each cycle) to remove any excess precursor from the processing chamber and / or any excess plasma-generated material and / or reaction byproducts from the reaction chamber.

[0087] As used herein, the term "purge" can refer to the process of supplying a purge gas to the reaction chamber between a precursor pulse and a plasma pulse, or between a precursor pulse and a reactant pulse. It should be understood that during purging, the substrate is not exposed to substances generated by the plasma. For example, when using direct plasma, the plasma can be shut off during purging. For example, purging can be provided between a precursor pulse and a reactant pulse, using a purge gas such as nitrogen or an inert gas, thereby avoiding or at least minimizing gas-phase interactions between the precursor and the reactant. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporary purging, the purging steps can be used, for example, in a temporal sequence of supplying a first precursor to the reaction chamber, supplying a purge gas to the reaction chamber, and supplying a second precursor to the reaction chamber, wherein the substrate on which the deposited layer is located is not moved. For example, in the case of spatial purging, the purging steps can take the form of moving the substrate from a first position where the first precursor is continuously supplied via a purge gas curtain to a second position where the second precursor is continuously supplied.

[0088] As used herein, "precursor" includes gases or materials that can be converted into a gaseous state and can be represented as containing elements that can be incorporated during the deposition process described herein.

[0089] The term "nitrogen reactant" can refer to a gas or material that can be converted into a gaseous state and can be represented by a chemical formula including nitrogen. In some cases, the chemical formula includes both nitrogen and hydrogen. In other cases, nitrogen reactants do not include diatomic nitrogen.

[0090] Furthermore, in this disclosure, any two numbers of a variable may constitute a working range of the variable, and any indicated range may include or exclude endpoints. Additionally, any indicated variable value (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and include equivalent values, and may refer to the mean, median, representative value, multi-value, etc. Furthermore, in some embodiments of this disclosure, the terms “comprising,” “consisting of,” and “having” independently mean “generally or broadly comprising,” “including,” “substantially composed of,” or “consisting of.”

[0091] In this disclosure, in some embodiments, any limiting meaning does not necessarily exclude the general and conventional meaning.

[0092] This document describes a method for forming silicon-containing materials on a substrate. A single-crystal silicon wafer can be a suitable substrate. Other substrates can also be suitable, such as single-crystal germanium wafers, gallium arsenide wafers, quartz, sapphire, glass, steel, aluminum, silicon-on-insulator substrates, plastics, etc. The substrate may include a surface layer on which a layer deposited by the method described herein is formed. Suitable surface layers include conductive layers, such as metals or certain nitrides. Suitable nitrides include titanium nitride. Other suitable surface layers include high-k dielectric layers, such as hafnium oxide. In some embodiments, the substrate includes a hydroxyl-terminated surface. In other words, in some embodiments, the substrate contains OH groups on its surface. This can advantageously improve the deposition of silicon-containing layers using the method described herein.

[0093] The method includes positioning a substrate on a substrate support in a reaction chamber. The method then includes performing multiple deposition cycles. Each deposition cycle includes a first precursor pulse and a plasma pulse. The first precursor pulse includes exposing the substrate to a first precursor. The plasma pulse may suitably include exposing the substrate to a plasma process. Thus, a layer comprising amorphous silicon is formed on the substrate.

[0094] It should be understood that the first precursor pulse and the plasma pulse are executed sequentially in a non-overlapping manner, i.e., one after the other. Optionally, a purging process may be performed between the first precursor pulse and the plasma pulse.

[0095] In some implementations, the first precursor pulse and plasma pulse are executed non-sequentially, i.e., the pulses overlap and there is no purge between pulses. Optionally, a purge pulse may be present after the deposition cycle. In other words, one or more deposition cycles comprising a precursor pulse and a plasma pulse may be performed, followed by a purge pulse.

[0096] The layer containing amorphous silicon may be composed of silicon, or may be substantially composed of silicon. In some embodiments, the layer comprises amorphous silicon and nonmetals. In other embodiments, the layer containing amorphous silicon comprises one or more additional elements, such as oxygen, carbon, and nitrogen. Thus, in some embodiments, the layer containing amorphous silicon may comprise one or more of silicon oxide, amorphous silicon, polycrystalline silicon, silicon carbide, silicon nitride, silicon carbide, silicon oxynitride, silicon carbonitride, and silicon oxycarbonitride. In some embodiments, the layer containing amorphous silicon comprises silicon nitride.

[0097] In some implementations, the layer is formed on a three-dimensional structure (such as a trench structure).

[0098] In some implementations, the first precursor has the following general formula:

[0099] PX n (SiR3) 3-n ,

[0100] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer with a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0101] In some embodiments, X is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, amino, dimethylamino, diethylamino, ethylmethylamino, diisopropylamino, tert-butylamino, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0102] In some embodiments, R is hydrogen. In some embodiments, R is a halogen selected from F, Cl, Br, or I. In some embodiments, R is a hydrocarbon group containing one to ten carbon atoms. In some embodiments, R is an alkoxy group containing one to six carbon atoms. In some embodiments, R is silyl, dimethyl, or trimethyl. In some embodiments, the R group is independently selected from the following groups: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, -SiH3, -Si2H5, or -Si3H7.

[0103] In some implementations, the first precursor has a structure according to formula i):

[0104] i),

[0105] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent connected to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups.

[0106] In some embodiments, X is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, amino, dimethylamino, diethylamino, ethylmethylamino, diisopropylamino, tert-butylamino, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0107] In some embodiments, R is hydrogen. In some embodiments, R is a halogen selected from F, Cl, Br, or I. In some embodiments, R is a hydrocarbon group containing one to ten carbon atoms. In some embodiments, R is an alkoxy group containing one to six carbon atoms. In some embodiments, R is silyl, dimethyl, or trimethyl. In some embodiments, the R group is independently selected from the following groups: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, -SiH3, -Si2H5, or -Si3H7.

[0108] In some implementations, the first precursor has a structure according to formula ii):

[0109] ii),

[0110] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0111] In some embodiments, X is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, amino, dimethylamino, diethylamino, ethylmethylamino, diisopropylamino, tert-butylamino, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0112] In some embodiments, R is hydrogen. In some embodiments, R is a halogen selected from F, Cl, Br, or I. In some embodiments, R is a hydrocarbon group containing one to ten carbon atoms. In some embodiments, R is an alkoxy group containing one to six carbon atoms. In some embodiments, R is silyl, dimethyl, or trimethyl. In some embodiments, the R group is independently selected from the following groups: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, -SiH3, -Si2H5, or -Si3H7.

[0113] In some implementations, the first precursor has a structure according to formula iii):

[0114] iii),

[0115] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R is chosen independently.

[0116] In some embodiments, R is hydrogen. In some embodiments, R is a halogen selected from F, Cl, Br, or I. In some embodiments, R is a hydrocarbon group containing one to ten carbon atoms. In some embodiments, R is an alkoxy group containing one to six carbon atoms. In some embodiments, R is silyl, dimethyl, or trimethyl. In some embodiments, the R group is independently selected from the following groups: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, isopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, -SiH3, -Si2H5, or -Si3H7.

[0117] In some embodiments, the first precursor comprises a molecule containing a phosphorus atom bonded to three substituents. At least one substituent contains a silicon atom. Possible other substituents are independently selected from the group consisting of alkyl, halogen, hydrogen, amino, alkoxy, alkyl, and aryl. At least one silicon atom is further bonded to one or more substituents independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, silyl, alkyl, and aryl.

[0118] In some embodiments, the first precursor is selected from the group consisting of trimethylsilylphosphine, tri(trimethylsilyl)phosphine, silylphosphine, dimethylsilylphosphine, bis(disyl)phosphine, disylphosphine, tri(trisilyl)phosphine, bis(trisilyl)phosphine, trisilylphosphine, dichlorosilylphosphine, dichlorosilylphosphine, bis(disyl)chlorophosphine, disyldichlorophosphine, trisilyldichlorophosphine, bis(trisilyl)chlorophosphine, dimethylsilylphosphine, dimethylsilylmethylphosphine, bis(disyl)methylphosphine, disyldimethylphosphine, tri(disyl)phosphine, trisilyldimethylphosphine and bis(trisilyl)methylphosphine.

[0119] The method disclosed herein, using trimethylsilylphosphine as a first precursor, can advantageously enable self-limiting plasma-enhanced atomic layer deposition (PEALD) processes that exhibit self-limiting growth at temperatures up to 500°C. PEALD growth at such high temperatures can form highly etch-resistant silicon-containing layers, with high growth per cycle and high conformability.

[0120] In some embodiments, the methods described herein may be chemical vapor deposition (CVD) or plasma-enhanced chemical vapor deposition (PECVD). In a CVD process, precursors and / or reactants are fed into the reaction chamber at least partially simultaneously.

[0121] In some implementations, the first precursor may be used together with a nitrogen-containing reactive substance in the implementations described herein to form a silicon-containing layer.

[0122] In some implementations, the reactive substance is generated by plasma from the reactants (e.g., nitrogen-containing plasma).

[0123] In some implementations, the first precursor pulse includes a precursor sub-pulse and a precursor sub-purge. The precursor sub-pulse and precursor sub-purge may be repeated a predetermined number of times, for example, at least once and at most ten times, until the precursor pulse ends.

[0124] This article further describes a method for depositing a silicon-containing layer on a substrate in a reaction chamber. The method includes providing a silicon precursor in a gaseous phase to the reaction chamber, providing a phosphorus precursor in a gaseous phase to the reaction chamber, and providing a nitrogen-containing reactive material to the reaction chamber.

[0125] In some embodiments, the silicon precursor comprises silicon and at least one substituent selected from the group consisting of hydrogen, halogens, and nitrogen-containing substituents. In some embodiments, the nitrogen-containing substituent is selected from the group consisting of amino, alkylamino, and dialkylamino. In some embodiments, the silicon precursor is selected from SiH4, Si2H6, Si3H8, cyclopentylsilane, cyclohexylsilane, neopentylsilane, SiH3Cl, SiH2Cl2, SiHCl3, SiCl4, SiH3Br, SiH2Br2, SiHBr3, SiBr4, SiH3I, SiH2I2, SiHI3, SiI4, Si(NMe2)4, SiH(NMe2)3, SiCl(NMe2)3, Si(NH2)(NMe3)3, SiH2(NEt2)2, SiH2(NHtBu)2, SiH3[N(iPr2)], SiH3[N(sBu2)], N(SiH3)3, N(SiMe3)3, NH(SiH3)2, NH(SiMe3)2 The group consists of Si2(NHEt)6, NH[SiH2N(SiH3)2]2, and SiH2[N(SiH3)2]2.

[0126] In some embodiments, the phosphorus precursor comprises phosphorus and substituents selected from the group consisting of hydrogen, halogens, and nitrogen-containing substituents. In some embodiments, the nitrogen-containing substituents are selected from the group consisting of amino, alkylamino, and dialkylamino. In some embodiments, the phosphorus precursor is selected from PH3, t BuPH2, EtPH2, phenylphosphine, 1,2-diphosphine ethane, (2-methylpropyl)phosphine, cyclohexylphosphine and 1,2-diphosphine, PCl3, PCl5, PBr3, PBr5, PI3, MePCl2, EtPCl2, PrPCl2 i PrPCl2, BuPCl2 t BuPCl2, t Bu2PCl、 i Pr2PCl, Et2PCl, Me2PCl s Bu2PCl、 t BuMePCl、 t The group consists of Bu2PBr, P(NMe2)3, PH(NMe2)2, PH2(NMe2), P(NEt2)3, PCl2(NEt2), PCl[N(iPr)2]2, tris(N-pyrrolyl)phosphine, PCl(NEt2)2, PCl2(NMe2), PCl2[N(iPr)2], P(NH)(NMe2)3, PCl(NMe2)2 and PMe(NMe2)2.

[0127] In some implementations, the plasma is a directly capacitively coupled plasma, and the plasma pulse includes a plasma-on sub-pulse and a plasma-off sub-pulse. During the plasma-on sub-pulse, plasma is generated, and during the plasma-off sub-pulse, plasma generation is stopped.

[0128] Plasma pulses may suitably include exposing the substrate to plasma processing. Plasma processing includes generating plasma. The plasma can be a remote plasma, an indirect plasma, or a direct plasma.

[0129] Plasma can be appropriately generated by plasma gas. Plasma gas is a gas, vapor, gas mixture, or combination thereof that is supplied to the space in which plasma is generated. Suitable plasma gases include H2, N2, and inert gases such as He and Ar.

[0130] In some embodiments, the reactive material is generated directly above the substrate. In other words, the plasma is a direct capacitively coupled plasma generated between the spray head ejector and the substrate. In some embodiments, the direct capacitively coupled plasma may employ a plasma power of at least 175 W to at most 300 W or at most 1000 W.

[0131] In some implementations, the reactive substances include those selected from nitrogen, nitrogen atoms, nitrogen plasma, nitrogen radicals, etc. , and At least one compound of the group consisting of free radicals.

[0132] In some embodiments, the reactive substance includes at least one compound selected from the group consisting of oxygen, oxygen radicals, or other oxygen-containing reactive substances.

[0133] In some embodiments, the reactive substances do not include oxygen-containing or nitrogen-containing reactive substances. In some embodiments, the reactive gas includes hydrogen or an inert gas. In some embodiments, the inert gas may include argon.

[0134] In some embodiments, the plasma is N2 plasma. In some embodiments, the plasma is H2 / N2- plasma. In some embodiments, the plasma is ammonia plasma.

[0135] In some embodiments, the reactive material is generated remotely from the substrate. In some embodiments, a remote plasma generator is used to generate the reactive material.

[0136] In some embodiments, the substrate is maintained at a temperature of at least 100°C to at most 600°C, or at least 300°C to at most 500°C, or at least 300°C to at most 400°C, or at about 350°C during the deposition cycle.

[0137] In some embodiments, the method includes introducing a first precursor from a first precursor source into the reaction chamber. The first precursor source may be suitably maintained at a temperature of at least 20°C to at most 200°C, or at least 20°C to at most 100°C, or at least 30°C to at most 80°C, or at least 40°C to at most 60°C, for example, at 50°C.

[0138] In some embodiments, during the deposition process, the reaction chamber is maintained at a pressure of at least 10 Pa to at most 8000 Pa, at least 40 Pa to at most 2000 Pa, or at least 60 Pa to at most 1000 Pa, or at least 300 Pa to at most 3000 Pa, or at least 700 Pa to at most 2000 Pa.

[0139] By performing an appropriate number of deposition cycles, a layer comprising amorphous silicon of desired thickness can be formed on a substrate. The total number of deposition cycles included in the method as described herein depends in particular on the desired total layer thickness. In some embodiments, the method includes at least 2 to at most 5 deposition cycles, or at least 5 to at most 10 deposition cycles, or at least 10 to at most 20 deposition cycles, or at least 20 to at most 50 deposition cycles, or at least 50 to at most 100 deposition cycles, or at least 100 to at most 200 deposition cycles, or at least 200 to at most 500 deposition cycles, or at least 500 to at most 1000 deposition cycles, or at least 1000 to at most 2000 deposition cycles, or at least 2000 to at most 5000 deposition cycles, or at least 5000 to at most 10000 deposition cycles. For example, the layer containing amorphous silicon may have a thickness of at least 1 nm to at most 20 nm, or at least 2 nm to at most 50 nm, such as 2 nm, 5 nm, 10 nm and 15 nm.

[0140] Therefore, silicon-containing materials with a thickness of, for example, 0.3 to 2 angstroms per cycle can be formed.

[0141] In some embodiments, the layer has a growth rate per cycle ranging from 0.3 to 2.0 A / cycle. In some embodiments, the layer has a growth rate per cycle ranging from 0.5 to 1.8 A / cycle. In some embodiments, the layer has a growth rate per cycle ranging from 0.7 to 1.6 A / cycle. In some embodiments, the layer has a growth rate per cycle ranging from 0.9 to 1.4 A / cycle.

[0142] In some embodiments, the layer contains less than 20%, or less than 10%, or less than 5% phosphorus impurities. In some embodiments, the layer contains 0%-5% phosphorus impurities. In some embodiments, the layer contains less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5% phosphorus impurities. In some embodiments, the layer contains 100 ppm to 4% phosphorus impurities. In some embodiments, the layer contains less than 1% phosphorus impurities. In some embodiments, the layer contains less than 1000 ppm phosphorus impurities. In some embodiments, the layer contains no phosphorus impurities. All percentages given in this paragraph are atomic percentages calculated based on the total number of atoms in the deposited layer.

[0143] In some embodiments, the deposited layer has a carbon content of up to 50%. In some embodiments, the carbon content is 0%-35%, or 0%-20%, or 0%-15%, or 0%-10%. In some embodiments, the carbon content is <5%, or <3%, or <2%, or <1%, or 0.5%, or <0.1%. In some embodiments, the carbon content is >1 ppm, or >0.001%, or >0.01%, or 0.1%, or >0.5%. All percentages given in this paragraph are atomic percentages calculated based on the total number of atoms in the deposited layer.

[0144] In some embodiments, the deposited layer has a hydrogen content of 0%-35%, or 0%-20%, or 0%-15%, or 0%-10%. In some embodiments, the hydrogen content is less than 5%. All percentages given in this paragraph are atomic percentages calculated based on the total number of atoms in the deposited layer.

[0145] In some embodiments, the deposited layer has a nitrogen content of 0%-60%, or 0%-50%, or 0%-35%, or 0%-20%, or 0%-15%, or 0%-10%. All percentages given in this paragraph are atomic percentages calculated based on the total number of atoms in the deposited layer.

[0146] In some embodiments, the deposited layer has a silicon content of greater than 95%, or greater than 90%, or greater than 80%, or greater than 70%, or greater than 60%, or greater than 50%, or greater than 40%, or greater than 30%, or greater than 20%. All percentages given in this paragraph are atomic percentages calculated based on the total number of atoms in the deposited layer.

[0147] According to some embodiments, silicon-containing layers with various wet etch rates (WER) can be deposited. When using a full-coverage WER at 0.5% dHF (nm / min), the silicon nitride film can have a WER value of less than about 5, preferably less than about 4, more preferably less than about 2, and most preferably less than about 1. In some embodiments, it can be less than about 0.3.

[0148] In some embodiments, the layer has a wet etching rate of less than 2.5 nm / min in 1.5% dilute hydrofluoric acid.

[0149] In some embodiments, a silicon-containing layer with compressive stress can be deposited. In some embodiments, a silicon-containing layer with tensile stress can be deposited. In some embodiments, the stress is between -2000 MPa and +2000 MPa. In some embodiments, the stress is between -100 MPa and +100 MPa.

[0150] In some embodiments, a silicon-containing layer having an elastic modulus can be deposited. In some embodiments, the elastic modulus is greater than 20 GPa, or greater than 50 GPa, or greater than 100 GPa, or greater than 200 GPa, or greater than 300 GPa.

[0151] In some implementations, the layer has a step coverage of more than about 80%. In some implementations, the layer has a step coverage of more than about 90%.

[0152] In some embodiments, the deposited silicon-containing layer exhibits thickness and compositional inhomogeneity across the three-dimensional structure. In other words, the layer and its composition have different values ​​in all parts or regions of the three-dimensional structure. In some embodiments, the thickness and compositional inhomogeneity are less than 30%, or less than 15%, or less than 10%, or less than 5%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.1%.

[0153] This paper further describes the process of obtaining a layer containing amorphous silicon by depositing a precursor having a structure according to the following general formula:

[0154] PX n (SiR3)3-n ,

[0155] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer with a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0156] This article further describes a composition constructed for deposition layers, the composition comprising a chemical precursor having a structure according to the following general formula:

[0157] PX n (SiR3) 3-n ,

[0158] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer with a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0159] This article further describes a container that contains a chemical precursor having a structure according to the following general formula:

[0160] PX n (SiR3) 3-n ,

[0161] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer with a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0162] On the other hand, a silicon-containing layer is deposited using a thermal atomic layer deposition process. In other words, this process does not involve plasma pulses. In this process, chemical precursors are prepared according to the following general formula:

[0163] PX n (SiR3) 3-n ,

[0164] The precursor is provided in gaseous form to a reaction chamber containing a substrate, and a second precursor is also provided in gaseous form to the reaction chamber. In this general formula, P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer having a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl, and R is a substituent connected to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl. Each R and X is chosen independently.

[0165] In some implementations, a chemical precursor is chemisorbed onto the surface of a substrate. A second precursor then reacts with the chemisorbed chemical precursor.

[0166] In some embodiments, the second precursor is selected from the list consisting of NH3, N(HxRy)3 (where R is methyl, ethyl, or isopropyl, x is 0, 1, or 2, and y is 1, 2, or 3), N2H4, H2O, MX (where M is any metal, and X is a halide), Si(HyXz) (where X is a halide ion, y is 4-z, and z is 1, 2, 3, or 4), and CxHyIz (where if x=1, then y=1, 2, 3, or 4, and z=4-y; or if x=2, then y=1, 2, 3, 4, 5, or 6, and z=6-y; or if x=3, then y=1, 2, 3, 4, 5, 6, 7, or 8, and z=8-y). In some embodiments, the second precursor is selected from the list consisting of CIH3, CI2H2, CI3H, and CI4.

[0167] In some implementations, the process is carried out at temperatures of 100 to 600 °C (such as 300 to 450 °C).

[0168] In some aspects, a process for depositing silicon-containing layers is provided, wherein the process is a plasma-enhanced chemical vapor deposition (PECVD) process. In other words, the first precursor pulse and the plasma pulse are executed non-sequentially, i.e., the pulses overlap and there is no purge between pulses. In some aspects, both the precursor flow and the plasma power are continuously on for an extended period of time, i.e., the process is not a pulsed process.

[0169] In these respects, plasma pulses involve supplying reactant gases into the reaction chamber and simultaneously activating plasma power. Depending on the desired layer, the reactants can be oxygen-containing, nitrogen-containing, or inert gas-containing reactants. If the reactant is oxygen-containing, the deposited film is oxidized and the resulting film is silicon oxide. If the reactant is nitrogen-containing, the deposited film is nitrided and the resulting film is silicon nitride. If the reactant is an inert gas-containing reactant or a reactant containing both inert gas and hydrogen, the deposited film can be amorphous silicon or phosphorus-doped amorphous silicon. In some embodiments, the reactants may also contain carbon. In these embodiments, the resulting film can be silicon carbide or silicon carbonitride.

[0170] In some aspects, a process for depositing a silicon-containing layer is provided, wherein the process is a thermochemical vapor deposition process. In this process, a chemical precursor is provided in gaseous form to a reaction chamber having a substrate. In this process, the chemical precursor is provided according to the following general formula:

[0171] PX n (SiR3) 3-n ,

[0172] Where P is phosphorus, Si is silicon bonded to phosphorus via Si-P bonds, n is an integer with a value of 0, 1, or 2, X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups, and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl groups. Each R and X is chosen independently.

[0173] The deposition process device is heated to above 400 °C. In some embodiments, the temperature during the deposition process is between 400 and 500 °C. In some embodiments, the temperature during the deposition process is between 400 and 600 °C. In some embodiments, a reactive gas is provided to the reaction chamber in a second step. When the desired deposited layer contains silicon and nitrogen, the reactive gas may contain NH3 or H2H4. When the desired deposited layer contains silicon and oxygen, the reactive gas may contain O2, O3, or H2O.

[0174] In some embodiments, layers deposited by any of the processes described above can be used for gap-filling applications. This means providing a substrate with gaps into a reaction chamber. A chemical precursor is deposited into the substrate. A plasma pulse makes the chemical precursor flowable; in other words, it becomes polymeric and fills the gaps in the substrate. This flowability of the precursor enables seamless gap filling.

[0175] In some embodiments, layers deposited by any of the above processes can be used as spacers in a semiconductor structure. In some embodiments, layers deposited by any of the above processes can be used as protective pads, etch stop layers, or spacers in multiple patterning.

[0176] This document further describes a semiconductor processing apparatus. The apparatus includes a reaction chamber. The reaction chamber includes a substrate support for supporting a substrate.

[0177] The system also includes a heater. The heater is configured and arranged to heat the substrate in the reaction chamber.

[0178] The system also includes a plasma module. The plasma module includes a radio frequency power supply configured and arranged to generate plasma. In some embodiments, the plasma module is arranged in a remote plasma configuration, wherein the plasma can be generated outside the reaction chamber, and wherein the plasma-generated active material can be guided to the substrate. In some embodiments, the plasma module is arranged in an indirect plasma configuration, wherein the plasma can be generated in a plasma generation space included within the reaction chamber, the plasma generation space being separated from a substrate-containing space included within the reaction chamber by a conductive mesh or perforated plate, the substrate-containing space comprising the substrate. In some embodiments, the plasma module is arranged in a direct plasma configuration, wherein the plasma is generated within the reaction chamber, and wherein the plasma is not physically isolated from the substrate.

[0179] The system also includes appropriate sources. For example, the system may include a plasma gas source fluidly connected to the plasma module, and a first precursor source fluidly connected to the reaction chamber via one or more precursor valves. Alternatively, instead of including a first precursor source, the system may include a silicon precursor source and a phosphorus precursor source fluidly connected to the reaction chamber via one or more precursor valves.

[0180] The system also includes a controller. This controller is configured to cause the semiconductor processing device to perform the methods described herein.

[0181] Optionally, the system is configured to provide a first precursor, or a silicon precursor and a phosphorus precursor, to the reaction chamber via a carrier gas. Suitable carrier gases include inert gases. In other words, in some embodiments, the semiconductor processing system includes a gas injection system that includes a precursor delivery system that uses a carrier gas to transport the precursor to one or more reaction chambers.

[0182] Figure 1A schematic diagram of an embodiment of the system (100) as described herein is shown. The system (100) includes a reaction chamber (110) in which plasma (120) is generated. Specifically, the plasma (120) is generated between a spray head ejector (130) and a substrate support (140). This is a direct plasma configuration employing capacitively coupled plasma.

[0183] In the illustrated configuration, the system (100) includes two alternating current (AC) power supplies: a high-frequency power supply (121) and a low-frequency power supply (122). In the illustrated configuration, the high-frequency power supply (121) supplies radio frequency (RF) power to the spray head nozzles, and the low-frequency power supply (122) supplies AC signals to the substrate support (140). The RF power can be provided, for example, at a frequency of 13.56 MHz or higher, such as at a frequency of at least 100 kHz to at most 50 MHz, or at a frequency of at least 50 MHz to at most 100 MHz, or at a frequency of at least 100 MHz to at most 200 MHz, or at a frequency of at least 200 MHz to at most 500 MHz, or at a frequency of at least 500 MHz to at most 1000 MHz, or at a frequency of at least 1000 MHz to at most 2000 MHz. Low-frequency alternating current signals may be provided, for example, at a frequency of 2 MHz or lower, such as at a frequency of at least 100 kHz to at most 200 kHz, or at a frequency of at least 200 kHz to at most 500 kHz, or at a frequency of at least 500 kHz to at most 1000 kHz, or at a frequency of at least 1000 kHz to at most 2000 kHz.

[0184] Process gas containing precursors, reactants, or both is supplied to a conical gas distributor (150) via a gas line (160). The process gas then reaches the reaction chamber (110) through orifices (131) in a spray nozzle injector (130).

[0185] Although the high-frequency power supply (121) is shown as electrically connected to the spray head injector and the low-frequency power supply (122) is shown as electrically connected to the substrate support (140), other configurations are possible. For example, in some embodiments (not shown), both the high-frequency and low-frequency power supplies may be electrically connected to the spray head injector; or both the high-frequency and low-frequency power supplies may be electrically connected to the substrate support; or the high-frequency power supply may be electrically connected to the substrate support while the low-frequency power supply may be electrically connected to the spray head injector.

[0186] Figure 2 A schematic diagram of another embodiment of the system (200) as described herein is shown. Figure 2The configuration can be described as an indirect plasma system. The system (200) includes a reaction chamber (210) separated from a plasma generation space (225) in which plasma (220) is generated. Specifically, the reaction chamber (210) is separated from the plasma generation space (225) by a spray nozzle ejector, and the plasma (220) is generated between the spray nozzle ejector (230) and the top plate (226) of the plasma generation space.

[0187] In the illustrated configuration, the system (200) includes three alternating current (AC) power supplies: one high-frequency power supply (221) and two low-frequency power supplies (222, 223): a first low-frequency power supply (222) and a second low-frequency power supply (223). In the illustrated configuration, the high-frequency power supply (221) supplies radio frequency (RF) power to the plasma generation space top plate, the first low-frequency power supply (222) supplies AC signals to the spray head ejectors (230), and the second low-frequency power supply (223) supplies AC signals to the substrate support (240). The substrate (241) is disposed on the substrate support (240). The RF power may be provided, for example, at a frequency of 13.56 MHz or higher. The low-frequency AC signals from the first and second low-frequency power supplies (222, 223) may be provided, for example, at a frequency of 2 MHz or lower.

[0188] Process gases containing precursors, reactants, or both are supplied to the plasma generation space (225) via gas lines (260) passing through the top plate (226) of the plasma generation space. Active substances (such as ions and radicals) generated from the process gases by the plasma (225) reach the reaction chamber (210) through holes (231) in the spray nozzle ejector (230).

[0189] Figure 3 A schematic diagram of another embodiment of the system (300) as described herein is shown. Figure 3 The configuration can be described as a remote plasma system. The system (300) includes a reaction chamber (310) operatively connected to a remote plasma source (325) in which plasma (320) is generated. Any kind of plasma source can be used as the remote plasma source (325), such as inductively coupled plasma, capacitively coupled plasma, or microwave plasma.

[0190] Specifically, the active material is supplied from the plasma source (325) to the reaction chamber (310) via the active material conduit (360), to the conical distributor (350), and through the holes (331) in the spray plate injector (330) to the reaction chamber (310). Thus, the active material can be supplied to the reaction chamber in a uniform manner.

[0191] In the illustrated configuration, the system (300) includes three alternating current (AC) power supplies: one high-frequency power supply (321) and two low-frequency power supplies (822, 823): a first low-frequency power supply (322) and a second low-frequency power supply (323). In the illustrated configuration, the high-frequency power supply (321) supplies radio frequency (RF) power to the plasma generation space top plate, the first low-frequency power supply (322) supplies AC signals to the spray head ejectors (330), and the second low-frequency power supply (323) supplies AC signals to the substrate support (340). The substrate (341) is disposed on the substrate support (340). The RF power may be provided, for example, at a frequency of 13.56 MHz or higher. The low-frequency AC signals of the first and second low-frequency power supplies (322, 323) may be provided, for example, at a frequency of 2 MHz or lower.

[0192] In some implementations (not shown), an additional high-frequency power supply may be electrically connected to the substrate support. This allows direct plasma to be generated within the reaction chamber.

[0193] A process gas containing precursors, reactants, or both is supplied to the plasma source (325) via a gas line (360). Active substances (such as ions and radicals) generated from the process gas by the plasma (325) are directed to the reaction chamber (310).

[0194] The currently provided method can be executed on any suitable device, including, for example, Figure 4 The implementation scheme of the semiconductor processing system shown. Figure 4This is a schematic diagram of a plasma-enhanced atomic layer deposition (PEALD) apparatus that can be used in some embodiments of the present invention. In this diagram, plasma can be generated between the electrodes by providing a pair of parallel, facing conductive planar electrodes (402, 404) inside (411) of the reaction chamber (403), applying RF power (e.g., 13.56 MHz and / or 27 MHz) from a power source (425) to one side, and electrically grounding the other side (412). Of course, the semiconductor processing apparatus does not need to generate plasma during the step of providing the precursor to the reaction chamber, or during purging between subsequent processing steps, and RF power does not need to be applied to either electrode during these steps or purging. A temperature regulator can be disposed in the lower platform (402), i.e., the lower electrode. A substrate (401) is placed on it and its temperature is kept constant at a given temperature. The upper electrode (404) can also be used as a spray plate, and various gases (such as plasma gas, reactant gas and / or dilution gas (if any) and precursor gas) can be introduced into the reaction chamber (403) through gas lines (421) and gas lines (422) and through the spray plate (404). In addition, a circular pipe (413) with an exhaust line (417) is provided in the reaction chamber (403) through which the gas inside the reaction chamber (403) (411) is discharged. Furthermore, a transfer chamber (405) is provided below the reaction chamber (403) and is provided with a gas sealing line (424) to introduce sealing gas into the interior (411) of the reaction chamber (403) through the interior (416) of the transfer chamber (405), wherein a partition plate (414) for separating the reaction zone and the transfer zone is provided.

[0195] Note that the gate valve, which allows the wafer to be transferred into or out of the transfer chamber (405), is omitted from this figure. The transfer chamber is also equipped with an exhaust line (406).

[0196] Figure 5A schematic diagram of an embodiment of the method described herein is shown. The method includes the step (511) of positioning a substrate on a substrate support. The method then includes sequentially performing a plurality of deposition cycles (519). The deposition cycle (519) includes a first precursor pulse (512) and a plasma pulse (516). The first precursor pulse (512) includes exposing the substrate to a first precursor (512). The plasma pulse (516) includes exposing the substrate to an active material generated by the plasma. The active material can be generated using remote, direct, or indirect plasma configurations as explained elsewhere herein. It should be understood that the first precursor pulse (512) and the plasma pulse (516) do not overlap, or substantially do not overlap. In other words, the first precursor pulse (512) and the plasma pulse (516) are performed sequentially. In some embodiments, the first precursor pulse (512) and the plasma pulse (516) overlap at least partially. In some embodiments, the precursor pulse (512) and the plasma pulse (516) are separated by a purge (515, 517). In other words, in some embodiments, a first precursor pulse (512) is followed by a post-precursor purge (515), and a plasma pulse (516) is followed by a post-plasma purge (517). The purge can be accomplished, for example, by exposing the substrate to an inert gas. Exemplary inert gases include He, Ne, Ar, Xe, and Kr. This forms a silicon-containing material on the substrate. The method ends (518) when the desired amount of silicon-containing material has been formed on the substrate.

[0197] Figure 6 A schematic diagram of an embodiment of the method described herein is shown. The method includes the step (611) of positioning a substrate on a substrate support. The method then includes sequentially performing a plurality of deposition cycles (619). The deposition cycle (619) includes a silicon precursor pulse (612), a phosphorus precursor pulse (614), and a plasma pulse (616). It should be understood that each of the pulses can be performed in any order. In other words, the cycle (619) may begin with a silicon precursor pulse (612), followed by a phosphorus precursor pulse (614), and finally a plasma pulse (616). Alternatively, the cycle (619) may begin with a phosphorus pulse (614), followed by a silicon precursor pulse (612), and finally a plasma pulse (616). The cycle may also include a plasma pulse following each precursor pulse. Then, the cycle (61) may begin with a silicon precursor pulse (612), followed by a plasma pulse (616), followed by a phosphorus precursor pulse (614), and finally a second plasma pulse (616). Alternatively, the cycle (619) can begin with a phosphorus pulse (614), followed by a plasma pulse (616), then a silicon precursor pulse (612), and finally a second plasma pulse (616).

[0198] The silicon precursor pulse (612) includes exposing the substrate to the silicon precursor (612). The phosphorus precursor pulse (614) includes exposing the substrate to the phosphorus precursor (614). The plasma pulse (616) includes exposing the substrate to an active material generated by a plasma. The active material can be generated using remote, direct, or indirect plasma configurations as explained elsewhere herein. It should be understood that the silicon precursor pulse (612), phosphorus precursor pulse (614), and plasma pulse (616) do not overlap, or substantially do not overlap. In other words, the silicon precursor pulse (612), phosphorus precursor pulse (614), and plasma pulse (616) are performed sequentially. In some embodiments, the precursor pulses (612, 614) and plasma pulse (616) are separated by a purge (613, 615, 617). In other words, in some embodiments, a silicon precursor pulse (612) is followed by a post-precursor purge (613), a phosphorus precursor pulse (614) by a post-precursor purge (615), and a plasma pulse (616) by a post-plasma purge (617). The purging can be accomplished, for example, by exposing the substrate to an inert gas. Exemplary inert gases include He, Ne, Ar, Xe, and Kr. In some embodiments, the silicon precursor pulse (612), phosphorus precursor pulse (614), and plasma pulse (616) at least partially overlap. This forms a silicon-containing material on the substrate. The method ends (618) when the desired amount of silicon-containing material has been formed on the substrate.

[0199] Figure 7 A schematic diagram of a substrate (700) including a gap (7710) is shown. The gap (710) includes a sidewall (711) and a distal end (712). The substrate also includes a proximal surface (720), i.e., the surface of the substrate outside the gap. In some embodiments, the sidewall (711) and the distal end (712) comprise the same material. In some embodiments, at least one of the sidewall (711) and the distal end (712) comprises a dielectric, such as a silicon-containing dielectric, such as silicon oxide, silicon nitride, silicon carbide, and mixtures thereof. In some embodiments, the dielectric comprises hydrogen. In some embodiments, at least one of the sidewall (711) and the distal end (712) comprises a metal, such as a transition metal, a post-transition metal, and a rare earth metal. In some embodiments, the metal comprises Cu, Co, W, Ru, Mo, Al, or alloys thereof.

[0200] In some embodiments, the sidewall (711) and the distal end (712) have the same or substantially the same composition. In some embodiments, the sidewall (711) and the distal end (712) have different compositions. In some embodiments, the sidewall and the distal end (712) comprise a dielectric. In some embodiments, the sidewall (711) and the distal end (712) comprise a metal. In some embodiments, the sidewall (711) comprises a metal, and the distal end (712) comprises a dielectric. In some embodiments, the sidewall (711) comprises a dielectric, and the distal end comprises a metal.

[0201] In some embodiments, the proximal surface (720) has the same composition as the sidewall (711). In some embodiments, the proximal surface (720) has a different composition than the sidewall (711). In some embodiments, the proximal surface (720) has a different composition than the distal end (712). In some embodiments, the proximal surface (720) has the same composition as the distal end (712).

[0202] In some embodiments, the proximal surface (720), sidewalls (711), and distal end (712) comprise the same material. In some embodiments, the proximal surface (720), sidewalls (711), and distal end (712) comprise a dielectric. In some embodiments, the proximal surface (720), sidewalls (711), and distal end (712) comprise a metal. In some embodiments, the proximal surface (720), sidewalls (711), and distal end (712) comprise a semiconductor.

[0203] In some embodiments, the layer formed according to embodiments of this disclosure has a stepped coverage of at least 90% to at most 110%, or at least 95% to at most 105%, or at least 99% to at most 101%, or about 100% to about 25 in / on structures such as gaps (710) having an aspect ratio (height / width) greater than about 2, about 5, about 10, about 25, about 25, about 50, about 100%, or about 100%. It should be understood that the term "stepped coverage" refers to the growth rate of the layer on the distal end (712) of the recess divided by the growth rate of the layer on the proximal surface (720), expressed as a percentage.

[0204] The descriptions presented herein are not intended as actual views of any particular material, structure, or device, but are merely idealized illustrations used to describe embodiments of this disclosure.

[0205] The specific implementations shown and described are illustrative of the invention and are not intended to limit the scope of aspects and implementations in any way. In fact, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various 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.

[0206] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific implementations or instances should not be considered limitingly, as many variations are possible. The specific 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 may be omitted.

[0207] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various methods, systems, and configurations disclosed herein, as well as other features, functions, actions, and / or characteristics, and any and all equivalents thereof.

Claims

1. A layer comprising amorphous silicon and nonmetals obtained by depositing a precursor having a structure according to the following general formula: PX n (SiR3) 3-n , Where P is phosphorus; Si is silicon bonded to phosphorus through Si-P bonds; n is an integer with a value of 0, 1, or 2; and X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; and R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl; Each X and R is chosen independently.

2. The layer according to claim 1, wherein the layer contains less than 4 atomic% of phosphorus impurities.

3. The layer according to claim 1, wherein the layer has a wet etching rate of less than 1.5 nm / min in 1.5% dilute hydrofluoric acid.

4. The layer according to claim 1, wherein the layer has a growth rate of 0.3 to 2.0 angstroms per cycle.

5. The layer of claim 1, wherein the layer has a step coverage of more than about 80%.

6. The layer of claim 1, wherein the layer has a step coverage of more than about 90%.

7. A method for depositing an amorphous silicon layer on a substrate in a reaction chamber, the method comprising: The substrate is provided into the reaction chamber; The first precursor is provided to the reaction chamber in gaseous form; as well as The reactive substance is provided into the reaction chamber. The first precursor has the general formula: PX n (SiR3) 3-n , Where P is phosphorus; Si is silicon bonded to phosphorus through Si-P bonds; n is an integer with a value of 0, 1, or 2; and X is a substituent bonded to phosphorus, selected from the group consisting of hydrocarbon, halogen, hydrogen, amino, alkoxy, alkyl, and aryl groups; R is a substituent attached to Si, selected from the group consisting of hydrogen, halogen, hydrocarbon, alkoxy, silyl, alkyl, and aryl; Each R and X is chosen independently.

8. The method of claim 7, wherein the reactive substance is generated by reactants via plasma.

9. The method according to claim 7 or 8, wherein the reactive substance comprises a nitrogen atom, nitrogen plasma, nitrogen radical, or nitrogen free radical. , and At least one compound of the group consisting of free radicals.

10. The method according to any one of claims 7 to 9, wherein the reactive substance is generated directly above the substrate.

11. The method according to any one of claims 7 to 9, wherein the reactive substance is generated remotely from the substrate.

12. The method of claim 11, wherein a remote plasma generator is used to generate the reactive material.

13. The method according to any one of claims 7 to 12, wherein the first precursor is selected from the group consisting of tris(trimethylsilyl)phosphine, tris(trimethylsilyl)phosphine, silylphosphine, dis(disyl)phosphine, disylphosphine, tris(trisyl)phosphine, bis(trisyl)phosphine, trisylphosphine, dichlorosilylphosphine, dichlorosilylphosphine, bis(disyl)chlorophosphine, disyldichlorophosphine, trisyldichlorophosphine, bis(trisyl)chlorophosphine, dimethylsilylphosphine, disylmethylphosphine, tris(disyl)phosphine, bis(disyl)methylphosphine, disyldimethylphosphine, trisyldimethylphosphine and bis(trisyl)methylphosphine.

14. The method according to any one of claims 7 to 13, wherein the amorphous silicon layer comprises amorphous silicon and nonmetal.

15. The method of claim 14, wherein the amorphous silicon layer is selected from the group consisting of silicon nitride, silicon oxide, silicon carbonitride, silicon oxynitride, and silicon oxycarbonitride.

16. The method according to any one of claims 7 to 15, wherein the amorphous silicon layer is formed on a three-dimensional structure.

17. The method according to any one of claims 7 to 16, further comprising a purging step after the steps of providing the first precursor and providing the reactive substance.

18. The method according to any one of claims 7 to 17, wherein the method is performed by a cyclic vapor deposition process.

19. The method of claim 18, wherein the method is performed by a plasma-enhanced atomic layer deposition process.

20. A semiconductor processing apparatus, the semiconductor processing apparatus comprising: - A reaction chamber, the reaction chamber including a substrate support for supporting a substrate; - A heater, the heater being constructed and arranged to heat the substrate in the reaction chamber; - A plasma module, the plasma module including a radio frequency power supply configured and arranged to generate plasma; - A plasma gas source, which is in fluid communication with the plasma module; - A first precursor source, which is fluidly connected to the reaction chamber via one or more precursor valves; and - A controller configured to cause the semiconductor processing device to perform the method according to claim 7.

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