Substrate processing method for filling one or more gaps on a surface of a substrate

Abstract

A method of filling gaps with a flowable oxide film is provided. In one embodiment of the disclosure, the method includes forming a flowable silicon nitride film and then converting the silicon nitride film to a silicon oxide film. The silicon nitride film can be formed by supplying a power-activated oligomeric silicon source and a nitrogen source. The silicon nitride film can be converted to a silicon oxide film by supplying an oxygen source while applying vacuum UV radiation. The vacuum UV radiation can be applied in a pulsed mode.

Description

[0001] Cross-reference to related applications

[0002] This application is a continuation-in-part of U.S. Application Serial No. 18 / 795,432, entitled "SUBSTRATE PROCESSING METHOD," filed August 6, 2024. Application '432 claims priority to U.S. Provisional Patent Application Serial No. 63 / 531,387, entitled "SUBSTRATE PROCESSING METHOD," filed August 8, 2023, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to a method for filling gaps, and more specifically to a method for filling gaps using a flowable dielectric film for vacuum UV radiation. Background Technology

[0004] Several methods exist for filling gaps with high aspect ratios in the fabrication of microelectronic devices. Conventional PECVD methods form a thick film profile at the top of the gap. Conventional PEALD methods leave a slit or void in the center of the gap because the films grown on the two sidewalls of the gap meet each other, making it easy to leave a slit between them.

[0005] Flowable PECVD methods offer the advantage of not leaving gaps or voids in the membrane. The flowable membrane, filling these gaps, needs to be cured to transform into a solid membrane. For this purpose, annealing at high temperatures or UV radiation in a vapor atmosphere has been utilized. High-temperature annealing is performed at temperatures exceeding 700°C, but this results in an undesirable high thermal budget. With UV radiation in a vapor atmosphere, membrane curing is limited to the surface area, and the membrane transformation is uneven. UV radiation also requires a long curing time to achieve the desired membrane properties, leading to low yields.

[0006] Therefore, a new method is needed to rapidly and uniformly harden flowable membranes at low temperatures. Summary of the Invention

[0007] This disclosure relates to a method for filling gaps, and more specifically to a method for filling gaps using a flowable dielectric film for vacuum UV radiation.

[0008] In one or more embodiments, a method for forming a film on a patterned substrate may include forming a flowable silicon nitride film in a gap at a first temperature, including: supplying a silicon-containing gas and a nitrogen-containing gas to a reaction chamber, and applying power to the reaction chamber and activating the nitrogen-containing gas, wherein the silicon-containing gas can react with the activated nitrogen-containing gas and can form a silicon nitride film; and converting the silicon nitride film into a silicon oxide film at a second temperature, including: supplying an oxygen-containing gas to the reaction chamber and converting the silicon nitride film into a silicon oxide film, wherein vacuum UV radiation may be applied simultaneously with the supply of the oxygen-containing gas.

[0009] In one or more embodiments, vacuum UV radiation may be applied for 10 minutes or less.

[0010] In one or more embodiments, vacuum UV radiation can be applied in a pulsed mode, and the duty cycle of the pulsed mode can be 20% or less.

[0011] In one or more embodiments, the intensity of vacuum UV radiation can be approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0012] In one or more embodiments, the first temperature may be between about 20°C and about 100°C or between about 40°C and about 70°C.

[0013] In one or more embodiments, the second temperature may be between about 70°C and about 150°C or between about 80°C and about 120°C.

[0014] In one or more embodiments, the silicon nitride film may include at least one of SiN, SiCN, or a mixture thereof.

[0015] In one or more embodiments, the silicon-containing gas may include at least one of the following: dimer-trimethylsilylamine, trimer-trimethylsilylamine, tetramer-trimethylsilylamine, pentamer-trimethylsilylamine, hexamer-trimethylsilylamine, heptamer-trimethylsilylamine, octamer-trimethylsilylamine, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,1,3,3-tetramethyldisilazane or mixtures thereof.

[0016] In one or more embodiments, the nitrogen-containing gas may include at least one of NH3, NH4, N2H2, N2H4, or a mixture thereof.

[0017] In one or more embodiments, the silicon oxide film may include at least one of SiO, SiCO, or a mixture thereof.

[0018] In one or more embodiments, the oxygen-containing gas may include at least one of O2, O3, or a mixture thereof.

[0019] After the substrate is transferred from one reaction chamber to another, in which a silicon nitride film can be converted into a silicon oxide film, vacuum UV radiation can be applied in the other reaction chamber while oxygen-containing gas is supplied therein.

[0020] In one or more embodiments, the power is between about 40W and about 200W or in the range between about 50W and about 150W.

[0021] In one or more embodiments, the method may further include performing membrane densification at a third temperature in a reaction chamber different from the reaction chamber for forming and converting the membrane, to densify the silicon oxide membrane, while supplying it with a process gas.

[0022] In one or more embodiments, membrane densification can be performed by at least one of plasma treatment, heat treatment, or a combination thereof.

[0023] In one or more embodiments, the third temperature may be between about 50°C and about 800°C or between about 100°C and about 600°C.

[0024] In one or more embodiments, the processing gas during heat treatment may include at least one of an inert gas, O2, O3, H2O, H2O2, N2, or a mixture thereof.

[0025] In one or more embodiments, the process gas during plasma processing may include at least one of H2, He, or a mixture thereof.

[0026] In one or more embodiments, power between about 300 W and about 700 W can be applied to the reaction chamber during plasma processing.

[0027] In one or more embodiments, a method for filling gaps in a substrate is disclosed. The method may include forming a flowable silicon nitride film in the gap, comprising: supplying a silicon-containing gas and a nitrogen-containing gas to a reaction chamber; applying power to the reaction chamber to activate the nitrogen-containing gas, wherein the silicon-containing gas can react with the activated nitrogen-containing gas to form a silicon nitride film, converting the silicon nitride film into a silicon oxynitride film (SiON), while simultaneously supplying an oxygen-containing gas to the reaction chamber; and applying vacuum UV radiation to the silicon oxynitride film.

[0028] In one or more embodiments, the method can be performed at a temperature of about 70°C or lower.

[0029] In one or more embodiments, the oxygen-containing gas may include ozone (O3).

[0030] In one or more embodiments, the ozone concentration can be approximately 200 g / m³. 3 and approximately 400g / m 3 Within the range between.

[0031] In one or more embodiments, the method may further include heat-treating the silicon oxynitride film or applying power while supplying at least one of Ar, O2, N2, or a mixture thereof.

[0032] In one or more embodiments, the wet etching rate of the silicon oxynitride film can be determined by the ratio of the time for converting the silicon nitride film into a silicon oxynitride film to the time for treating the silicon oxynitride film under vacuum UV radiation.

[0033] In one or more embodiments, at a 1:1 ratio, the wet etching rate of the silicon oxynitride film can be approximately 15 nm / min.

[0034] In one or more embodiments, the power can be in the range of about 10W and about 1000W.

[0035] In one or more embodiments, the intensity of vacuum UV radiation is approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0036] According to one or more embodiments, a method is provided for filling one or more gaps on the surface of a substrate. An exemplary method includes: providing a substrate comprising one or more gaps in a reaction chamber; forming a silicon nitride film in the one or more gaps; providing an oxygen-containing gas to the reaction chamber; performing an H2O2 treatment; and performing a vacuum UV treatment.

[0037] In some embodiments, forming a silicon nitride film includes supplying a silicon-containing gas to a reaction chamber, supplying a nitrogen-containing gas to a reaction chamber, and forming an activating substance containing the nitrogen-containing gas, wherein the silicon-containing gas reacts with the activating substance containing the nitrogen-containing gas to form a silicon nitride film in one or more gaps. In some embodiments, the silicon nitride film comprises at least one of SiN, SiCN, or a mixture thereof. In some embodiments, the silicon-containing gas comprises silylamine or silazane. In some embodiments, the silicon-containing gas comprises at least one of the following: dimer-trimethylsilylamine, trimer-trimethylsilylamine, tetramer-trimethylsilylamine, pentamer-trimethylsilylamine, hexamer-trimethylsilylamine, heptamer-trimethylsilylamine, octamer-trimethylsilylamine, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,1,3,3-tetramethyldisilazane or a mixture thereof. In some embodiments, the nitrogen-containing gas comprises at least one of the following: N2, N2O, NO2, NH3, NH4, N2H2, or N2H4, or mixtures thereof. In some embodiments, the temperature of the reaction chamber during the formation of the silicon nitride film is about 100°C or lower, or between about 20°C and 100°C, or between about 40°C and 70°C. In some embodiments, the formation of the silicon nitride film is a cyclic deposition process. In some embodiments, the step of forming the silicon nitride film is performed multiple times. In some embodiments, one or more of the following steps are performed multiple times: supplying a silicon-containing gas to the reaction chamber, supplying a nitrogen-containing gas to the reaction chamber, and forming an activating material containing the nitrogen gas. In some embodiments, the silicon nitride film is an initial flowable film.

[0038] In some embodiments, providing oxygen-containing gas to the reaction chamber includes converting a silicon nitride membrane into a silicon oxide membrane. In some embodiments, the oxygen-containing gas comprises O2 or O3. In some embodiments, the oxygen-containing gas comprises ozone (O3) and O2, and in some embodiments, the concentration of ozone in the O2 is about 200 g / m³. 3 and approximately 400g / m 3 The temperature of the reaction chamber is between about 70°C and about 150°C, or between about 80°C and about 120°C, during the provision of oxygen-containing gas in some embodiments.

[0039] In some embodiments, performing H2O2 treatment includes supplying H2O2 to the reaction chamber. In some embodiments, performing H2O2 treatment includes supplying a first gas comprising H2O2 and H2O into the reaction chamber, wherein the volume concentration of H2O2 in the first gas is between about 1% and 30%. In some embodiments, the duration of H2O2 treatment is between about 1 minute and 600 minutes, or between about 10 minutes and 360 minutes, or between about 10 minutes and 60 minutes. In some embodiments, the pressure in the reaction chamber during H2O2 treatment is between about 1 Torr and 3800 Torr, or between about 1 Torr and 760 Torr, or between about 1 Torr and 200 Torr, or between about 1 Torr and about 100 Torr. In some embodiments, the temperature in the reaction chamber during H2O2 treatment is between about 0°C and about 1000°C, or between about 50°C and 600°C, or between about 0°C and 300°C, or between about 40°C and 250°C.

[0040] In some embodiments, performing vacuum UV processing includes providing vacuum UV radiation to a substrate. In some embodiments, the vacuum UV radiation comprises a wavelength between about 10 nm and about 200 nm. In some embodiments, the vacuum UV radiation is pulsed. In some embodiments, the duty cycle of the vacuum UV radiation is 20% or less. In some embodiments, the intensity of the vacuum UV radiation is about 80 mW / cm². 2 and approximately 120mW / cm 2 In some embodiments, no oxygen-containing gas is supplied to the reaction chamber during vacuum UV treatment. In some embodiments, the only gas supplied to the reaction chamber during vacuum UV treatment is an inert gas. In some embodiments, one or more of O2 and O3 are supplied to the reaction chamber during vacuum UV treatment.

[0041] In some embodiments, one or more of the following steps are performed multiple times: forming a silicon nitride film, providing oxygen-containing gas, performing H2O2 treatment, and performing vacuum UV treatment. In some embodiments, a first cycle includes the steps of forming a silicon nitride film, providing oxygen-containing gas, performing H2O2 treatment, and performing vacuum UV treatment. In some embodiments, the first cycle is performed multiple times.

[0042] In some embodiments, the method further includes performing a membrane densification step. In some embodiments, the membrane densification step includes one or more of plasma treatment and heat treatment. In some embodiments, plasma treatment includes exposing a substrate to plasma. In some embodiments, the temperature of the reaction chamber during heat treatment is between about 300°C and 1000°C. In some embodiments, the membrane densification step is performed between about 1 Torr and 3800 Torr.

[0043] This synopsis is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the following detailed description of exemplary embodiments of this disclosure. This synopsis is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Attached Figure Description

[0044] Figure 1 A substrate processing method according to an embodiment of the present disclosure is shown.

[0045] Figure 2 A substrate processing method according to another embodiment of the present disclosure is shown.

[0046] Figure 3 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0047] Figure 4 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown.

[0048] Figure 5 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown.

[0049] Figure 6A The molecular structure of the dimer-TSA silicon source is shown.

[0050] Figure 6B The molecular structure of the trimer-TSA silicon source is shown.

[0051] Figure 7 The reaction mechanism of the method according to embodiments of the present disclosure is illustrated.

[0052] Figure 8 The definition of duty cycle is shown.

[0053] Figures 9A to 9E A flowable gap-filling process according to an embodiment of the present disclosure is illustrated.

[0054] Figure 10 The IR (infrared spectral) analysis data showing the membrane composition according to the conversion conditions are shown.

[0055] Figure 11 XPS (X-ray photoelectron spectroscopy) analysis data showing the membrane composition according to an embodiment of the present disclosure are shown.

[0056] Figure 12 The wet etching rate of the SiO film, depending on the heat treatment conditions, is shown.

[0057] Figure 13 The wet etch rate ratio (WERR) of SiO films, depending on the heat treatment conditions, is shown.

[0058] Figure 14 Infrared spectral analysis results showing the bonding structure of SiO films depending on heat treatment conditions at 450°C are presented.

[0059] Figure 15 A substrate processing method according to another embodiment of the present disclosure is shown.

[0060] Figure 16 A timing diagram of a substrate processing method for forming a silicon oxynitride film according to an embodiment of the present disclosure is shown.

[0061] Figure 17 The wet etching rate of silicon oxynitride films is shown based on the ratio of conversion time in ozone (O3) to vacuum UV radiation treatment time.

[0062] Figure 18 Infrared spectral analysis results are shown, illustrating the bonding structure of a silicon oxynitride film formed according to an embodiment of the present disclosure.

[0063] Figure 19 The etching selectivity between silicon oxynitride and silicon oxide films is shown, depending on the etching conditions.

[0064] Figure 20 A scanning electron microscope (SEM) image of a SiON film filling the gaps is shown.

[0065] Figure 21 A substrate processing method according to another embodiment of the present disclosure is shown.

[0066] Figure 22 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0067] Figure 23 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown.

[0068] Figure 24 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown.

[0069] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. Detailed Implementation

[0070] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific embodiments described below.

[0071] As used herein, the term "substrate" can refer to any one or more underlying materials, including any one or more underlying materials that can be modified or on which devices, circuits, or films can be formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. A substrate can be in any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. Substrates can be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0072] The continuous substrate can extend beyond the boundary of the processing chamber where the deposition process takes place. In some processes, the continuous substrate can move through the processing chamber, allowing the process to continue until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate supply system to allow the continuous substrate to be manufactured and output in any suitable form.

[0073] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Unless otherwise stated, expressions such as “at least one of…” modify the entire column of elements when following an element in the column, and not necessarily any individual element in that column.

[0074] As used in this article, the singular forms “a,” “one,” and “the” are intended to include the plural forms as well, unless the context otherwise indicates.

[0075] In some embodiments, "film" refers to a layer extending in a direction perpendicular to the thickness direction. In some embodiments, "layer" refers to a material of a certain thickness formed on a surface, and can be synonymous with a film or non-film structure. A film or layer may consist of discrete single films or layers or multiple films or layers having certain properties, and the boundaries between adjacent films or layers may or may not be clear, and may or may not be based on the physical, chemical and / or any other properties, formation process or sequence and / or function or purpose of adjacent films or layers. A layer or film may be continuous or discontinuous. Furthermore, a single film or layer may be formed using one or more deposition cycles and / or one or more deposition and processing cycles.

[0076] As used herein, the term "structure" can refer to a device structure that is partially or fully fabricated. For example, a structure can be a substrate or a substrate having one or more layers and / or features formed thereon.

[0077] As used herein, the term "cyclic deposition process" or "cyclic deposition process" can refer to a vapor phase deposition process in which deposition cycles (typically multiple consecutive deposition cycles) are performed in a processing chamber. Cyclic deposition processes can include, for example, cyclic chemical vapor deposition (CCVD) and / or atomic layer deposition (ALD) processes.

[0078] In this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any indicated range may include or exclude endpoints. Furthermore, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and includes equivalents, and in some embodiments may refer to an average, median, representative value, or multi-value. Additionally, in this disclosure, the terms “comprising,” “including,” “consisting of,” and “having,” etc., may independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of” in some embodiments. The meaning of any definition in this disclosure does not necessarily exclude the common and customary meanings in some embodiments.

[0079] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0080] The specific embodiments shown and described are illustrative of the invention and its best mode, and are not intended to limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, fabrication, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0081] Figure 1 A substrate processing method according to an embodiment of the present disclosure is shown.

[0082] In step 110 of substrate processing method 100, the substrate may be provided to a reaction chamber. More specifically, the substrate may be loaded onto a base mounted on a heating block. The heating block provides thermal energy to heat the substrate to a processing temperature. The substrate may have semiconductor circuitry including 3D structures and gaps formed thereon. In some embodiments of this disclosure, the depth of the gaps may be 200 nm or less. The reaction chamber may include apparatus for processing the substrate therein. In the reaction chamber, deposition, gap filling, etching, or any other substrate processing process using a gas activation source such as plasma and / or UV may be performed on the substrate.

[0083] In step 120, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source can be supplied to the reaction chamber. The silicon-containing gas may include a free-flowing oligomeric silicon source.

[0084] In step 130, power may be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas can react with the silicon-containing gas to form a flowable silicon nitride film. Steps 120 and 130 may be performed at a first temperature.

[0085] In steps 120 and 130, when the molecular structure of the supplied silicon source is too simple, such as when the silicon source is a monomer or monomolecule, its vapor pressure may be high. Therefore, the silicon source may be prone to volatiles, and thus, the silicon source may lose its fluidity.

[0086] On the other hand, when the molecular structure of the silicon source is complex, its molecular weight is large, resulting in a low vapor pressure and potentially excessively low fluidity. Therefore, process efficiency may decrease in processes requiring flowability exceeding appropriate levels. For example, when a flowable film is used to fill the gaps, insufficient flowability of the film may create voids within the gaps.

[0087] Therefore, as a silicon source used in the exemplary embodiments of this disclosure, an oligomeric silicon source having a molecular structure that is neither overly simple nor overly complex, for example, having 2 to 10 chain structures, can be used. The oligomeric silicon source may comprise, for example, a dimer-trimethylsilylamine (TSA), a trimer-TSA, a tetramer-TSA, a pentamer-TSA, a hexamer-TSA, a heptamerimer-TSA, an octamer-TSA, or another trimethylsilylamine.

[0088] In some embodiments, oligomeric silicon sources can be supplied to the reaction chamber separately, and for example, dimer-TSA as a silicon source can be supplied to the reaction chamber separately, while in other embodiments, trimer-TSA as a silicon source can be supplied to the reaction chamber separately. Additionally, in some embodiments, two or more oligomeric silicon sources can be supplied to the reaction chamber together. For example, in some embodiments, dimer-TSA and trimer-TSA can be supplied simultaneously as silicon sources; in some other embodiments, trimer-TSA and tetramer-TSA can be supplied simultaneously as silicon sources; and in other embodiments, dimer-TSA, trimer-TSA, and tetramer-TSA can be supplied simultaneously to the reaction chamber.

[0089] In some embodiments, the silicon-containing gas may comprise a silazane silicon source. For example, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetramethyldisilazane, or mixtures thereof may be supplied to the reaction chamber as silicon sources.

[0090] On the other hand, the nitrogen-containing gas as a nitrogen source may include at least one of N2, N2O, NO2, NH3, NH4, N2H2, N2H4, or mixtures thereof. The nitrogen source may be supplied at a rate between about 10 sccm and about 100 sccm, or more specifically between about 20 sccm and about 50 sccm. The nitrogen source may be activated by power and may further contain nitrogen-containing free radicals.

[0091] exist Figure 1 In steps 120 and 130, a silicon nitride film can be formed by applying power to the reaction chamber and activating a nitrogen source. The power can be in the range of about 40 W to about 200 W, or more specifically, in the range of about 50 W to about 150 W. The activated nitrogen source can react with a silicon source to form a silicon nitride film. The silicon nitride film may include at least one of SiN, SiCN, or mixtures thereof.

[0092] Silicon nitride films can be formed via an oligomerization and condensation reaction mechanism. An oligomeric silicon source supplied to a substrate can flow on the substrate, and as it flows, bonding can occur between oligomer source molecules to form a structure with at least about 10 chain structures. This is called oligomerization. Oligomerization can be promoted through a condensation reaction between oligomer source molecules. In the condensation reaction, hydrogen atoms can be removed from the Si-H bonds of the silicon source as a reaction byproduct. The oligomers bonded through the condensation reaction can form cross-linked structures while flowing within the fluid silicon nitride film. The reaction mechanism of oligomerization and condensation will be discussed later. Figure 7 A more detailed description is provided below.

[0093] Figure 1 Steps 120 and 130 can be performed at a first temperature that can maintain the fluidity of the silicon source. In some embodiments, steps 120 and 130 can be performed at 100°C or lower, or more specifically between about 30°C and about 70°C.

[0094] In step 140, an oxygen-containing gas, serving as an oxygen source, may be supplied to the reaction chamber. The oxygen source may include at least one of O2, O3, or a mixture thereof. The supplied oxygen source may permeate into the silicon nitride film, causing the silicon nitride film to be converted into a silicon oxide film. The silicon oxide film may include at least one of SiO, SiCO, or a mixture thereof.

[0095] In step 150, vacuum UV radiation can be applied to the silicon nitride film while oxygen-containing gas is continuously supplied, so as to improve the conversion efficiency of becoming a silicon oxide film. Figure 1 Steps 140 and 150 can be performed at a second temperature.

[0096] Vacuum UV is defined as UV radiation occurring in a vacuum or near-vacuum pressure region. Compared to UV radiation with different wavelength ranges, UV radiation in these pressure regions is known to have wavelengths shorter than 200 nm and is strongly absorbed by oxygen molecules. In other words, vacuum UV radiation can strongly excite oxygen sources and induce high-density reactive oxygen species. Therefore, the photoconversion efficiency of oxide films formed in an oxygen atmosphere can be significantly improved, and the stoichiometry of oxide films can be enhanced.

[0097] However, in embodiments of this disclosure, since vacuum UV radiation is applied simultaneously with the supply of oxygen-containing gas, substrate processing is required at low process pressures to ensure that the UV radiation has the wavelength range of vacuum UV. Preferably, the process pressure can be 100 Torr or lower. For example, Figure 1 Steps 140 and 150 can be performed at a pressure of 100 Torr or lower.

[0098] Therefore, using vacuum UV radiation in an oxygen atmosphere can have the technical benefit of further promoting the conversion of silicon nitride films into silicon oxide films. Furthermore, compared to conversion in an O3 atmosphere without vacuum UV, using vacuum UV radiation can reduce oligomerization and condensation times, as shown in Figure 9 and Table 1 below. Thus, substrate processing time (e.g., yield) can be improved.

[0099] On the other hand, when vacuum UV radiation is applied, its intensity can reach approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0100] Steps 140 and 150 for the conversion can be performed at a second temperature. In some embodiments, the second temperature can be between about 70°C and about 150°C, or more specifically between about 80°C and about 120°C.

[0101] In steps 140 and 150, the oxygen-containing gas may be supplied at a flow rate between about 50 sccm and about 3000 sccm, or more specifically at a flow rate between about 100 sccm and about 1500 sccm.

[0102] In another embodiment, after the substrate is transferred to a different reaction chamber than the one in which the silicon nitride film is converted into a silicon oxide film, oxygen-containing gas can be supplied therein while vacuum UV radiation is applied.

[0103] Optionally, vacuum UV radiation can be applied after conversion step 150 to further improve the light conversion efficiency of the oxide film.

[0104] In step 160, it can be checked whether the film has reached the target thickness. Steps 120 to 150 can be performed once or repeated multiple times (M≥1). Then, the substrate processing can end (in step 180).

[0105] Optionally, the film can be further densified 170 to densify the silicon oxide film.

[0106] Membrane densification can be performed by heat treatment. The heat treatment can be performed for about 300 seconds to about 3000 seconds between about 50°C and about 800°C, or more specifically between about 100°C and about 600°C.

[0107] In some embodiments, heat treatment can be performed simultaneously with the supply of the treatment gas. The treatment gas may include at least one of an inert gas, O2, O3, H2O, H2O2, N2, or a mixture thereof. For example, the treatment gas may be supplied at a flow rate between about 200 sccm and about 5000 sccm, more specifically between about 500 sccm and 2000 sccm.

[0108] Processing gases with more oxygen can improve membrane quality. Oligosilicon sources can contain hydrogen, thus creating a hydrogen component in the membrane. Therefore, processing gases with more oxygen can provide a sufficient amount of oxygen to the membrane, leading to the removal of hydrogen from the membrane and improving membrane quality (e.g., membrane purity, wet etching rate, etc.).

[0109] For example, during the membrane densification step 170, at least one of H2O2, O3, or a mixture thereof may be supplied for heat treatment. Therefore, the Si-OH and / or NH bonds in the membrane may decrease, while the Si-O bonds in the membrane may increase. In some embodiments, H2O2 at a concentration of 1 to 10% may be supplied.

[0110] In another embodiment of this disclosure, the heat treatment may be performed in a separate reaction chamber from the one in which film deposition and conversion are carried out.

[0111] In some embodiments, membrane densification can be performed by plasma treatment. Plasma treatment can be performed by applying power while supplying a treatment gas. The treatment gas may include at least one of H2, He, or mixtures thereof, and a power of 300W to 700W may be applied to activate the treatment gas.

[0112] The process gas used for plasma processing can be supplied at a flow rate between about 50 sccm and about 5000 sccm, more specifically between about 500 sccm and about 2000 sccm.

[0113] Plasma treatment can be performed between approximately 50°C and 800°C, or more specifically between approximately 100°C and approximately 600°C. The plasma treatment can be performed in a different reaction chamber than the one used to form the silicon nitride film and convert it into a silicon oxide film.

[0114] In some embodiments, membrane densification can be performed by plasma treatment followed by heat treatment. The plasma treatment and heat treatment can be carried out in situ in the same reaction chamber.

[0115] Figure 2 A substrate processing method according to another embodiment of the present disclosure is shown.

[0116] In step 210, the substrate can be introduced into the reaction chamber.

[0117] In step 220, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source can be supplied to the reaction chamber. The silicon-containing gas may include a free-flowing oligomeric silicon source.

[0118] In step 230, power may be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas can react with the silicon-containing gas to form a flowable silicon nitride film. Steps 220 and 230 may be performed at a first temperature.

[0119] In step 240, an oxygen-containing gas, serving as an oxygen source, may be supplied to the reaction chamber. The oxygen source may include at least one of O2, O3, or a mixture thereof. The supplied oxygen source may permeate into the silicon nitride film, converting at least a portion of the silicon nitride film into a silicon oxide film. The silicon oxide film may include at least one of SiO, SiCO, or a mixture thereof.

[0120] In step 250, vacuum UV radiation can be applied to the silicon nitride film in pulse mode while oxygen-containing gas is continuously supplied to improve the conversion efficiency of becoming a silicon oxide film. Figure 1 Steps 240 and 250 can be performed at a second temperature.

[0121] In step 250, vacuum UV radiation can be applied in pulse mode, which is consistent with... Figure 1 In contrast to step 150, vacuum UV radiation is applied in a continuous mode. In the continuous vacuum UV mode, the surface of the film can be hardened first, and internal transformation within the film can be prevented.

[0122] Conversely, in pulsed vacuum UV mode, the reaction of oxygen molecules in the film with UV light can be further promoted, and the conversion can be more uniform from top to bottom. Therefore, applying vacuum UV in pulsed mode can improve the uniformity of film properties by increasing the depth of the gap.

[0123] As mentioned above, vacuum UV strongly excites oxygen molecules. Therefore, the conversion rate can be faster than when using conventional UV light, resulting in increased yield.

[0124] The duty cycle of the vacuum UV pulse mode can be 20% or less. Figure 8 The definition of duty cycle is shown. Duty cycle is defined as the ratio of b to a. In some embodiments, the duty cycle of the vacuum UV pulse mode can be 5%, where "a" is 60 seconds and "b" is 3 seconds.

[0125] On the other hand, when vacuum UV radiation is applied, its intensity can reach approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0126] Optionally, vacuum UV radiation can be applied after conversion step 250 to further improve the light conversion efficiency of the oxide film.

[0127] In step 260, it can be checked whether the film has reached the target thickness. Steps 220 to 250 can be performed once or repeated multiple times (M≥1). Then, the substrate processing can end (in step 280).

[0128] Optionally, the film can be further densified 270 to densify the silicon oxide film.

[0129] Membrane densification can be performed by heat treatment. The heat treatment can be performed for about 300 seconds to about 3000 seconds between about 50°C and about 800°C, or more specifically between about 100°C and about 600°C. In some embodiments, the heat treatment can be performed simultaneously with the supply of a process gas. The process gas may include at least one of an inert gas, O2, O3, H2O, H2O2, N2, or mixtures thereof. In another embodiment of this disclosure, the heat treatment can be performed in a separate reaction chamber from the reaction chamber where membrane deposition and conversion can be carried out.

[0130] Processing gases with more oxygen can improve membrane quality. Oligosilicon sources can contain hydrogen, thus creating a hydrogen component in the membrane. Therefore, processing gases with more oxygen can provide a sufficient amount of oxygen to the membrane, leading to the removal of hydrogen from the membrane and improving membrane quality (e.g., membrane purity, wet etching rate, etc.).

[0131] For example, during the membrane densification step 270, at least one of H2O2, O3, or a mixture thereof may be supplied for heat treatment. Therefore, the Si-OH and / or NH bonds in the membrane may decrease, while the Si-O bonds in the membrane may increase. In some embodiments, H2O2 at a concentration of 1 to 10% may be supplied.

[0132] In some embodiments, membrane densification can be performed by plasma treatment. Plasma treatment can be performed by applying power while supplying a treatment gas. The treatment gas may include at least one of H2, He, or mixtures thereof, and a power of 300W to 700W may be applied to activate the treatment gas.

[0133] Plasma treatment can be performed between approximately 50°C and 600°C, or more specifically between approximately 100°C and approximately 500°C. The plasma treatment can be performed in a different reaction chamber than the one used to form the silicon nitride film and convert it into a silicon oxide film.

[0134] In some embodiments, membrane densification can be performed by plasma treatment followed by heat treatment. The plasma treatment and heat treatment can be carried out in situ in the same reaction chamber.

[0135] Figure 21 A substrate processing method according to another embodiment of the present disclosure is shown.

[0136] Method 2100 includes the following steps: providing a substrate containing one or more gaps in a reaction chamber (step 2110), forming a silicon nitride film in the one or more gaps (step 2120), providing an oxygen-containing gas (step 2130), performing an H2O2 treatment (step 2140), performing a vacuum UV treatment on the substrate (step 2150), optionally repeating the steps of forming the silicon nitride film, providing the oxygen-containing gas, performing the H2O2 treatment, and performing the vacuum UV treatment multiple times (loop 2160), and performing film densification (step 2170).

[0137] In step 2100, a substrate including one or more gaps may be introduced into the reaction chamber. According to examples of this disclosure, the reaction chamber may form part of a physical vapor deposition (PVD) reactor or a chemical vapor deposition reactor (such as a chemical vapor deposition (CVD) reactor, an atomic layer deposition (ALD) reactor, etc.). Various steps of the methods described herein may be performed in a single reaction chamber or in multiple reaction chambers (e.g., the reaction chamber of a cluster tool).

[0138] During step 2110, the substrate may be brought to a desired temperature and / or the reaction space may be brought to a desired pressure, such as a temperature and / or pressure suitable for subsequent steps. For example, the temperature within the reaction space (e.g., the temperature of the substrate, substrate support, or environment) may be between about 30°C and about 100°C. For example, the pressure within the reaction space may be less than or equal to 20 Torr, or between about 5 Torr and 10 Torr.

[0139] Method 2100 continues to form a silicon nitride film in one or more gaps (step 2120). In some embodiments, forming the silicon nitride film includes supplying a silicon-containing gas to the reaction chamber, supplying a nitrogen-containing gas to the reaction chamber, and forming an activating material containing the nitrogen-containing gas, wherein the silicon-containing gas reacts with the activating material containing the nitrogen-containing gas to form a silicon nitride film in one or more gaps. In some embodiments, the silicon nitride film comprises at least one of SiN, SiCN, or a mixture thereof. In some embodiments, the silicon-containing gas comprises silylamine or silazane. In some embodiments, the silicon-containing gas comprises at least one of the following: dimer-trimethylsilylamine, trimer-trimethylsilylamine, tetramer-trimethylsilylamine, pentamer-trimethylsilylamine, hexamer-trimethylsilylamine, heptamer-trimethylsilylamine, octamer-trimethylsilylamine, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,1,3,3-tetramethyldisilazane or mixtures thereof. In some embodiments, the nitrogen-containing gas comprises at least one of the following: N2, N2O, NO2, NH3, NH4, N2H2 or N2H4 or mixtures thereof. In some embodiments, the temperature of the reaction chamber during the formation of the silicon nitride film is about 100°C or lower, or between about 20°C and 100°C, or between about 40°C and 70°C. In some embodiments, the formation of the silicon nitride film is a cyclic deposition process, such as atomic layer deposition (ALD). In some embodiments, the formation of the silicon nitride film includes a chemical vapor deposition (CVD) process. In some embodiments, the steps of forming the silicon nitride film are performed multiple times. In some embodiments, one or more of the following steps are performed multiple times: supplying a silicon-containing gas to the reaction chamber, supplying a nitrogen-containing gas to the reaction chamber, and forming an activating material containing the nitrogen gas. In some embodiments, the silicon nitride film is an initial flowable film. In some embodiments, step 2120 may be substantially the same as a combination of steps 120 and 130 in method 100 or a combination of steps 220 and 230 in method 200.

[0140] Method 2100 continues by supplying oxygen-containing gas to the reaction chamber (step 2130). In some embodiments, supplying oxygen-containing gas to the reaction chamber includes converting the silicon nitride film into a silicon oxide film. In some embodiments, the oxygen-containing gas comprises O2 or O3. In some embodiments, the oxygen-containing gas comprises ozone (O3) and O2, and in some embodiments, the concentration of ozone in the O2 is about 200 g / m³. 3 and approximately 400g / m 3Within the range between. In some embodiments, the temperature of the reaction chamber during the provision of oxygen-containing gas is between about 70°C and about 150°C, or between about 80°C and about 120°C. In some embodiments, step 2130 may be substantially the same as step 140 in method 100 or step 240 in method 200. In some embodiments, the membrane is exposed to vacuum UV in step 2130.

[0141] Method 2100 continues with the H2O2 treatment (step 2140). In some embodiments, performing the H2O2 treatment includes providing H2O2 to the reaction chamber. In some embodiments, performing the H2O2 treatment includes providing a first gas containing H2O2 and H2O into the reaction chamber. In some embodiments, performing the H2O2 treatment includes providing a first gas containing H2O2 and H2O into the reaction chamber, wherein the volume concentration of H2O2 in the first gas is between about 1% and 30%. In some embodiments, the duration of the H2O2 treatment is between about 1 minute and 600 minutes, or between about 10 minutes and 360 minutes, or between about 10 minutes and 60 minutes. In some embodiments, the pressure in the reaction chamber during the H2O2 treatment is between about 1 Torr and 3800 Torr, or between about 1 Torr and 760 Torr, or between about 1 Torr and 200 Torr, or between about 1 Torr and 100 Torr. In some embodiments, the temperature in the reaction chamber during H2O2 treatment is between about 0°C and about 1000°C, or between about 50°C and 600°C, or between about 0°C and 300°C, or between about 40°C and 250°C. In some embodiments, H2O2 treatment reduces the amount of Si-H bonds in the deposited film.

[0142] Method 2100 continues by performing a vacuum UV treatment on the substrate (step 2150). In some embodiments, performing the vacuum UV treatment includes providing vacuum UV radiation to the substrate. In some embodiments, the vacuum UV radiation includes wavelengths between about 10 nm and about 200 nm. In some embodiments, the vacuum UV radiation is pulsed. In some embodiments, the duty cycle of the UV radiation is 20% or less. In some embodiments, the intensity of the vacuum UV radiation is about 80 mW / cm². 2 and approximately 120mW / cm 2 In some embodiments, one or more of O2 and O3 are supplied to the reaction chamber during the vacuum UV treatment. In some embodiments, no oxygen-containing gas is supplied to the reaction chamber during the vacuum UV treatment. In some embodiments, only an inert gas is supplied to the reaction chamber during the vacuum UV treatment. In some embodiments, the vacuum UV treatment converts the silicon nitride film into a silicon oxide film. In some embodiments, step 2140 may be substantially the same as step 150 in method 100 or step 250 in method 200.

[0143] In some embodiments, the provision of oxygen-containing gas and the performance of vacuum UV treatment overlap at least partially in time. In some embodiments, the provision of oxygen-containing gas begins, and after a period of time, the performance of vacuum UV treatment begins while the supply of oxygen-containing gas continues. In some embodiments, the performance of H2O2 treatment occurs after the provision of oxygen-containing gas.

[0144] Method 2100 may optionally continue to perform the first cycle multiple times. In some embodiments, the first cycle includes one or more of the following steps: forming a silicon nitride film, providing oxygen-containing gas, performing H2O2 treatment, and performing vacuum UV treatment. In some embodiments, the first cycle is performed multiple times. In some embodiments, the first cycle is performed multiple times until the desired thickness is reached. In some embodiments, the first cycle is performed until one or more gaps are filled.

[0145] Method 2100 continues with membrane densification (step 2170). In some embodiments, the membrane densification step includes one or more of plasma treatment and thermal treatment. In some embodiments, plasma treatment includes exposing the substrate to plasma. In some embodiments, the temperature of the reaction chamber during thermal treatment is between about 300°C and 1000°C. In some embodiments, the membrane densification step is performed between about 1 Torr and 3800 Torr. In some embodiments, during the membrane densification step, one or more of an inert gas, N2, H2O2, and H2O are supplied to the reaction chamber. In some embodiments, H2O2 and H2O are supplied to the reaction chamber, wherein the volume concentration of H2O2 relative to H2O is between about 1% and 30%. In some embodiments, step 2170 may be substantially the same as step 170 in method 100 or step 270 in method 200.

[0146] The various steps of the methods described herein can be performed in a single reaction chamber or in multiple reaction chambers (e.g., the reaction chamber of a clustering tool). In some embodiments, methods 100, 200, or 2100 can be performed in a single reaction space. In some embodiments, one or more sub-steps of methods 100, 200, or 2100 can be performed in different reaction spaces or different reaction chambers.

[0147] Additionally, unless otherwise specified, the carrier gas and / or inert gas may co-flow throughout methods 100, 200, or 2100. For example, the carrier gas and / or inert gas may be one or more of helium, argon, or nitrogen.

[0148] Figure 3 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0149] according to Figure 3 The substrate processing method can correspond to Figure 1 Step T1 can correspond to Figure 1 Steps 120 and 130. In step T1, a silicon nitride film can be formed by supplying silicon-containing gas and nitrogen-containing gas and applying RF power to the reaction chamber. Step T1 can be performed for between approximately 10 seconds and approximately 60 seconds.

[0150] Step T2 can correspond to Figure 1 Steps 140 and 150. In step T2, the silicon nitride film can be converted into a silicon oxide film by supplying oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying vacuum UV radiation. As mentioned above, during step T2, the process pressure can be 100 Torr or less to maintain the wavelength of the vacuum UV at 200 nm or less. Therefore, the light conversion efficiency of the vacuum UV can be improved. Step T2 can be performed for between approximately 300 seconds and approximately 1800 seconds.

[0151] On the other hand, when vacuum UV radiation is applied, its intensity can reach approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0152] Steps T1 and T2 can be performed once or repeated multiple times (M≥1). Then, in step T3, heat treatment can optionally be performed, which can harden and densify the silicon oxide film. Step T3 can correspond to... Figure 1 Step 170. Heat treatment can be performed simultaneously with the supply of a processing gas such as an inert gas, O2, O3, H2O, H2O2, and N2, or a mixture thereof. Step T3 can be performed for between approximately 300 seconds and approximately 3000 seconds.

[0153] Figure 4 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0154] according to Figure 4 The substrate processing method can correspond to Figure 2 Step T1' can correspond to Figure 2 Steps 220 and 230. In step T1', a silicon nitride film can be formed by supplying silicon-containing gas and nitrogen-containing gas and applying RF power to the reaction chamber.

[0155] Step T2' can correspond to Figure 2 Steps 240 and 250. In step T2', the silicon nitride film can be converted into a silicon oxide film by supplying oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying vacuum UV radiation. Figure 3 On the contrary, Figure 4 In this process, vacuum UV radiation can be applied in pulsed mode. The duty cycle of the vacuum UV pulsed mode can be 20% or less.

[0156] As mentioned earlier, during step T2', the process pressure can be 100 Torr or lower to maintain the wavelength of vacuum UV radiation at 200 nm or less. Therefore, the light conversion efficiency of vacuum UV radiation can be improved.

[0157] On the other hand, when vacuum UV radiation is applied, its intensity can reach approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0158] Steps T1' and T2' can be performed once or repeated multiple times (M≥1). Then, in step T3', heat treatment can optionally be performed, which can harden and densify the silicon oxide film. Step T3' can correspond to... Figure 2 Step 270. Heat treatment can be performed simultaneously with the supply of the treatment gas. The treatment gas supplied during heat treatment may include at least one of an inert gas, O2, O3, H2O, H2O2, N2, or a mixture thereof. Step T3' can be performed for between approximately 300 seconds and approximately 3000 seconds.

[0159] Figure 5 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown. Figure 5 It can be Figure 3 Another embodiment.

[0160] exist Figure 5 In step T1, a silicon nitride film can be formed by supplying silicon-containing gas and nitrogen-containing gas and applying RF power to the reaction chamber.

[0161] exist Figure 5 In step T2, the silicon nitride film can be converted into a silicon oxide film by supplying oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying vacuum UV radiation. In some embodiments, Figure 5 In step T2, vacuum UV can be supplied in pulse mode.

[0162] exist Figure 5 In step T3, plasma treatment can be performed to densify the silicon oxide film. Plasma treatment can be carried out by applying power while supplying a treatment gas. The treatment gas supplied in step T3 may include at least one of H2, He, or a mixture thereof.

[0163] exist Figure 5 In step T4, heat treatment can be performed to further densify the silicon oxide film. Heat treatment can be performed simultaneously with the supply of the processing gas. The processing gas supplied in step T4 may include at least one of inert gas, O2, O3, H2O, H2O2, N2, or mixtures thereof.

[0164] Figure 22 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0165] according to Figure 22 The substrate processing method can correspond to Figure 21 In some embodiments, T1 corresponds to Figure 21 Step 2120. In some embodiments, T1 includes forming a silicon nitride film. In T1, silicon-containing gas and nitrogen-containing gas are supplied to the reaction chamber, and RF power is applied to the reaction chamber. In some embodiments, the duration of T1 is between about 10 seconds and about 60 seconds.

[0166] In some embodiments, T2 corresponds to Figure 21 Step 2130. In some embodiments, T2 includes supplying oxygen-containing gas to the reaction chamber. In some embodiments, T2 includes converting the silicon nitride film into a silicon oxide film by supplying oxygen-containing gas to the silicon nitride film. In some embodiments, the film is exposed to vacuum UV during T2. In some embodiments, the duration of T2 is between about 300 seconds and about 1800 seconds.

[0167] In some embodiments, T3 corresponds to Figure 21 Step 2140. In some embodiments, T3 includes performing H2O2 treatment by supplying H2O2 to the reaction chamber. In some embodiments, the duration of T3 is between about 1 minute and about 600 minutes, or between about 1 minute and 360 minutes, or between about 10 minutes and 60 minutes.

[0168] In some embodiments, T4 corresponds to Figure 21 Step 2150. In some embodiments, T4 includes applying vacuum UV radiation to the membrane while supplying an inert gas, such as N2 or Ar. In some embodiments, T4 includes converting the silicon nitride membrane into a silicon oxide membrane by supplying an oxygen-containing gas to the silicon nitride membrane and activating the oxygen-containing gas by applying vacuum UV radiation. In some embodiments, no oxygen-containing gas is supplied to the reaction chamber during T4.

[0169] T1, T2, T3, and T4 are executed once or repeated multiple times (M≥1). In some embodiments, T5 corresponds to... Figure 21 Step 2170. In some embodiments, T5 includes performing a membrane densification treatment. Figure 22 In the embodiments depicted, only inert gas is supplied to the reaction chamber during T5. In other embodiments, a process gas comprising one or more of inert gas, O2, O3, H2O, H2O2, and N2 may be supplied to the reaction chamber. In other embodiments, plasma processing may be performed during T5. In some embodiments, the duration of T5 is between about 300 seconds and about 3000 seconds.

[0170] Figure 23 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown. Figure 23 T1', T2', T3', and T5' can be respectively with Figure 22 T1, T2, T3 and T5 are basically the same.

[0171] In some embodiments, T4' corresponds to Figure 21 Step 2150. In some embodiments, T4' includes applying pulsed vacuum UV radiation while supplying an inert gas (e.g., N2, Ar). In some embodiments, T4' includes converting the silicon nitride film into a silicon oxide film by supplying an oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying pulsed vacuum UV radiation. In some embodiments, no oxygen-containing gas is supplied to the reaction chamber during T4'. In some embodiments, the duration of T4 is between about 300 seconds and about 1800 seconds. In some embodiments, the duty cycle of the vacuum UV pulse mode is 20% or less.

[0172] Figure 24 A timing diagram of a substrate processing method according to another embodiment of the present disclosure is shown. Figure 24 T1'', T2'', T3'', and T4'' can be respectively connected with Figure 22 T1, T2, T3 and T4 or Figure 23 T1', T2', T3', and T4' are basically the same. T5b'' can be... Figure 22 T5 or Figure 23 It is basically the same as T5'.

[0173] exist Figure 24 During T5a'', plasma treatment can be performed to densify the silicon oxide film. In some embodiments, plasma treatment is performed by applying RF power while supplying a treatment gas. In some embodiments, the treatment gas supplied during T5a'' includes at least one of H2, He, or a mixture thereof.

[0174] Figure 6A The molecular structure of dimer-TSA is shown, which consists of two chains containing monomer-TSA. Figure 6B The molecular structure of trimer-TSA is shown, which consists of three chains containing monomer-TSA.

[0175] Figure 7 The reaction mechanism of the method according to embodiments of the present disclosure is illustrated.

[0176] exist Figure 7 In the process, the trimer-TSA source flows along the surface of the substrate. Under NH3 plasma conditions, the trimer-TSA source undergoes oligomerization and condensation to form a cross-linked network structure.

[0177] The supply of a nitrogen source can promote crosslinking during the oligomerization process. More specifically, silicon nitride films can contain dangling bonds, such as Si-H (denoted as "A") and NH (denoted as "B"), as... Figure 7 As shown, dangling bonds can lead to micropores within the membrane, resulting in porosity and deterioration of membrane strength. Therefore, the supplied nitrogen source can react with hydrogen atoms to remove them and prevent porosity formation.

[0178] Nitrogen sources can further promote the formation of oligomerization, condensation, and cross-linking network structures between source molecules by removing hydrogen atoms.

[0179] Figures 9A to 9E A flowable gap-filling process according to an embodiment of the present disclosure is illustrated.

[0180] exist Figure 9A In this process, a silicon-containing gas can be supplied to a substrate with gaps. The silicon-containing gas can be fluid, and the source molecules can be neither too simple nor too complex. For example, an oligomeric silicon source with molecules having a chain structure of 2 to 10 can be provided.

[0181] exist Figure 9B In this process, silicon-containing gas can continue to flow along the surface of the substrate, and source molecules can bond together to form chain structures with about 10 chains (this is called oligomerization). The bonding between silicon source molecules can continue, and hydrogen atoms can be removed from the source molecule structure as byproducts, resulting in the enhancement of the chain structure (this is called condensation).

[0182] exist Figure 9B In this process, a nitrogen-containing gas can be supplied separately and activated by applying power. For example, NH3 can be supplied and NH3 plasma can be generated by power. The activated nitrogen source can react with the silicon source to form a flowable silicon nitride film. Furthermore, the nitrogen source can further remove dangling hydrogen atoms from the film, thus further promoting oligomerization and condensation of the film and the formation of cross-linked structures.

[0183] The supply of nitrogen source has another technical benefit: by removing dangling hydrogen, the formation of micropores and voids in the membrane can be prevented. In some embodiments, Figure 9A and Figure 9B These steps can be performed simultaneously.

[0184] exist Figure 9C In this process, oxygen-containing gas can be supplied and the silicon nitride film can be converted. As described above, vacuum UV radiation can be applied to excite the oxygen source. In some embodiments, vacuum UV radiation can be applied in a pulsed mode to achieve uniform conversion across the entire film.

[0185] exist Figure 9DDuring this process, oligomerization and condensation can be enhanced, and cross-linked network structures can be formed. Figures 9A to 9D The steps can be performed once or repeated multiple times.

[0186] exist Figure 9E In the process, heat treatment can be performed to harden and densify the film.

[0187] Figure 10 The IR (infrared spectral) analysis data showing the membrane composition according to the conversion conditions are shown.

[0188] Table 1 shows the following... Figure 10 The three transformation conditions shown are for the formation of a silicon oxide film.

[0189] Table 1—Conversion conditions as shown in Figure 9

[0190]

[0191] As shown in Table 1, under condition A, the silicon nitride film is converted into a silicon oxide film by supplying O3 for 10 minutes followed by heat treatment at 450°C. However, vacuum UV radiation is not applied. Figure 10 In the results, the peaks for condition A show Si-H bonding peaks, Si-O bonding peaks, and Si-N bonding peaks. This means that condition A may lead to insufficient conversion.

[0192] In condition B, the silicon nitride film is converted into a silicon oxide film by providing O3 for 60 minutes followed by heat treatment at 450°C. However, vacuum UV radiation is not applied. Figure 10 In the results, the peaks for condition B show Si-O bonding peaks and weak Si-N bonding peaks, but no Si-H bonding peaks were detected. This means that a longer conversion time may lead to sufficient conversion. However, it may increase substrate processing time.

[0193] In condition C, the silicon nitride film is converted into a silicon oxide film by supplying O3 for 10 minutes followed by heat treatment at 450°C. In condition C, unlike conditions A and B, vacuum UV radiation is applied in pulsed mode. Figure 10 In condition C, the peaks show Si-O bonding peaks and weak Si-N bonding peaks, but no Si-H bonding peaks were detected, similar to condition B. That is, although the duration of vacuum UV irradiation is short (e.g., 10 minutes), it results in sufficient conversion, and the film quality is the same as when the conversion gas is supplied without vacuum UV irradiation for a longer conversion time (e.g., 60 minutes). Therefore, using vacuum UV irradiation in the conversion step has significant technical benefits in reducing substrate processing time without degrading conversion efficiency or reducing film quality.

[0194] Table 2 shows the test conditions for a flowable gap filling process according to embodiments of the present disclosure.

[0195] Table 2—Test conditions for flowable gap filling processes

[0196]

[0197] Figure 11 XPS (X-ray photoelectron spectroscopy) analysis data showing the membrane composition according to an embodiment of the present disclosure are shown.

[0198] exist Figure 11 In an embodiment of this disclosure, while applying vacuum UV radiation, a silicon nitride film is converted into a silicon oxide film by supplying oxygen. For example... Figure 11 As shown, the membrane has a stoichiometric composition, with a Si:O ratio of 1:2 and a carbon and nitrogen content of less than 5%.

[0199] Figure 12 The wet etching rate of the SiO film, depending on the heat treatment conditions, is shown.

[0200] like Figure 12 As shown, the wet etch rate (WER) of the SiO film can be measured under three heat treatment conditions: dry annealing at 450°C, wet annealing at 600°C, and H2O2 annealing, respectively. The wet etch rate can be measured by immersing a substrate coated with the heat-treated SiO film in a 100:1 diluted hydrofluoric acid solution in deionized water (dHF) for 1 minute and measuring the thickness of the etched SiO film. Figure 12 In this context, WER is the average value measured after etching the film three times in dHF solution.

[0201] exist Figure 12 Dry annealing can be performed by supplying N2 at 450°C and 600°C for 30 minutes each. Wet annealing can be performed by supplying H2O (steam) at 450°C and 600°C for 30 minutes each. H2O2 annealing can be performed by supplying H2O2 at 450°C and 600°C for 30 minutes each.

[0202] exist Figure 12 Among the various annealing conditions, the SiO film treated under H2O2 annealing exhibits the lowest wet etching rate, resulting in the formation of the hardest SiO film.

[0203] Figure 13 The wet etch rate ratio (WERR) of SiO films, depending on the heat treatment conditions, is shown. WERR is the ratio of the wet etch rate of the SiO film to the wet etch rate of the SiO film thermally formed at 1000°C.

[0204] exist Figure 13 Among the various annealing conditions, SiO films treated under H2O2 annealing exhibit the lowest wet etch rate ratio, resulting in the formation of the hardest SiO films.

[0205] Figure 14 Infrared spectral analysis results showing the bonding structure of SiO films depending on heat treatment conditions at 450°C are presented.

[0206] like Figure 14 As shown, compared with dry annealing and wet annealing, when H2O2 annealing is performed, the NH peak (at approximately 1150 cm⁻¹) is significantly higher. -1 (at) and Si-OH peak (at approximately 950 cm⁻¹) -1 The lowest intensity was observed at the [location name]. In other words, H2O2 annealing can more effectively remove hydrogen from the film and improve film quality (e.g., film purity, wet etching rate, etc.).

[0207] Figure 15 A substrate processing method according to another embodiment of the present disclosure is shown. Figure 15 The method can be performed at 70°C or lower.

[0208] In step 310 of the substrate processing method 300, the substrate may be provided to a reaction chamber. More specifically, the substrate may be loaded onto a base mounted on a heating block. The heating block provides thermal energy to heat the substrate to a processing temperature. The substrate may have semiconductor circuitry including 3D structures and gaps formed thereon. In some embodiments of this disclosure, the depth of the gaps may be 200 nm or less. The reaction chamber may include apparatus for processing the substrate therein. In the reaction chamber, deposition, gap filling, etching, or any other substrate processing process using a gas activation source such as plasma and / or UV may be performed on the substrate.

[0209] In step 320, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source can be supplied to the reaction chamber. The silicon-containing gas may include a free-flowing oligomeric silicon source.

[0210] The silicon-containing gas may include at least one of the following: dimer-trimethylsilylamine, trimer-trimethylsilylamine, tetramer-trimethylsilylamine, pentamer-trimethylsilylamine, hexamer-trimethylsilylamine, heptamer-trimethylsilylamine, octamer-trimethylsilylamine, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,1,3,3-tetramethyldisilazane or mixtures thereof.

[0211] Nitrogen-containing gases may include at least one of N2, N2O, NO2, NH3, NH4, N2H2, N2H4, or mixtures thereof.

[0212] In step 330, power can be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas can react with the silicon-containing gas to form a flowable silicon nitride (SiN) film. Steps 320 and 330 can be performed simultaneously. The power can be applied in situ or remotely. The power can be in the range of approximately 10 W to approximately 1000 W.

[0213] In step 340, the conversion of the silicon nitride film into a silicon oxynitride film (SiON) can be performed simultaneously with the supply of oxygen-containing gas to the reaction chamber. The oxygen-containing gas may include ozone (O3). The ozone concentration may be approximately 200 g / m³. 3 and approximately 400g / m 3 Within the lower range between.

[0214] In step 350, vacuum UV radiation can be applied to the silicon nitride film while an inert gas (e.g., Ar) is supplied. In step 350, an oxygen-containing gas may not be supplied to prevent the silicon nitride film from completely converting into a silicon oxide film. In other words, the silicon nitride film can be partially converted into a silicon oxide film, resulting in the formation of a silicon oxynitride film.

[0215] Low substrate processing temperatures of approximately 70°C or lower may result in lower ozone activity. Approximately 200 g / m³ 3 and approximately 400g / m 3 The low concentration of ozone in the region can provide less oxygen to the silicon nitride film. Therefore, the silicon nitride film may not be completely converted into a silicon oxide film, resulting in the formation of a silicon oxynitride film.

[0216] As a result, a silicon oxynitride film can be formed. The intensity of vacuum UV radiation can reach approximately 80 mW / cm². 2 and approximately 120mW / cm 2 Within the range between.

[0217] In step 360, it can be checked whether the silicon oxynitride film has reached the target thickness. Steps 320 to 350 can be performed once or repeated multiple times (M≥1). Then, the substrate processing can end (in step 380).

[0218] Optionally, in step 370, the silicon oxynitride film may also be treated to process the silicon oxynitride film (e.g., annealing, densification, etc.). The silicon oxynitride film can be treated by heat treatment or by applying power while supplying at least one of Ar, O2, N2, or a mixture thereof.

[0219] Figure 16 A timing diagram of a substrate processing method for forming a silicon oxynitride film according to an embodiment of the present disclosure is shown. Figure 16 It can correspond to Figure 15 .

[0220] exist Figure 16 In step T1, a silicon nitride film can be formed by supplying silicon-containing gas and nitrogen-containing gas while applying power to the reaction chamber.

[0221] In step T2", the silicon nitride film can be converted into a silicon oxynitride film by supplying oxygen-containing gas. The oxygen-containing gas may include ozone (O3).

[0222] In step T3", vacuum UV radiation can be applied to the silicon oxynitride film. In step T3", oxygen-containing gas may not be supplied to prevent the silicon nitride film from completely converting into a silicon oxide film. Therefore, the silicon nitride film may partially convert into a silicon oxide film. In other words, a silicon oxynitride film can be formed.

[0223] According to embodiments of this disclosure, the wet etching rate of the silicon oxynitride film can be determined by the ratio of the conversion time of the silicon nitride film to the silicon oxynitride film to the vacuum UV radiation treatment time.

[0224] Figure 17 The wet etching rate of silicon oxynitride films is shown based on the ratio of conversion time in ozone (O3) to vacuum UV radiation treatment time. The wet etching can be performed for 180 seconds in a hydrofluoric acid solution diluted 200:1 in deionized water (dHF).

[0225] like Figure 17 As shown, at a 1:1 ratio, the wet etching rate of the silicon oxynitride film can be approximately 15 nm / min. Therefore, the wet etching ratio can be controlled by the ratio between the conversion time and the vacuum UV irradiation time.

[0226] Figure 18 Infrared spectral analysis results are shown, illustrating the bonding structure of the silicon oxynitride film formed according to embodiments of the present disclosure. For example... Figure 18 As shown, the peak of the silicon oxynitride (SiON) film is at approximately 1100 cm⁻¹. -1 It is shown here.

[0227] Figure 19 The etching selectivity between silicon oxynitride and silicon oxide films is shown, depending on the etching conditions.

[0228] exist Figure 19In deionized water (dHF), wet etching can be performed in hydrofluoric acid diluted 200:1 at 20°C for 180 seconds. Dry etching in CF4 can be performed by supplying CF4 etching gas to the reaction chamber while applying 100W of power to the reaction chamber at 60 mTorr and 60°C for 30 seconds. Dry etching in CHF3 can be performed by supplying CHF3 etching gas to the reaction chamber while applying 100W of power to the reaction chamber at 60 mTorr and 60°C for 30 seconds.

[0229] like Figure 19 As shown, under each etching condition, the etching rate exhibits a significant difference between SiON and SiO films. Depending on the etching conditions, the etching rate also shows a significant difference between the same films. That is, embodiments of this disclosure can be applied to substrate processing methods that require high etch selectivity under specific etch conditions. Therefore, for example, selective etching processes can be performed on non-planar surfaces of the substrate.

[0230] Figure 20 A scanning electron microscope (SEM) image of the SiON film filling the gaps is shown. Figure 20 As shown, the gaps can be filled with SiON films without any voids.

[0231] Table 3 shows the test conditions for filling the gaps with a flowable SiON film according to embodiments of the present disclosure.

[0232] Table 3—Test conditions for filling gaps with flowable SiON films

[0233]

[0234] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples herein should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in another order, or in some cases omitted.

[0235] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of various processes, systems and configurations, as well as other features, functions, actions and / or properties disclosed herein and any and all their equivalents.

Claims

1. A method for filling one or more gaps on the surface of a substrate, the method comprising: A substrate including one or more gaps is provided in the reaction chamber; A silicon nitride film is formed in one or more gaps, wherein forming the silicon nitride film includes: Supply silicon-containing gas to the reaction chamber, Nitrogen-containing gas is supplied to the reaction chamber, and An activating material containing nitrogen gas is formed, wherein a silicon-containing gas reacts with the activating material containing nitrogen gas to form a silicon nitride film in one or more gaps; Provide oxygen-containing gas to the reaction chamber; Performing H2O2 treatment includes supplying H2O2 to the reaction chamber; and Performing vacuum UV treatment involves exposing the substrate to vacuum UV radiation. The reaction chamber is maintained at a temperature between approximately 0°C and approximately 300°C during the H2O2 treatment.

2. The method according to claim 1, wherein, The duration of the H2O2 treatment ranges from approximately 1 minute to 600 minutes.

3. The method according to claim 1, wherein, The pressure in the reaction chamber during the H2O2 treatment was between approximately 1 Torr and 3800 Torr.

4. The method according to claim 1, wherein, During the H2O2 treatment, the temperature in the reaction chamber was between approximately 0°C and 300°C.

5. The method according to claim 1, wherein, Performing the H2O2 treatment involves supplying a first gas containing H2O2 and H2O into a reaction chamber, wherein the volume concentration of H2O2 in the first gas is between about 1% and 30%.

6. The method according to claim 1, wherein, The vacuum UV radiation is pulsed.

7. The method according to claim 6, wherein, The duty cycle of the vacuum UV radiation is 20% or less.

8. The method according to claim 1, wherein, The intensity of the vacuum UV radiation is approximately 80 mW / cm². 2 and approximately 120mW / cm 2 between.

9. The method according to claim 1, wherein, The temperature during the formation of the silicon nitride film is approximately 100°C or lower.

10. The method according to claim 1, wherein, The temperature during the supply of the oxygen-containing gas to the reaction chamber is between approximately 70°C and approximately 150°C.

11. The method according to claim 1, wherein, The silicon-containing gas includes dimer-trimethylsilylamine, trimer-trimethylsilylamine, tetramer-trimethylsilylamine, pentamer-trimethylsilylamine, hexamer-trimethylsilylamine, heptamer-trimethylsilylamine, octamer-trimethylsilylamine, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, or 1,1,3,3-tetramethyldisilazane.

12. The method according to claim 1, wherein, The nitrogen-containing gas includes N2, N2O, NO2, NH3, NH4, N2H2, or N2H4.

13. The method according to claim 1, wherein, The oxygen-containing gas includes O2 or O3.

14. The method according to claim 1, wherein, The steps of forming the silicon nitride film, providing the oxygen-containing gas, performing the H2O2 treatment, and performing the vacuum UV treatment are performed multiple times.

15. The method of claim 1, further comprising performing a membrane densification step, wherein, The film densification step includes one or more of plasma treatment and thermal treatment, wherein the plasma treatment includes exposing the substrate to plasma, and wherein the temperature of the reaction chamber during the thermal treatment is between about 300°C and 1000°C.

16. The method according to claim 15, wherein, The film densification step includes exposing the substrate to H2O2.

17. The method according to claim 16, wherein, The membrane densification step is performed between approximately 1 Torr and 3800 Torr.

18. The method according to claim 1, wherein, No oxygen-containing gas is supplied to the reaction chamber during the vacuum UV treatment.

19. The method according to claim 1, wherein, During the step of supplying the oxygen-containing gas to the reaction chamber, the silicon nitride film is converted into a silicon oxide film or a silicon oxynitride film.

20. The method according to claim 1, wherein, The silicon nitride film is an initially flowable film.

21. A method for filling one or more gaps on the surface of a substrate, the method comprising: A substrate comprising one or more gaps on the surface of a substrate is provided within the reaction chamber; The first loop is executed multiple times. The first loop includes: An initial flowable silicon nitride film is formed in one or more gaps. Supply oxygen-containing gas to the reaction chamber. Performing H2O2 treatment includes supplying H2O2 to the reaction chamber, and Performing vacuum UV processing includes exposing the substrate to vacuum UV radiation; and Perform the membrane densification step, The formation of initial flowable silicon nitride includes: Supply silicon-containing gas to the reaction chamber, Nitrogen-containing gas is supplied to the reaction chamber, and Activated substances that form nitrogen-containing gases In this process, a silicon-containing gas reacts with a nitrogen-containing gas to form an initial flowable silicon nitride film in one or more gaps. The membrane densification step includes one or more of plasma treatment and heat treatment. During the heat treatment, the temperature in the reaction chamber is between approximately 300°C and 1000°C. During H2O2 treatment, the reaction chamber is maintained at a temperature between approximately 0°C and 300°C.

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