Substrate processing method

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to methods of filling gaps, and more particularly, to methods of filling gaps with flowable dielectric films using vacuum UV radiation. Background Art

[0002] In the manufacture of microelectronic devices, there are some methods to fill high aspect ratio gaps. The conventional PECVD method forms a thick film profile in the upper part of the gap. The conventional PEALD method leaves a seam or void in the center part of the gap because the films grown on the two sidewalls of the gap meet each other, making it easy to leave a seam therebetween.

[0003] The flowable PECVD method has the advantage of leaving no seams or gaps in the film. The flowable film filling the gap needs to be hardened in order to be converted into a solid film. For this purpose, high temperature annealing or UV radiation in a steam atmosphere has been used. High temperature annealing is performed above 700°C, but it results in an undesirably high thermal budget. Under UV radiation in a steam atmosphere, the hardening of the film is limited to the surface area and the conversion of the film is not uniform. UV radiation also requires a long curing time (hardening time) to obtain the desired film properties, resulting in low yields.

[0004] Therefore, a new method for rapidly and uniformly hardening flowable films through depth at low temperatures is needed. Summary of the invention

[0005] The present disclosure relates to a method of filling a gap, and more particularly, to a method of filling a gap with a flowable dielectric film using vacuum UV radiation.

[0006] 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, activating the nitrogen-containing gas, wherein the silicon-containing gas can react with the activated nitrogen-containing gas to 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 can be applied while supplying the oxygen-containing gas.

[0007] In one or more embodiments, vacuum UV radiation may be applied for 10 minutes or less.

[0008] In one or more embodiments, the vacuum UV radiation may be applied in a pulse mode, and the duty cycle of the pulse mode may be 20% or less.

[0009] In one or more embodiments, the intensity of vacuum UV radiation may be about 80 mW / cm 2 and about 120mW / cm2 in the range between.

[0010] 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.

[0011] 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.

[0012] In one or more embodiments, the silicon nitride film may include at least one of SiN, SiCN, or a mixture thereof.

[0013] In one or more embodiments, the silicon-containing gas may include at least one of the following: dimer-trisilylamine, trimer-trisilylamine, tetramer-trisilylamine, pentamer-trisilylamine, hexamer-trisilylamine, heptamer-trisilylamine, octamer-trisilylamine, 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.

[0014] In one or more embodiments, the nitrogen-containing gas may include NH 3 NH 4 、N 2 H 2 、N 2 H 4 or at least one of a mixture thereof.

[0015] In one or more embodiments, the silicon oxide film may include at least one of SiO, SiCO, or a mixture thereof.

[0016] In one or more embodiments, the oxygen-containing gas may include O 2 , O 3 or at least one of a mixture thereof.

[0017] After the substrate is transferred from a reaction chamber in which a silicon nitride film may be converted into a silicon oxide film to another reaction chamber, vacuum UV irradiation may be applied in the reaction chamber while supplying an oxygen-containing gas therein.

[0018] In one or more embodiments, the power ranges between about 40W and about 200W or between about 50W and about 150W.

[0019] In one or more embodiments, the method may further include performing film densification at a third temperature in a reaction chamber different from the reaction chamber in which the film is formed and converted to densify the silicon oxide film while supplying a process gas thereto.

[0020] In one or more embodiments, film densification may be performed by at least one of plasma treatment, thermal treatment, or a mixture thereof.

[0021] 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.

[0022] In one or more embodiments, during the thermal treatment, the process gas may include an inert gas, O 2 , O 3 , H 2 O, H 2 O 2 、N 2 or at least one of a mixture thereof.

[0023] In one or more embodiments, during plasma processing, the process gas may include H 2 , He or at least one of a mixture thereof.

[0024] In one or more embodiments, during plasma processing, a power between about 300 W and about 700 W may be applied to the reaction chamber.

[0025] In one or more embodiments, a method for filling a substrate gap is disclosed. The method may include forming a flowable silicon nitride film in the gap, including: supplying a silicon-containing gas and a nitrogen-containing gas to a reaction chamber; and applying power to the reaction chamber to activate the nitrogen-containing gas, wherein the silicon-containing gas may react with the activated nitrogen-containing gas to form a silicon nitride film, while supplying an oxygen-containing gas to the reaction chamber to convert the silicon nitride film into a silicon oxynitride film (SiON); and applying vacuum UV radiation to the silicon oxynitride film.

[0026] In one or more embodiments, the method may be performed at about 70° C. or below.

[0027] In one or more embodiments, the oxygen-containing gas may include ozone (O 3 ).

[0028] In one or more embodiments, the concentration of ozone can be about 200 g / m 3 and about 400g / m 3 in the range between.

[0029] In one or more embodiments, the method may further include heat treating the silicon oxynitride film or applying power while supplying Ar, O 2 、N 2 or at least one of a mixture thereof.

[0030] In one or more embodiments, the wet etching rate of the silicon oxynitride film may be determined by a ratio of a time to convert the silicon nitride film into the silicon oxynitride film and a time to treat the silicon oxynitride film under vacuum UV radiation.

[0031] In one or more embodiments, the wet etching rate of the silicon oxynitride film may be about 15 nm / minute at a ratio of 1:1.

[0032] In one or more embodiments, the power may range between about 10W and about 1000W.

[0033] In one or more embodiments, the intensity of the vacuum UV radiation is about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0034] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 A substrate processing method according to an embodiment of the present disclosure is shown.

[0036] Figure 2 A substrate processing method according to another embodiment of the present invention is shown.

[0037] Figure 3 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0038] Figure 4 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0039] Figure 5 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0040] Fig. 6A The molecular structure of the dimer-TSA silicon source is shown.

[0041] Figure 6B The molecular structure of the trimer-TSA silicon source is shown.

[0042] Figure 7 The reaction mechanism of the method according to an embodiment of the present disclosure is shown.

[0043] Figure 8 The definition of duty cycle is shown.

[0044] 9A to 9EA flowable gap filling process according to an embodiment of the present disclosure is shown.

[0045] Fig.10 IR (infrared spectroscopy) analysis data showing film composition according to conversion conditions are shown.

[0046] Fig.11 XPS (X-ray Photoelectron Spectroscopy) analysis data showing the film constitution according to an example of the present disclosure is shown.

[0047] Fig.12 The wet etching rate of the SiO film depending on the heat treatment conditions is shown.

[0048] Fig.13 The wet etching rate ratio (WERR) of the SiO film depending on the heat treatment conditions is shown.

[0049] Fig.14 Infrared spectrum analysis results showing the bonding structure of the SiO film depending on the heat treatment conditions at 450° C. are shown.

[0050] Fig.15 A substrate processing method according to another embodiment of the present invention is shown.

[0051] Fig.16 A timing diagram of a substrate processing method for forming a silicon oxynitride film according to an embodiment of the present invention is shown.

[0052] Fig.17 The ozone (O 3 ) is the ratio of the conversion time in vacuum to the UV radiation treatment time.

[0053] Fig.18 An infrared spectrum analysis result showing a bonding structure of a silicon oxynitride film formed according to an embodiment of the present invention is shown.

[0054] Fig.19 The etching selectivity between the silicon oxynitride film and the silicon oxide film depending on the etching conditions is shown.

[0055] Fig. 20 A scanning electron microscope (SEM) image of the SiON film filling the gap is shown.

[0056] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0057] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specifically disclosed embodiments described below.

[0058] As used herein, the term "substrate" may refer to any one or more underlying materials, including any one or more underlying materials that may be modified or on which a device, circuit, or film may be formed. A "substrate" may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. A substrate may be in any form, such as a powder, a plate, or a workpiece. A plate-like substrate may include wafers of various shapes and sizes. A substrate may be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0059] The continuous substrate may extend beyond the boundaries of the processing chamber in which the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber so that the process continues until the end of the substrate is reached. The continuous substrate may be provided from a continuous substrate feed system to allow the continuous substrate to be manufactured and output in any suitable form.

[0060] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device but are merely idealized representations used to describe embodiments of the present disclosure.

[0061] The specific embodiments shown and described are illustrations of the present invention and its best mode and are not intended to limit the scope of these aspects and embodiments in any way. In fact, for the sake of brevity, the traditional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, 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 actual systems, and / or may not exist in some embodiments.

[0062] Figure 1 A substrate processing method according to an embodiment of the present disclosure is shown.

[0063] In step 110 of the substrate processing method 100, a substrate may be provided to a reaction chamber. In more detail, the substrate may be loaded onto a pedestal mounted on a heating block. The heating block may provide thermal energy to heat the substrate to a processing temperature. The substrate may have a semiconductor circuit including a 3D structure and a gap formed thereon. In some embodiments of the present disclosure, the depth of the gap may be 200nm or less. The reaction chamber may include equipment for processing the substrate therein. In the reaction chamber, deposition, gap filling, etching, or any other substrate processing process using a gas activation source (e.g., plasma and / or UV) may be performed on the substrate.

[0064] In step 120, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source may be supplied to the reaction chamber. The silicon-containing gas may include an oligomeric silicon source having fluidity.

[0065] In step 130, power may be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas may react with the silicon-containing gas to form a flowable silicon nitride film. Steps 120 and 130 may be performed at a first temperature.

[0066] In steps 120 and 130, when the molecular structure of the supplied silicon source is too simple, for example, when the silicon source is a monomer or a single molecule, its vapor pressure may be high. Therefore, the silicon source may be easily volatilized, and thus the silicon source may lose fluidity.

[0067] On the other hand, when the molecular structure of the silicon source is complex, its molecular weight is large and therefore its vapor pressure is low, so the fluidity of the silicon source may be too low. Therefore, in a process requiring fluidity higher than an appropriate size, the processing efficiency may be reduced. For example, when a flowable film is used to fill a gap and the fluidity of the flowable film is insufficient, voids may appear in the gap.

[0068] Therefore, as the silicon source used in the exemplary embodiment of the present disclosure, an oligomeric silicon source having a molecular structure that is neither too simple nor too complex may be used, for example, having a chain structure of 2 to about 10. The oligomeric silicon source may include, for example, dimer-trisilylamine (TSA), trimer-TSA, tetramer-TSA, pentamer-TSA, hexamer-TSA, heptamer-TSA, octamer-TSA, or another trisilylamine.

[0069] In some embodiments, the oligomeric silicon sources can be supplied to the reaction chamber separately, for example, dimer-TSA as a silicon source can be supplied to the reaction space separately, and in other embodiments, trimer-TSA as a silicon source can be supplied to the reaction chamber separately. In addition, 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 as silicon sources at the same time, in some other embodiments, trimer-TSA and tetramer-TSA can be supplied as silicon sources at the same time, and in other embodiments, dimer-TSA, trimer-TSA and tetramer-TSA can be supplied to the reaction chamber at the same time.

[0070] In some embodiments, the silicon-containing gas may include 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 a mixture thereof may be supplied to the reaction chamber as a silicon source.

[0071] On the other hand, the nitrogen-containing gas as a nitrogen source may include N 2 、N 2 O、NO 2 NH 3 NH 4 、N 2 H 2 、N 2 H 4 Or at least one of a mixture thereof. The nitrogen source may be supplied 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 include nitrogen-containing free radicals.

[0072] exist Figure 1 In steps 120 and 130, a silicon nitride film may be formed by applying power to the reaction chamber and activating a nitrogen source. The power may be in a range between about 40 W and about 200 W, or more specifically between about 50 W and about 150 W. The activated nitrogen source may react with the silicon source and form a silicon nitride film. The silicon nitride film may include at least one of SiN, SiCN, or a mixture thereof.

[0073] The silicon nitride film can be formed by a reaction mechanism of oligomerization and condensation. An oligomeric silicon source supplied to a substrate can flow on the substrate, and while flowing, bonding can occur between the oligomeric source molecules to form a structure having a chain structure of at least about 10. This is called oligomerization. Oligomerization can be promoted by a condensation reaction between the oligomeric 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 by the condensation reaction can form a cross-linked structure by cross-linking while flowing within the silicon nitride film having fluidity. The reaction mechanism of oligomerization and condensation will be described later. Figure 7 Described in more detail in .

[0074] Figure 1 Steps 120 and 130 may be performed at a first temperature, wherein the fluidity of the silicon source may be maintained. In some embodiments, steps 120 and 130 may be performed at 100° C. or less, or more specifically between about 30° C. and about 70° C.

[0075] In step 140, an oxygen-containing gas as an oxygen source may be supplied to the reaction chamber. The oxygen source may include O 2 , O 3 The supplied oxygen source may penetrate 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.

[0076] In step 150, vacuum UV radiation may be applied to the silicon nitride film while continuously supplying an oxygen-containing gas to improve the conversion efficiency of the silicon oxide film. Figure 1 Steps 140 and 150 may be performed at the second temperature.

[0077] Vacuum UV is defined as UV in a vacuum or near-vacuum pressure zone. Compared with UV with a different wavelength range, UV in these pressure zones is known to have a wavelength shorter than 200nm wavelength and is strongly absorbed by oxygen molecules. In other words, vacuum UV radiation can strongly excite oxygen sources and induce a high density of active oxygen. Therefore, the light conversion efficiency entering the oxide film in an oxygen atmosphere can be significantly improved, and the stoichiometry of the oxide film can be improved.

[0078] However, in the embodiment of the present disclosure, since vacuum UV radiation is applied while supplying oxygen-containing gas, it is necessary to perform substrate processing at a low processing pressure so that the UV has a wavelength range of vacuum UV. Preferably, the processing pressure may be 100 Torr or less. For example, Figure 1 Steps 140 and 150 may be performed at a pressure of 100 Torr or less.

[0079] Therefore, the use of vacuum UV radiation in an oxygen atmosphere can have the technical benefit of further promoting the conversion of silicon nitride film into silicon oxide film. 3 Compared to conversion in atmosphere without vacuum UV, the use of vacuum UV radiation can reduce the time for oligomerization and the time for condensation. Therefore, the substrate processing time (eg, throughput) can be improved.

[0080] On the other hand, when vacuum UV radiation is applied, its intensity can be about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0081] Steps 140 and 150 for converting 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.

[0082] 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, between about 100 sccm and about 1500 sccm.

[0083] In another embodiment, after the substrate is transferred to the reaction chamber, vacuum UV radiation may be applied in a reaction chamber different from the reaction chamber in which the silicon nitride film is converted into the silicon oxide film while supplying an oxygen-containing gas therein.

[0084] Optionally, vacuum UV radiation may be applied after the conversion step 150 to further improve the light conversion efficiency to the oxide film.

[0085] In step 160, it may be checked whether the film reaches the target thickness. Steps from 120 to 150 may be performed once or repeated multiple times (M≥1). Then, the substrate treatment process may end (in step 180).

[0086] Optionally, film densification 170 may be further performed to densify the silicon oxide film.

[0087] The film densification may be performed by heat treatment. The heat treatment may be performed between about 50° C. and about 800° C., or more specifically between about 100° C. and about 600° C., for about 300 seconds to about 3000 seconds.

[0088] In some embodiments, the heat treatment may be performed while supplying a process gas. The process gas may include an inert gas, 2 , O 3 , H 2 O, H 2 O 2 、N 2 For example, the process gas may be supplied at a flow rate between about 200 sccm and about 5000 sccm, more specifically, between about 500 sccm and about 2000 sccm.

[0089] A process gas with more oxygen can improve film quality. The oligomeric silicon source can contain hydrogen, resulting in a hydrogen component in the film. Therefore, a process gas with more oxygen can provide a sufficient amount of oxygen to the film, thereby removing hydrogen from the film and improving film quality (e.g., film purity, wet etch rate, etc.).

[0090] For example, during the film densification step 170, H may be supplied. 2 O 2 , O 3 or a mixture thereof for heat treatment. Thus, Si-OH and / or NH bonds in the film may be reduced, while Si-O bonds in the film may be increased. In some embodiments, H may be supplied at a concentration of 1 to 10%. 2 O 2 .

[0091] In another embodiment of the present disclosure, the heat treatment may be performed in another reaction chamber different from the reaction chamber where the film deposition and conversion are performed.

[0092] In some embodiments, film densification may be performed by plasma treatment. Plasma treatment may be performed by applying power while supplying a process gas. The process gas may include H 2, He or a mixture thereof, and a power of 300W to 700W may be applied to activate the process gas.

[0093] The process gas used for the plasma treatment may be supplied at a flow rate between about 50 sccm and about 5000 sccm, more specifically, between about 500 sccm and about 2000 sccm.

[0094] The plasma treatment may be performed between about 50° C. and 800° C., or more specifically, between about 100° C. and about 600° C. The plasma treatment may be performed in a reaction chamber different from a reaction chamber in which the silicon nitride film is formed and converted into a silicon oxide film.

[0095] In some embodiments, film densification can be performed by plasma treatment followed by thermal treatment. Plasma treatment and thermal treatment can be performed in situ in the same reaction chamber.

[0096] Figure 2 A substrate processing method according to another embodiment of the present invention is shown.

[0097] In step 210, a substrate may be introduced into a reaction chamber.

[0098] In step 220, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source may be supplied to the reaction chamber. The silicon-containing gas may include an oligomeric silicon source having fluidity.

[0099] In step 230, power may be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas may react with the silicon-containing gas to form a flowable silicon nitride film. Steps 220 and 230 may be performed at a first temperature.

[0100] In step 240, an oxygen-containing gas may be supplied to the reaction chamber as an oxygen source. The oxygen source may include O 2 , O 3 The supplied oxygen source may penetrate into the silicon nitride film to convert 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.

[0101] In step 250, vacuum UV radiation may be applied to the silicon nitride film in a pulse mode while continuously supplying an oxygen-containing gas to improve the conversion efficiency of the silicon oxide film. Figure 1 Steps 240 and 250 may be performed at a second temperature.

[0102] In step 250, vacuum UV radiation may be applied in a pulsed mode, which is similar to Figure 1In contrast to step 150 of , vacuum UV radiation is applied in a continuous mode in step 150. In the continuous vacuum UV mode, the surface of the film can be hardened first, and internal conversion within the film can be prevented.

[0103] In contrast, 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 through the depth in the gap.

[0104] As mentioned above, vacuum UV strongly excites oxygen molecules. Therefore, the conversion rate may be faster than using traditional UV light, resulting in increased yields.

[0105] The duty cycle of 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.

[0106] On the other hand, when vacuum UV radiation is applied, its intensity can be about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0107] Optionally, vacuum UV radiation may be applied after the conversion step 250 to further improve the light conversion efficiency to the oxide film.

[0108] In step 260, it may be checked whether the film reaches the target thickness. Steps from 220 to 250 may be performed once or repeated multiple times (M≥1). Then, the substrate treatment process may end (in step 280).

[0109] Optionally, film densification 270 may be further performed to densify the silicon oxide film.

[0110] The film densification may be performed by heat treatment. The heat treatment may be performed between about 50° C. and about 800° C., or more specifically between about 100° C. and about 600° C. for about 300 seconds to about 3000 seconds. In some embodiments, the heat treatment may be performed while supplying a process gas. The process gas may include an inert gas, O 2 , O 3 , H 2 O, H 2 O 2 、N 2 or at least one of a mixture thereof. In another embodiment of the present disclosure, the thermal treatment may be performed in another reaction chamber different from the reaction chamber in which the film deposition and the conversion may be performed.

[0111] A process gas with more oxygen can improve film quality. The oligomeric silicon source can contain hydrogen, resulting in a hydrogen component in the film. Therefore, a process gas with more oxygen can provide a sufficient amount of oxygen to the film, thereby removing hydrogen from the film and improving film quality (e.g., film purity, wet etch rate, etc.).

[0112] For example, during the film densification step 270, H may be supplied. 2 O 2 , O 3 or a mixture thereof for heat treatment. Thus, Si-OH and / or NH bonds in the film may be reduced, while Si-O bonds in the film may be increased. In some embodiments, H may be supplied at a concentration of 1 to 10%. 2 O 2 .

[0113] In some embodiments, film densification may be performed by plasma treatment. Plasma treatment may be performed by applying power while supplying a process gas. The process gas may include H 2 , He or a mixture thereof, and a power of 300W to 700W may be applied to activate the process gas.

[0114] The plasma treatment may be performed between about 50° C. and 600° C., or more specifically, between about 100° C. and about 500° C. The plasma treatment may be performed in a reaction chamber different from a reaction chamber in which the silicon nitride film is formed and converted into a silicon oxide film.

[0115] In some embodiments, film densification can be performed by plasma treatment followed by thermal treatment. Plasma treatment and thermal treatment can be performed in situ in the same reaction chamber.

[0116] Figure 3 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0117] according to Figure 3 The substrate processing method may correspond to Figure 1 Step T1 may correspond to Figure 1 Steps 120 and 130 are performed. In step T1, a silicon nitride film may be formed by supplying a silicon-containing gas and a nitrogen-containing gas and applying RF power to the reaction chamber. Step T1 may be performed for between about 10 seconds and about 60 seconds.

[0118] Step T2 may correspond to Figure 1Steps 140 and 150 are performed. In step T2, the silicon nitride film may be converted into a silicon oxide film by supplying an oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying vacuum UV radiation. As described above, in order to maintain the wavelength of the vacuum UV at 200 nm or less, during step T2, the processing pressure may be 100 Torr or less. Therefore, the light conversion efficiency of the vacuum UV may be improved. Step 2 may be performed for between about 300 seconds and about 1800 seconds.

[0119] On the other hand, when vacuum UV radiation is applied, its intensity can be about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0120] Steps T1 and T2 may be performed once or repeated multiple times (M≥1). Thereafter, in step T3, heat treatment may be optionally performed, and the silicon oxide film may be hardened and densified. Step T3 may correspond to Figure 1 Step 170. In the case of supplying an inert gas such as O 2 , O 3 , H 2 O, H 2 O 2 and N 2 The step T3 may be performed for between about 300 seconds and about 3000 seconds.

[0121] Figure 4 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown.

[0122] according to Figure 4 The substrate processing method may correspond to Figure 2 Step T1' may correspond to Figure 2 In step T1', a silicon nitride film may be formed by supplying a silicon-containing gas and a nitrogen-containing gas and applying RF power to the reaction chamber.

[0123] Step T2' may correspond to Figure 2 Steps 240 and 250. In step T2', the silicon nitride film may be converted into a silicon oxide film by supplying an 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 the embodiment of the present invention, vacuum UV radiation can be applied in pulse mode. The duty cycle of vacuum UV pulse mode can be 20% or less.

[0124] As described above, in order to maintain the wavelength of vacuum UV radiation at 200 nm or less, during the T2 step, the processing pressure may be 100 Torr or less. Thus, the light conversion efficiency of vacuum UV radiation may be improved.

[0125] On the other hand, when vacuum UV radiation is applied, its intensity can be about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0126] Steps T1' and T2' may be performed once or repeated multiple times (M ≥ 1). Thereafter, in step T3', heat treatment may be optionally performed, and the silicon oxide film may be hardened and densified. Step T3' may correspond to Figure 2 Step 270. The heat treatment may be performed while the process gas is supplied. The process gas supplied during the heat treatment may include an inert gas, O 2 , O 3 , H 2 O, H 2 O 2 、N 2 or at least one of a mixture thereof. Step T3' may be performed for between about 300 seconds and about 3000 seconds.

[0127] Figure 5 A timing diagram of a substrate processing method according to an embodiment of the present disclosure is shown. Figure 5 Can be Figure 3 Another embodiment of .

[0128] exist Figure 5 In step T1, a silicon nitride film may be formed by supplying a silicon-containing gas and a nitrogen-containing gas and applying RF power to a reaction chamber.

[0129] exist Figure 5 In step T2, the silicon nitride film may be converted into a silicon oxide film by supplying an oxygen-containing gas to the silicon nitride film and activating the oxygen-containing gas by applying vacuum UV radiation. Figure 5 In step T2, vacuum UV may be provided in a pulsed mode.

[0130] exist Figure 5 In step T3, plasma treatment may be performed to densify the silicon oxide film. The plasma treatment may be performed by applying power while supplying a treatment gas. The treatment gas supplied in step T3 may include H 2 , He or at least one of a mixture thereof.

[0131] exist Figure 5 In step T4, heat treatment may be performed to further densify the silicon oxide film. The heat treatment may be performed while supplying a process gas. The process gas supplied in step T4 may include an inert gas, an O 2 , O 3 , H 2 O, H 2 O2 、N 2 or at least one of a mixture thereof.

[0132] Fig. 6A The molecular structure of dimer-TSA is shown, which includes two chain structures containing monomer-TSA. Figure 6B The molecular structure of trimer-TSA is shown, which includes three chain structures containing monomer-TSA.

[0133] Figure 7 The reaction mechanism of the method according to an embodiment of the present disclosure is shown.

[0134] exist Figure 7 In the process, the trimer-TSA source flows along the substrate surface. 3 Under plasma conditions, it undergoes oligomerization and condensation to form a cross-linked network structure.

[0135] The supply of nitrogen source can promote cross-linking during the oligomerization process. In more detail, as Figure 7 As shown, the silicon nitride film may contain dangling bonds such as Si-H (denoted as 'A') and NH (denoted as 'B'). These dangling bonds may cause micropores within the film, resulting in voids and a decrease in film strength. Therefore, the supplied nitrogen source can react with the hydrogen atoms and remove them, thereby preventing the formation of voids.

[0136] Nitrogen sources can also further promote the formation of oligomerization, condensation and cross-linking network structures between source molecules by removing hydrogen atoms.

[0137] 9A to 9E A flowable gap filling process according to an embodiment of the present disclosure is shown.

[0138] exist Fig. 9A In the present invention, a silicon-containing gas may be supplied to a substrate having a gap. The silicon-containing gas may have fluidity, and the source molecule may be neither too simple nor too complex. For example, an oligomeric silicon source having a molecule having a chain structure of 2 to 10 may be provided.

[0139] exist Fig. 9B In the process, the silicon-containing gas can keep flowing along the substrate surface, and the source molecules can bond with each other and form a chain structure with about 10 chains (this is called oligomerization). The bonding between the silicon source molecules can continue, and hydrogen atoms can be removed from the source molecule structure as a by-product, resulting in a reinforcement of the chain structure (this is called condensation).

[0140] exist Fig. 9B In the case of nitrogen, a nitrogen-containing gas can be additionally supplied and activated by applying power to it. For example, NH 3 can be supplied, and NH 3Plasma can be generated by power. The activated nitrogen source can react with the silicon source and form a flowable silicon nitride film. In addition, the nitrogen source can further remove dangling bonded hydrogen atoms from the film, thereby further promoting the oligomerization and condensation of the film and the formation of a cross-linked structure.

[0141] The supply of a nitrogen source has another technical benefit, namely, by removing dangling bonded hydrogen, the formation of micropores and voids in the membrane can be prevented. In some embodiments, Fig. 9A and Fig. 9B The steps can be performed simultaneously.

[0142] exist Fig. 9C In the process, an 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 perform a uniform conversion across the film.

[0143] exist Fig.9D As the process continues, the oligomerization and condensation can be enhanced, and a cross-linked network structure can be formed. 9A to 9D The steps can be performed once or repeated multiple times.

[0144] exist Figure 8 In the process, heat treatment may be performed to harden and densify the film.

[0145] Fig.10 IR (infrared spectroscopy) analysis data showing film composition according to conversion conditions are shown.

[0146] Table 1 shows the Fig.10 The three conversion conditions to silicon oxide film are shown

[0147] Table 1 - Fig.10 Transformation conditions shown

[0148] Conversion gas Conversion time Vacuum UV Heat Treatment Condition A <![CDATA[O 3 ]]> 10 minutes Not applied 450℃ Condition B <![CDATA[O 3 ]]> 60 minutes Not applied 450℃ Condition C <![CDATA[O 3 ]]> 10 minutes Apply (pulse) 450℃

[0149] As shown in Table 1, in condition A, by supplying O 3 The silicon nitride film was converted into a silicon oxide film by heat treatment at 450°C for 10 minutes. However, no vacuum UV radiation was applied. Fig.10 , the peaks of condition A show Si-H bonding peaks, Si-O bonding peaks, and Si-N bonding peaks. That is, condition A may lead to insufficient conversion.

[0150] In condition B, by supplying O 3 The silicon nitride film was converted into a silicon oxide film by heat treatment at 450°C for 60 minutes. However, no vacuum UV radiation was applied. Fig.10, the peak of condition B shows Si-O bonding peak and weak Si-N bonding peak, but no Si-H bonding peak is detected. That is, a long conversion time can lead to sufficient conversion. However, this may increase the substrate processing time.

[0151] In condition C, by supplying O 3 The silicon nitride film was converted into a silicon oxide film by heat treatment at 450°C for 10 minutes. In condition C, contrary to condition A and condition B, vacuum UV radiation was applied in a pulse mode. Fig.10 , the peak of condition C shows a Si-O bonding peak and a weak Si-N bonding peak, but no Si-H bonding peak is detected, which is the same as condition B. That is, although vacuum UV radiation is applied for a short time (e.g., 10 minutes), it leads to sufficient conversion, and the film quality is the same as the film quality when the conversion time is long (e.g., 60 minutes) when the conversion gas is supplied without applying vacuum UV radiation. Therefore, the use of vacuum UV radiation in the conversion step has the technical benefit of significantly reducing the substrate processing time without deteriorating the conversion efficiency and reducing the film quality.

[0152] Table 2 shows the test conditions of the flowable gap filling process according to an embodiment of the present invention.

[0153] Table 2 - Test conditions for flowable gap filling process

[0154]

[0155]

[0156] Fig.11 XPS (X-ray Photoelectron Spectroscopy) analysis data showing the film constitution according to an example of the present disclosure is shown.

[0157] exist Fig.11 In the embodiment of the present disclosure, the silicon nitride film is converted into a silicon oxide film by supplying oxygen while applying vacuum UV radiation. Fig.11 As shown, the film has a stoichiometrically complete film composition, wherein the Si:O ratio is 1:2, and the carbon and nitrogen compositions are less than 5%.

[0158] Fig.12 The wet etching rate of the SiO film depending on the heat treatment conditions is shown.

[0159] like Fig.12 As shown in Figure 2, three heat treatment conditions (i.e., dry annealing, wet annealing, and H annealing at 450°C and 600°C, respectively) can be used to characterize the thermal conductivity of the substrate. 2 O 2The wet etching rate (WER) of the SiO film can be measured by immersing the substrate coated with the heat-treated SiO film in a hydrofluoric acid solution diluted 100:1 in deionized water (dHF) for 1 minute and measuring the thickness of the SiO film etched away. Fig.12 In the figure, WER is the average value measured after etching the film three times in dHF solution.

[0160] exist Fig.12 In the experiment, N can be supplied at 450℃ and 600℃ respectively. 2 Dry annealing can be performed by supplying H at 450°C and 600°C, respectively. 2 Wet annealing can be performed by supplying H2O (steam) at 450°C and 600°C, respectively. 2 O 2 Up to 30 minutes to perform H 2 O 2 annealing.

[0161] exist Fig.12 In H 2 O 2 The SiO film processed under annealing had the lowest wet etching rate, resulting in the formation of the hardest SiO film compared with the other annealing conditions.

[0162] Fig.13 The wet etching rate ratio (WERR) of the SiO film depending on the heat treatment conditions is shown. The WERR is the ratio of the wet etching rate of the SiO film to the wet etching rate of the SiO film thermally formed at 1000°C.

[0163] exist Fig.13 In H 2 O 2 The SiO film processed under annealing may have the lowest wet etching rate ratio, resulting in the formation of the hardest SiO film compared to other annealing conditions.

[0164] Fig.14 Infrared spectrum analysis results showing the bonding structure of the SiO film depending on the heat treatment conditions at 450° C. are shown.

[0165] like Fig.14 As shown, compared with dry annealing and wet annealing, when H 2 O 2 During annealing, the NH peak (at about 1150cm -1 ) and the Si-OH peak (at about 950 cm -1 ) shows the lowest intensity. That is, H 2 O 2Annealing can more effectively remove hydrogen from the film and improve film quality (eg, film purity, wet etch rate, etc.).

[0166] Fig.15 A substrate processing method according to another embodiment of the present invention is shown. Fig.15 The method can be carried out at 70°C or below.

[0167] In step 310 of the substrate processing method 300, a substrate may be provided to a reaction chamber. In more detail, the substrate may be loaded onto a pedestal mounted on a heating block. The heating block may provide thermal energy to heat the substrate to a processing temperature. The substrate may have a semiconductor circuit including a 3D structure and a gap formed thereon. In some embodiments of the present disclosure, the depth of the gap may be 200nm or less. The reaction chamber may include equipment for processing the substrate therein. In the reaction chamber, deposition, gap filling, etching, or any other substrate processing process using a gas activation source (e.g., plasma and / or UV) may be performed on the substrate.

[0168] In step 320, a silicon-containing gas as a silicon source and a nitrogen-containing gas as a nitrogen source may be supplied to the reaction chamber. The silicon-containing gas may include an oligomeric silicon source having fluidity.

[0169] The silicon-containing gas may include at least one of dimer-trisilylamine, trimer-trisilylamine, tetramer-trisilylamine, pentamer-trisilylamine, hexamer-trisilylamine, heptamer-trisilylamine, octamer-trisilylamine, 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.

[0170] The nitrogen-containing gas may include N 2 、N 2 O、NO 2 NH 3 NH 4 、N 2 H 2 、N 2 H 4 or at least one of a mixture thereof.

[0171] In step 330, power may be applied to the reaction chamber to activate the nitrogen-containing gas. The activated nitrogen-containing gas may react with the silicon-containing gas to form a flowable silicon nitride (SiN) film. Steps 320 and 330 may be performed simultaneously. The power may be applied in situ or remotely. The power may be in a range between about 10 W and about 1000 W.

[0172] In step 340, the silicon nitride film may be converted into a silicon oxynitride film (SiON) while supplying an oxygen-containing gas to the reaction chamber. The oxygen-containing gas may include ozone (O 3 The concentration of ozone can be about 200g / m 3 and about 400g / m 3 In the low range between.

[0173] In step 350, vacuum UV radiation may be applied to the silicon nitride film while supplying an inert gas (e.g., Ar). In step 350, an oxygen-containing gas may not be supplied to prevent the silicon nitride film from being completely converted into a silicon oxide film. In other words, the silicon nitride film may be partially converted into a silicon oxide film, resulting in the formation of a silicon oxynitride film.

[0174] Low substrate processing temperatures of about 70°C or less may result in less active ozone. 3 and about 400g / m 3 The low concentration of ozone between the two may 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 nitride oxide film.

[0175] As a result, a silicon oxynitride film can be formed. The intensity of vacuum UV radiation can be about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

[0176] In step 360, it may be checked whether the silicon oxynitride film reaches the target thickness. Steps from 320 to 350 may be performed once or repeated multiple times (M≥1). Then, the substrate treatment process may end (in step 380).

[0177] Optionally, in step 370, the silicon oxynitride film may be further processed (e.g., annealed, densified, etc.). The processing of the silicon oxynitride film may be performed thermally or by applying power while supplying Ar, O, and / or 2 、N 2 or at least one of a mixture thereof.

[0178] Fig.16 A timing diagram of a substrate processing method for forming a silicon oxynitride film according to an embodiment of the present invention is shown. Fig.16 Can correspond to Fig.15 .

[0179] exist Fig.16 In step T1″, a silicon nitride film may be formed by supplying a silicon-containing gas and a nitrogen-containing gas while applying power to the reaction chamber.

[0180] In step T2″, the silicon nitride film may be converted into a silicon nitride oxide film by supplying an oxygen-containing gas. The oxygen-containing gas may include ozone (O3 ).

[0181] In step T3", vacuum UV radiation may be applied to the silicon oxynitride film. In step T3", oxygen-containing gas may not be supplied to prevent the silicon nitride film from being completely converted into a silicon oxide film. Therefore, the silicon nitride film may be partially converted into a silicon oxide film. In other words, a silicon oxynitride film may be formed.

[0182] According to an embodiment of the present invention, a wet etching rate of the silicon oxynitride film may be determined by a ratio of a conversion time of converting the silicon nitride film into the silicon oxynitride film to a vacuum UV radiation treatment time.

[0183] Fig.17 The ozone (O 3 ) to the vacuum UV radiation treatment time. The wet etching can be performed in a hydrofluoric acid solution diluted 200:1 in deionized water (dHF) for 180 seconds.

[0184] like Fig.17 As shown, the wet etching rate of the silicon oxynitride film may be about 15 nm / minute at a ratio of 1: 1. Therefore, the wet etching rate may be controlled by the ratio between the conversion time and the vacuum UV irradiation time.

[0185] Fig.18 FIG. 2 shows the infrared spectrum analysis result showing the bonding structure of the silicon oxynitride film formed according to an embodiment of the present invention. Fig.18 As shown, the peak of silicon oxynitride (SiON) film is shown at about 1100 cm -1 Place.

[0186] Fig.19 The etching selectivity between the silicon oxynitride film and the silicon oxide film depending on the etching conditions is shown.

[0187] exist Fig.19 In the case of wet etching, hydrofluoric acid diluted 200:1 in deionized water (dHF) can be used at 20°C for 180 seconds. 4 The dry etching in the reaction chamber can be 4 The etching gas was used while applying 100 W of power to the reaction chamber at 60 mTorr and 50°C for 30 seconds. 3 Dry etching in the reaction chamber can be achieved by supplying CHF 3 The etching gas was run while applying 100 W of power to the reaction chamber at 60 mTorr and 50° C. for 30 seconds.

[0188] like Fig.19As shown, under each etching condition, the etching rate between the SiON film and the SiO film shows a large difference. Depending on the etching conditions, the etching rate between the same films also shows a large difference. That is, the embodiments of the present disclosure can be applied to substrate processing methods that require large etching selectivity under specific etching conditions. Therefore, for example, a selective etching process can be performed on a non-planar surface of a substrate.

[0189] Fig. 20 A scanning electron microscope (SEM) image of the SiON film filling the gap is shown. Fig. 20 As shown, the gap can be filled with SiON film without voids.

[0190] Table 3 shows the test conditions for filling the gap with a flowable SiON film according to an embodiment of the present disclosure.

[0191] Table 3 - Test conditions for gap filling with flowable SiON films

[0192]

[0193]

[0194] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

[0195] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method for filling a gap in a substrate, the method comprising: Forming a flowable silicon nitride film in the gap at a first temperature includes: supplying a silicon-containing gas and a nitrogen-containing gas to the reaction chamber; and Applying power to the reaction chamber to activate the nitrogen-containing gas, wherein the silicon-containing gas reacts with the activated nitrogen-containing gas to form a silicon nitride film; Converting the silicon nitride film into a silicon oxide film at a second temperature includes: continuously supplying an oxygen-containing gas to the reaction chamber; and applying vacuum UV radiation to the silicon nitride film; The first temperature is different from the second temperature.

2. The method according to claim 1, wherein: The conversion of the silicon nitride film into the silicon oxide film is performed at a pressure of 100 Torr or less.

3. The method according to claim 2, wherein: The vacuum UV radiation was applied in pulse mode.

4. The method according to claim 3, wherein: The duty cycle of the pulse mode is 20% or less.

5. The method according to claim 1, wherein: The intensity of the vacuum UV radiation is about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

6. The method according to claim 1, wherein: The first temperature is about 100° C. or less.

7. The method according to claim 1, wherein: The second temperature is between about 70°C and about 150°C.

8. The method according to claim 7, wherein: The second temperature is between about 80°C and about 120°C.

9. The method according to claim 1, wherein: The silicon nitride film includes at least one of SiN, SiCN or a mixture thereof.

10. The method according to claim 1, wherein: The silicon-containing gas includes at least one of the following: dimer-trisilylamine, trimer-trisilylamine, tetramer-trisilylamine, pentamer-trisilylamine, hexamer-trisilylamine, heptamer-trisilylamine, octamer-trisilylamine, 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.

11. The method according to claim 1, wherein: The nitrogen-containing gas includes at least one of N2, N2O, NO2, NH3, NH4, N2H2, N2H4 or a mixture thereof.

12. The method according to claim 11, wherein: The nitrogen-containing gas is supplied at between about 10 sccm and about 100 sccm.

13. The method according to claim 12, wherein: The nitrogen-containing gas is supplied at between about 20 sccm and about 50 sccm.

14. The method according to claim 1, wherein: The silicon oxide film includes at least one of SiO, SiCO or a mixture thereof.

15. The method according to claim 1, wherein: The oxygen-containing gas includes at least one of O2, O3 or a mixture thereof.

16. The method according to claim 15, wherein: The oxygen-containing gas is supplied at between about 50 sccm and about 3000 sccm.

17. The method according to claim 16, wherein: The oxygen-containing gas is supplied at between about 100 sccm and about 1500 sccm.

18. The method according to claim 1, wherein: After the substrate is transferred to a reaction chamber, vacuum UV radiation is applied in a reaction chamber different from a reaction chamber in which the silicon nitride film is converted into a silicon oxide film while an oxygen-containing gas is supplied in the reaction chamber.

19. The method according to claim 1, wherein: The power is in a range between about 40W and about 200W.

20. The method according to claim 19, wherein: The power is in a range between about 50W and about 150W.

21. The method of claim 1, further comprising performing film densification at a third temperature in a reaction chamber different from a reaction chamber in which the film is formed and converted to densify the silicon oxide film while supplying a process gas thereto.

22. The method according to claim 21, wherein: The film densification is performed by at least one of plasma treatment, thermal treatment, or a mixture thereof.

23. The method according to claim 22, wherein: Film densification is performed by plasma treatment followed by thermal treatment.

24. The method according to claim 21, wherein: The third temperature is between about 50°C and about 800°C.

25. The method according to claim 24, wherein: The third temperature is between about 100°C and about 600°C.

26. The method of claim 22, wherein: During the thermal treatment, the process gas includes at least one of an inert gas, O2, O3, H2O, H2O2, N2, or a mixture thereof.

27. The method of claim 22, wherein: During plasma processing, the process gas includes at least one of H 2 , He, or a mixture thereof.

28. The method of claim 22, wherein: During plasma processing, between about 300 W and about 700 W of power is applied to the reaction chamber.

29. The method of claim 1, wherein: The method is performed once or repeated multiple times.

30. A method for filling a gap in a substrate, the method comprising: Forming a flowable silicon nitride film in the gap, comprising: supplying a silicon-containing gas and a nitrogen-containing gas to the reaction chamber; and Applying power to the reaction chamber to activate the nitrogen-containing gas, wherein the silicon-containing gas reacts with the activated nitrogen-containing gas to form a silicon nitride film; converting the silicon nitride film into a silicon oxynitride film (SiON) while supplying an oxygen-containing gas to the reaction chamber; and Vacuum UV radiation was applied to the silicon oxynitride film.

31. The method according to claim 30, wherein: The process is carried out at about 70°C or below.

32. The method of claim 30, wherein: The vacuum UV radiation was applied without supplying an oxygen-containing gas.

33. The method of claim 30, wherein: The oxygen-containing gas includes ozone (O3).

34. The method of claim 33, wherein: The ozone concentration is about 200 g / m 3 and about 400g / m 3 in the range between.

35. The method of claim 30, further comprising thermally treating the silicon oxynitride film by supplying at least one of Ar, O2, N2, or a mixture thereof.

36. The method of claim 30, further comprising treating the silicon oxynitride film by applying power and supplying at least one of Ar, O2, N2, or a mixture thereof.

37. The method of claim 30, wherein: The wet etching rate of the silicon oxynitride film is determined by the ratio of the time for converting the silicon nitride film into the silicon oxynitride film to the time for treating the silicon oxynitride film under vacuum UV irradiation.

38. The method of claim 37, wherein: The wet etching rate of the silicon oxynitride film is about 15 nm / min at a ratio of 1:

1.

39. The method of claim 30, wherein: The silicon-containing gas includes at least one of the following: dimer-trisilylamine, trimer-trisilylamine, tetramer-trisilylamine, pentamer-trisilylamine, hexamer-trisilylamine, heptamer-trisilylamine, octamer-trisilylamine, 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.

40. The method of claim 30, wherein: The nitrogen-containing gas includes at least one of N2, N2O, NO2, NH3, NH4, N2H2, N2H4 or a mixture thereof.

41. The method of claim 30, wherein: The power is in a range between about 10W and about 1000W.

42. The method of claim 30, wherein: The intensity of the vacuum UV radiation is about 80 mW / cm 2 and about 120mW / cm 2 in the range between.

43. The method of claim 30, wherein: The method is performed once or repeated multiple times.

Images