Substrate processing method

Abstract

A method of forming a film on a substrate includes providing the substrate to a reaction chamber and forming the film on the substrate by repeating cycles including supplying a first silicon source including acetoxy groups and supplying a hydrogen source while applying power from a power source to the reaction chamber, wherein the hydrogen source reacts with the acetoxy group of the first silicon source to form an adsorption site that is reactive with the acetoxy group, and wherein the film formed on the substrate comprises silicon oxycarbide (SiOC).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a method of processing a substrate, and more particularly, to a method of forming an oxide film on a substrate without supplying an oxygen source. BACKGROUND

[0002] As the line width of semiconductor devices is reduced, the RC delay (resistance-capacitance delay) of the insulating layer of the device causes a slow response time of the device. Therefore, a material having a low dielectric constant (hereinafter, referred to as a low-k material) is introduced. A SiOC film is generally used as the low-k material. The SiOC film is formed at a relatively low temperature to reduce the thermal budget when manufacturing the device. For this, a plasma enhanced atomic layer deposition (PEALD) method is employed. In the PEALD method, a reactant gas is activated by power to react with a source gas to form a film at a low temperature. To form the SiOC film by the PEALD method, a silicon source and an oxygen source activated by power are sequentially and intermittently supplied to form the film. However, the activated oxygen source causes damage to a sub-layer (e.g., oxidation of a conductive layer), resulting in low performance of the device.

[0003] Therefore, there is a need to form a SiOC film at a low temperature without damaging a sub-layer. SUMMARY

[0004] The present disclosure introduces a method of forming a film on a substrate, and more particularly, a SiOC film on a substrate without causing damage to a sub-layer.

[0005] In one or more embodiments, a method of forming a film on a substrate including a patterned structure can include providing the substrate in a reaction chamber, and forming the film on the substrate by repeating cycles, the cycles including supplying a first silicon source including acetoxy groups, and supplying a hydrogen source, wherein the hydrogen source can react with the acetoxy groups of the first silicon source to form adsorption sites reactive to the acetoxy groups, wherein the film formed on the substrate can include silicon oxycarbide (SiOC).

[0006] In one or more embodiments, the first silicon source can include acetoxy silane.

[0007] In one or more embodiments, the first silicon source can include at least one of triacetoxy methyl silane [(CH3CO2)3SiCH3], triacetoxy ethyl silane [(CH3CO2)3SiCH2CH3], diacetoxy dimethyl silane [(CH3CO2)2Si(CH3)2], triacetoxy (vinyl) silane [(CH3CO2)3SiCH=CH2], 1,3-diacetoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or a mixture thereof.

[0008] In one or more embodiments, the hydrogen source can include at least one of atomic hydrogen and dihydrogen or a mixture thereof.

[0009] In one or more embodiments, the adsorption sites can include hydroxyl groups (i.e., -OH).

[0010] In one or more embodiments, power can be applied to the reaction chamber concurrently with supplying the hydrogen source, where the power can be applied to activate the hydrogen source at a frequency between about 10 MHz and about 100 MHz at an intensity between about 100 W and about 300 W.

[0011] In one or more embodiments, the power can be applied to the reaction chamber in pulses.

[0012] In one or more embodiments, the method can be performed at between about 100 °C and about 500 °C.

[0013] In one or more embodiments, the film growth rate of the film can be about per cycle or greater.

[0014] In one or more embodiments, purging the reaction chamber after supplying the first silicon source can be performed by evacuating the reaction chamber.

[0015] In one or more embodiments, the method can further include supplying a second silicon source prior to or after supplying the first silicon source, the second silicon source including at least one of: an alkyl and an alkyl amine group, an alkyl and a silyl amine group, an alkyl and an alkoxy silyl group, an alkoxy silyl and an alkane group, an alkoxy and a silyl group, an alkyl and a silyl group, or a mixture thereof.

[0016] In one or more embodiments, the second silicon source can include at least one of: N,N-diethyl-2,4,6,8-tetramethyl-cyclotetrasiloxane-2-amine [C8H 25 NO4Si4], (dimethylamino)trimethylsilane [(CH3)2NSi(CH3)3], bis(dimethylamino)dimethylsilane [(CH3)2N]2Si(CH3)2, ethoxy(trimethyl)silane [C2H5OSi(CH3)3], diethoxy(dimethyl)silane [(C2H5O)2Si(CH3)2], triethoxymethylsilane [(C2H5O)3SiCH3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2Si(OC2H5)3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2CH2Si(OC2H5)3], 4,4,6,6-tetramethyl-3,7-dioxa-4,6-disilanonane [(C2H5O)(CH3)2SiCH2Si(CH3)2(OC2H5)], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H20 O2Si2], 1,3,5-triethoxy-1,3,5-trimethyl-1,3,5-trisilane [C 12 H 30 O3Si3], 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilane [C 15 H 36 O6Si3], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or mixtures thereof.

[0017] In one or more embodiments, purging can be performed by evacuating the reaction chamber at least one of after supplying the first silicon source and after supplying the second silicon source.

[0018] This summary is provided to introduce a selection of concepts in a simplified form. These concepts are further described below in the detailed description of example embodiments of the disclosure. This summary is not intended to identify 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 DRAWINGS

[0019] Figure 1 A method of forming a film according to an embodiment of the disclosure is shown.

[0020] Figure 2 A timing diagram of one embodiment of the method of Figure 1

[0021] Figures 3A to 3C Reaction mechanisms of the methods of Figure 1 Figure 2

[0022] Figure 4 A method of forming a film according to another embodiment of the disclosure is shown.

[0023] Figure 5 A timing diagram of one embodiment of the method of Figure 4

[0024] Reaction mechanisms of the methods of Figures 6A to 6D Figure 4 Figure 5

[0025] Figure 7 A TEM (Transmission Electron Microscope) image of a SiOC film formed on a patterned structure by using the method of the disclosure is shown.

[0026] Figure 8 ​​​​​​The film growth rate of the SiOC film according to the ratio of the supplied hydrogen source to the entire gas during power application is shown.

[0027] Figure 9 An exemplary apparatus for performing the method according to the present disclosure is shown.

[0028] 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 sizes of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0029] 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 obvious modifications and equivalents thereof. Accordingly, it is intended that the scope of the disclosed invention should not be limited by the specific disclosed embodiments described below.

[0030] As used herein, the term "substrate" may refer to any underlying material or materials, including any underlying material or materials that can be modified or on which a device, circuit, or film 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 a powder, a sheet, or a workpiece. Sheet-form 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.

[0031] 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, such that the process continues until the end of the substrate is reached. The continuous substrate may be supplied from a continuous substrate feed system to allow for the manufacture and output of the continuous substrate in any suitable form.

[0032] 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 the present disclosure.

[0033] The terms "first" and "second" do not necessarily mean that "first" must come before "second". The terms "first" and "second" are simply used to distinguish between the different attributes between them. Therefore, "second" can, in turn, come before "first".

[0034] The particular implementations shown and described are illustrative and are not intended to otherwise limit the scope of aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the systems can not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical couplings between the various elements. Many alternative or additional functional relationships or physical connections can be present in a practical system, and / or absent in some embodiments.

[0035] It should be understood that the configurations and / or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein can represent one or more of any number of processing strategies. As such, various acts illustrated can be performed in the sequence illustrated, in other sequences, or omitted in some embodiments.

[0036] 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 attributes disclosed herein, as well as any and all equivalents thereof.

[0037] Figure 1 A method 100 of forming a film is shown in accordance with embodiments of the present disclosure.

[0038] In step 110 of the method 100 of forming a film, a substrate can be provided in a reaction chamber. The substrate can include a patterned structure (e.g., a gap structure).

[0039] In step 120, a first silicon source can be provided to the substrate. The first silicon source can chemisorb on adsorption sites (e.g., -OH, hydroxyl groups) on the substrate surface. The first silicon source can include an acetoxy group. In one embodiment, the first silicon source can include an acetoxy silane. For example, the first silicon source can include at least one of triacetoxy methylsilane [(CH3CO2)3SiCH3], triacetoxy ethylsilane [(CH3CO2)3SiCH2CH3], diacetoxy dimethylsilane [(CH3CO2)2Si(CH3)2], triacetoxy (vinyl)silane [(CH3CO2)3SiCH=CH2], 1,3-diacetoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or mixtures thereof.

[0040] In step 130, a hydrogen source can be supplied to the substrate. The hydrogen source can be supplied while power is applied to the reaction chamber from a power source. The power can be applied in situ or remotely at an intensity between about 100 W and about 300 W at a frequency between about 10 MHz and about 100 MHz. In one embodiment of the disclosure, the power can be applied to the reaction chamber in a continuous mode. In another embodiment of the disclosure, the power can be applied to the reaction chamber in a pulsed mode.

[0041] The hydrogen source can include at least one of atomic hydrogen (H), diatomic hydrogen (H2), or a mixture thereof. The hydrogen source can react with the acetoxy group (i.e., H3C-C(=0)-0-) of the first silicon source to form an adsorption site reactive to the acetoxy group of the first silicon source in subsequent cycles. The adsorption site can be a hydroxyl group (i.e., -OH). The film formed on the substrate can include silicon oxycarbide (SiOC).

[0042] Steps 120 and 130 can be repeated multiple times, including cycles, until a desired thickness is reached. Then, in step 140, the method 100 of forming a film can end.

[0043] In one or more embodiments, the method 100 can be performed at a temperature between about 100 °C and about 500 °C.

[0044] In one or more embodiments, the method 100 can be performed at a pressure of about 3 Torr or less.

[0045] In one or more embodiments, a film growth rate of the film according to the method 100 can be about 0.1 A / cycle or greater. / cycle or greater.

[0046] In one or more embodiments of the disclosure, the method 100 can further include purging the reaction chamber after at least one of supplying the first silicon source (step 120) and supplying the hydrogen source (step 130).

[0047] In one or more embodiments of the disclosure, purging the reaction chamber after supplying the first silicon source can be performed by evacuating the reaction chamber.

[0048] Figure 2 A timing diagram of one embodiment of the method 100 of Figure 1 is shown.

[0049] In T1, a first silicon source can be supplied to a substrate loaded in a reaction chamber. The first silicon source can be delivered to the reaction chamber by a carrier gas (e.g., Ar). A purge gas (e.g., Ar) can be further supplied to the reaction chamber. The first silicon source can be chemisorbed on the substrate.

[0050] In T2, a purge can be performed to remove residual first silicon source from the reaction chamber. The purge in T2 can be performed by evacuating the reaction chamber. Alternatively, the purge in T2 can be performed by supplying a purge gas (e.g., Ar).

[0051] In T3, a hydrogen source can be supplied to the substrate while power is applied from the power source to the reaction chamber, thereby activating the hydrogen source. The activated hydrogen can react with the first silicon source adsorbed on the substrate, resulting in formation of adsorption sites (i.e., -OH, hydroxyl groups).

[0052] In T4, a purge can be performed by supplying a purge gas to remove byproducts from the reaction chamber. T1 to T4 can be repeated cyclically a number of times (M times) to form a film. The film can be a silicon oxycarbide (SiOC) film. Figure 1 and Figure 2 The method 100 in

[0053] Figures 3A to 3C The reaction mechanism of the method 100 in Figure 1 and Figure 2 is shown.

[0054] In Figure 3A , triacetoxy methylsilane [(CH3CO2)3SiCH3] 310 can be supplied as a first silicon source to a substrate 300. For example, the substrate can include a SiOC film. The surface of the film can include Si-based bonding structures. For example, the surface of the substrate can include -OH (hydroxyl groups) and -CH3 (methyl groups).

[0055] In Figure 3B , triacetoxy methylsilane 310 can chemisorb on the surface of the film. In more detail, the triacetoxy methylsilane can react with the hydroxyl groups (i.e., -OH) as adsorption sites including the surface of the film, resulting in formation of Si-O-Si bonding structures 320 and removal of acetoxy groups 330 (i.e., H3C-C(=0)-0-) as byproducts.

[0056] In Figure 3C , diatomic hydrogen (H2) as a hydrogen source can be supplied to the substrate while power is applied from a power source to the reaction chamber to generate a hydrogen plasma, resulting in formation of hydrogen radicals from the hydrogen plasma.

[0057] The hydrogen radicals can react with oxygen bonded to carbon, resulting in formation of hydroxyl groups (-OH) 340 and hydrogen (H) 350. The hydroxyl groups can act as adsorption sites for a silicon source supplied in a subsequent cycle. The carbon and hydrogen can remain in the film, forming a SiOC film, and can reduce the dielectric constant (k) of the film. Thus, a low-k SiOC film can be formed.

[0058] Figures 3A to 3C The multiple times can be repeated until a desired thickness (target thickness) is achieved.

[0059] Figure 4 A method of forming a film is shown in accordance with another embodiment of the disclosure.

[0060] In step 410 of the method 400 of forming a film, a substrate can be provided in a reaction chamber. The substrate can include a patterned structure (e.g., a gap structure).

[0061] In step 420, a second silicon source can be supplied to the substrate. The second silicon source can include at least one of an alkyl and alkyl amine group, an alkyl and silyl amine group, an alkyl and alkoxy silane group, an alkoxy silyl and alkane group, an alkoxy and silane group, an alkyl and silane group, or a mixture thereof.

[0062] The second silicon source can include at least one of N,N-diethyl-2,4,6,8- tetramethyl-cyclotetrasiloxane-2-amine [C8H 25 NO4Si4], (dimethylamino)trimethylsilane [(CH3)2NSi(CH3)3], bis(dimethylamino)dimethylsilane [(CH3)2N]2Si(CH3)2, ethoxy(trimethyl)silane [C2H5OSi(CH3)3], diethoxy(dimethyl)silane [(C2H5O)2Si(CH3)2], triethoxymethylsilane [(C2H5O)3SiCH3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2Si(OC2H5)3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2CH2Si(OC2H5)3], 4,4,6,6-tetramethyl-3,7-dioxa-4,6-disilanonane [(C2H5O)(CH3)2SiCH2Si(CH3)2(OC2H5)], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H 20 O2Si2], 1,3,5-triethoxy-1,3,5-trimethyl-1,3,5-trisilane [C 12 H 30 O3Si3], 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilane [C 15 H 36 O6Si3], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or a mixture thereof.

[0063] The second silicon source can react via a reactive group of the second silicon source (e.g., [C n H 2n+1 ]x N, alkylamine) chemisorbs on a hydroxyl group (i.e., -OH) as an adsorption site formed on the substrate. The alkyl group (-C n H 2n+1 ) can not react with the substrate and remain in the film. The space occupied by the alkyl group can subsequently create a hole in the film, thereby further reducing the dielectric constant of the film.

[0064] In step 430, a first silicon source can be supplied to the substrate. The first silicon source can chemisorb on an adsorption site (i.e., -OH, hydroxyl group) of the substrate surface. The first silicon source can include an acetoxy group. In one embodiment, the first silicon source can include an acetoxy silane. For example, the first silicon source can include at least one of triacetoxy methylsilane [(CH3CO2)3SiCH3], triacetoxy ethylsilane [(CH3CO2)3SiCH2CH3], diacetoxy dimethylsilane [(CH3CO2)2Si(CH3)2], triacetoxy (vinyl)silane [(CH3CO2)3SiCH=CH2], 1,3-diacetoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or a mixture thereof.

[0065] In step 440, a hydrogen source can be supplied to the substrate. The hydrogen source can be supplied while power is applied to the reaction chamber from a power source. The power can be applied in situ or remotely at a strength of between about 100 W and about 300 W at a frequency of between about 10 MHz and about 100 MHz. In one embodiment of the present disclosure, the power can be applied to the reaction chamber in a continuous mode. In another embodiment of the present disclosure, the power can be applied to the reaction chamber in a pulsed mode.

[0066] The hydrogen source can include at least one of atomic hydrogen (H), diatomic hydrogen (H2), or a mixture thereof. The hydrogen source can be activated by the applied power and can react with the acetoxy group (i.e., H3C-C(=O)-O-) of the first silicon source to form an adsorption site reactive to the acetoxy group of the first silicon source in a subsequent cycle. The adsorption site can be a hydroxyl group (i.e., -OH). The film formed on the substrate can include silicon oxycarbide (SiOC).

[0067] Since the second silicon source can chemisorb on the substrate and the space occupied by the non-reactive group (i.e., alkyl group) can result in a hole in the SiOC film, the dielectric constant of the film can be further reduced. Thus, a low-k SiOC film can be formed.

[0068] In Figure 4 , the method 400 can not use an oxygen source. Thus, damage to a sublayer (e.g., a conductive intermediate layer) by an oxygen plasma can be prevented. Thus, low electrical performance of a device can be correspondingly prevented.

[0069] Steps 420 and 440 can be repeated, including in a loop, until a target thickness is reached. Then, in step 450, the method 400 of forming a film can end.

[0070] In Figure 4 , the second silicon source can be supplied, and then the first silicon source can be supplied. In another embodiment, the first silicon source can be supplied, and then the second silicon source can be supplied. In other words, the second silicon source can be supplied before or after the first silicon source is supplied.

[0071] In one or more embodiments, the method 400 can be performed at a temperature between about 100 °C and about 500 °C.

[0072] In one or more embodiments, the method 400 can be performed at a pressure of about 3 Torr or less.

[0073] In one or more embodiments, a film growth rate of a film according to the method 400 can be greater than about 1 A / cycle. / cycle.

[0074] In one or more embodiments of the present disclosure, the method 400 can further include purging the reaction chamber in at least one of after supplying the first silicon source (step 430), after supplying the second silicon source (step 420), and after supplying the hydrogen source (step 440).

[0075] In one or more embodiments of the present disclosure, purging in at least one of after supplying the first silicon source and after supplying the second silicon source can be performed by evacuating the reaction chamber.

[0076] Figure 5 A timing diagram illustrating one embodiment of a method of Figure 4 is shown.

[0077] In T1’, a second silicon source can be supplied to a substrate loaded in a reaction chamber. The second silicon source can be delivered to the reaction chamber by a carrier gas (e.g., Ar). A purge gas (e.g., Ar) can also be supplied to the reaction chamber. The second silicon source can chemisorb on the substrate.

[0078] In T2’, a first silicon source can be supplied to the substrate loaded in the reaction chamber. The first silicon source can be delivered to the reaction chamber by a carrier gas (e.g., Ar). Optionally, a purge gas (e.g., Ar) can be further supplied to the reaction chamber. The first silicon source can chemisorb on the substrate.

[0079] In T3’, a purge can be performed to remove residual first silicon source and residual second silicon source from the reaction chamber. The purge in T3’ can be performed by evacuating the reaction chamber. Optionally, a purge gas (e.g., Ar) can be further supplied in T3’.

[0080] In T4', a hydrogen source can be supplied to the substrate while power is applied to the reaction chamber from a power source. The activated hydrogen can react with the first silicon source adsorbed on the substrate, resulting in the formation of adsorption sites (i.e., -OH, hydroxyl groups). Optionally, a purge gas (e.g., Ar) can be further supplied in T4'.

[0081] In T5', a purge can be performed by supplying a purge gas (e.g., Ar) to remove byproducts from the reaction chamber. T1' to T5' can be repeated cyclically for a number of times (N times) to form a film. The film can be silicon oxycarbide (SiOC).

[0082] Figure 4 The method 400 in Figure 5 may have the technical benefit of forming a SiOC film without supplying an oxygen source (i.e., oxygen radicals). Thus, damage to the sublayer by the oxygen source can be prevented.

[0083] Figures 6A to 6D The reaction mechanism of the method 400 in Figure 4 and Figure 5 is shown.

[0084] In Figure 6A , bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2) 610 can be supplied to the substrate 600 as a second silicon source. For example, the second silicon source 610 can include an alkyl (C n H 2n+1 , R1) and a reactive group (alkyl amine group, (C n H 2n+1 ) x N, R2). For example, the substrate can include a SiOC film. The surface of the film can include Si-based bonding structures. For example, the surface of the substrate can include -OH (hydroxyl group) as an adsorption site and -CH3 (methyl group).

[0085] The second silicon source 610 can react with the hydroxyl group as an adsorption site via the reactive group R2, resulting in the formation of a Si-O-Si bonding structure 620 as shown in Figure 6B . The alkyl group (-C n H 2n+1 , R1) of the second silicon source 610 can not react with the substrate and remain in the film. The space occupied by the alkyl group can result in a pore in the film, thereby further reducing the dielectric constant of the film.

[0086] In Figure 6B , triacetoxy methylsilane [(CH3CO2)3SiCH3] 630 can be supplied to the substrate as a first silicon source.

[0087] In Figure 6CIn particular, the first silicon source 630 can react with hydroxyl groups (i.e., -OH) formed on the surface of the substrate, resulting in the formation of Si-O-Si bonding structures 640 and the removal of acetoxy groups 650 (i.e., H3C-C(=0)-0-) as byproducts.

[0088] In Figure 6D particular, diatomic hydrogen (H2) as a hydrogen source can be supplied to the substrate while power is applied from a power source to the reaction chamber to generate a hydrogen plasma, resulting in the formation of hydrogen radicals from the hydrogen plasma.

[0089] The hydrogen radicals can react with oxygen bonded to carbon of the first silicon source, resulting in the formation of hydroxyl groups (-OH) 660 and hydrogen (H) 670. The hydroxyl groups 660 can act as adsorption sites for the first and second silicon sources supplied in subsequent cycles. Carbon and hydrogen can remain in the film, forming a SiOC film, and can reduce the dielectric constant (k) of the film. Thus, the dielectric constant (k) of the film can be even further reduced along with the pores created from the alkyl groups of the second precursor.

[0090] Figures 6A to 6D This can be repeated multiple times until a desired thickness (target thickness) is reached.

[0091] Figure 7 A TEM (Transmission Electron Microscope) image of a SiOC film formed on a patterned structure by the method of the present disclosure is shown. In Figure 7 particular, a SiOC film 700 can be formed by Figure 1 the method of Figure 2 In forming the SiOC film, triacetoxy methylsilane can be supplied as the first silicon source, followed by the supply of a hydrogen plasma. As Figure 7 shown, the film can be uniformly formed on the patterned structure.

[0092] Figure 8 A film growth rate of the SiOC film according to the ratio of the supplied hydrogen source to the entire gas during the application of power is shown.

[0093] In Condition A, a hydrogen source (e.g., H2) and a purge gas (e.g., Ar) are supplied at a flow rate of 1 : 1. That is, the gas flow ratio of the hydrogen source to the entire gas (e.g., H2+ Ar) is 50%.

[0094] In Condition B, only a hydrogen source is supplied. That is, the gas flow ratio of the hydrogen source to the entire gas is 100%.

[0095] As Figure 8 shown, the film growth rate in Condition A is about / cycle, and the film growth rate in Condition B is about / cycle, indicating that the film growth rate in condition B is higher than that in condition A. In condition B, the blocking effect of Ar radicals on hydrogen radicals does not occur. Therefore, in condition B, more adsorption sites (i.e., -OH) can be formed, and more Si-O-Si film structures can be formed accordingly.

[0096] Table 1 shows the execution Figure 1 Test conditions of the method, wherein a first silicon source is supplied.

[0097] Table 1 - Execution Figure 1 Test conditions for the method

[0098]

[0099] Figure 9 An example of an apparatus for executing the method according to the present disclosure is shown.

[0100] exist Figure 9 In the embodiment, the apparatus 1 may include a reaction chamber 2, a gas supply unit 3 for supplying gas into the reaction chamber 2, a substrate support unit 4 supporting a substrate 5 and arranged facing the gas supply unit 3, an exhaust unit 6 for evacuating the reaction chamber 2, an exhaust path 7 connecting the reaction chamber 2 to the exhaust unit 60, and a power supply unit 10. The power supply unit 10 may include a power generator (power source) 8, a matching network 9, and a power delivery unit 11 to apply power from the power supply unit 10 to the gas supply unit 3. The gas supply unit 3 may be a shower head made of a conductive material. The gas supply unit 3 may act as an electrode by being connected to the power supply unit 10 via the power delivery unit 11 to deliver power to the reaction chamber 2.

[0101] The power generator 8 can generate at least one of low frequency power (LRF) and high frequency power (HRF). The matching network 9 can match the impedance between the power generator 8 and the reaction chamber 2. The power delivery unit 11 can deliver power from the power supply unit 10 to the reaction chamber 2. The power delivery unit 11 can include a rod made of a conductive material and a power delivery cable.

[0102] The apparatus 1 may further include a gas source unit 20 including a first gas source 12 , a second gas source 13 , a third gas source 14 , a fourth gas source 16 and a fifth gas source 17 .

[0103] For example, the first gas source 12 may include a first silicon source including acetoxysilane. For example, the second gas source 13 may include a second silicon source including an alkyl group and an alkylamine group. The third gas source 14 may include an inert gas as a source carrier gas. The fourth gas source 16 may include a hydrogen source. The fifth gas source 17 may include an inert gas as a purge gas.

[0104] The first gas source 12 can supply a first silicon source gas to the reaction chamber 2 via the gas supply path 15 and the gas supply unit 3. The second gas source 13 can supply a second silicon source gas to the reaction chamber 2 via the gas supply path 15. The third gas source 14 can supply a carrier gas while the first and second silicon source gases are supplied to the reaction chamber 2 via the gas supply path 15.

[0105] The fourth gas source 16 can supply a hydrogen source gas to the reaction chamber 2 via the gas supply path 18 and the gas supply unit 3. The fifth gas source 17 can supply a purge gas to the reaction chamber 2 via the gas supply path 18.

[0106] In one or more embodiments, the substrate 5 can be processed in the reaction chamber 2 by a method including supplying the second silicon source gas to the substrate 5, and then supplying the first silicon source gas to the substrate 5. After the first silicon source gas is supplied, the reaction chamber 2 can be evacuated without supplying a gas.

[0107] After that, power can be applied to the reaction chamber 2 while the hydrogen source gas is supplied to the reaction chamber 2.

Claims

1. A method of forming a film on a substrate comprising a patterned structure, comprising: providing a substrate in a reaction chamber; and forming a film on the substrate by repeating cycles, the cycles comprising: supplying a first silicon source comprising acetoxy groups; and supplying a hydrogen source, wherein the hydrogen source reacts with the acetoxy groups of the first silicon source to form adsorption sites reactive to acetoxy groups, wherein the film formed on the substrate comprises silicon oxycarbide (SiOC).

2. The method of claim 1, wherein, The first silicon source comprises acetoxy silane.

3. The method of claim 2, wherein, The first silicon source includes at least one of triacetoxy methyl silane [(CH3CO2)3SiCH3], triacetoxy ethyl silane [(CH3CO2)3SiCH2CH3], diacetoxy dimethyl silane [(CH3CO2)2Si(CH3)2], triacetoxy (vinyl) silane [(CH3CO2)3SiCH=CH2], 1,3-diacetoxy- 1,3-dimethyl- 1,3-disilane [C8H 16 O4Si2], or mixtures thereof.

4. The method of claim 1, wherein, The hydrogen source comprises at least one of atomic hydrogen and dihydrogen or a mixture thereof.

5. The method of claim 1, wherein, The adsorption sites comprise hydroxyl groups (-OH).

6. The method of claim 1, wherein, The power is applied to the reaction chamber while the hydrogen source is being supplied, wherein the power can be applied to activate the hydrogen source at a frequency between about 10 MHz and about 100 MHz at an intensity between about 100 W and about 300 W.

7. The method of claim 6, wherein, The power is applied in-situ or remotely.

8. The method of claim 7, wherein, The power is applied to the reaction chamber in pulses.

9. The method of claim 1, wherein, The method is performed at a temperature between about 100 °C and about 500 °C.

10. The method of claim 1, wherein, The method is performed at a pressure of about 3 Torr or less.

11. The method of claim 1, wherein, The film growth rate of the film is about or more.

12. The method of claim 1, further comprising purging the reaction chamber at least one of after supplying the first silicon source and after supplying the hydrogen source.

13. The method of claim 12, wherein, Purging the reaction chamber after supplying the first silicon source is performed by evacuating the reaction chamber.

14. The method of claim 1, further comprising supplying a second silicon source comprising at least one of the following: alkyl and alkyl amine groups, alkyl and silyl amine groups, alkyl and alkoxysilyl groups, alkoxysilyl and alkyl groups, alkoxy and silyl groups, alkyl and silyl groups or a mixture thereof, before or after supplying the first silicon source.

15. The method of claim 14, wherein, The second silicon source comprises at least one of N,N-diethyl-2,4,6,8-tetramethyl- cyclotetrasiloxane-2-amine [C8H 25 NO4Si4], (dimethylamino)trimethylsilane [(CH3)2NSi(CH3)3], bis(dimethylamino)dimethylsilane [(CH3)2N]2Si(CH3)2, ethoxy(trimethyl)silane [C2H5OSi(CH3)3], diethoxy(dimethyl)silane [(C2H5O)2Si(CH3)2], triethoxymethylsilane [(C2H5O)3SiCH3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2Si(OC2H5)3], bis(triethoxysilyl)methane [(C2H5O)3SiCH2CH2Si(OC2H5)3], 4,4,6,6-tetramethyl-3,7-dioxa-4,6-disilanonane [(C2H5O)(CH3)2SiCH2Si(CH3)2(OC2H5)], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H 20 O2Si2], 1,3,5-triethoxy-1,3,5-trimethyl-1,3,5-trisilane [C 12 H 30 O3Si3], 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilane [C 15 H 36 O6Si3], 1,3-diethoxy-1,3-dimethyl-1,3-disilane [C8H 16 O4Si2], or mixtures thereof.

16. The method of claim 14, wherein, The film comprises pores.

17. The method of claim 14, wherein, The film growth rate of the film is greater than 18. The method of claim 14, further comprising purging the reaction chamber at least one of after supplying the first silicon source, after supplying the second silicon source and after supplying the hydrogen source.

19. The method of claim 16, purging at least one of after supplying the first silicon source and after supplying the second silicon source is performed by evacuating the reaction chamber.

20. An apparatus for performing the method of claim 1, comprising: a reaction chamber; a gas source unit; a gas supply unit for supplying gas to the reaction chamber; a substrate support unit for supporting a substrate, the substrate support unit configured to face the gas supply unit; and a power supply unit comprising a power source to apply power to the reaction chamber, wherein the gas source unit comprises a first silicon source comprising acetoxy groups and a hydrogen source; and wherein the acetoxy groups and the hydrogen source react to form a silicon oxycarbide (SiOC) film on the substrate. ​

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