Low temperature thermal deposition of silicon containing films using low water content hydrogen peroxide

Abstract

Methods for low temperature thermal deposition of silicon-containing thin films are provided. The methods enable selective deposition on a variety of substrates with high deposition rates and short cycle times.

Description

[0001] Cross-references to related applications This application claims priority to the following co-pending U.S. provisional applications: U.S. Provisional Application No. 63 / 569,828, filed March 26, 2024, and U.S. Provisional Application No. 63 / 642,956, filed May 6, 2024, the disclosures of which are incorporated herein by reference in their entirety. Background Technology

[0002] Silicon dioxide (SiO2) and silicon carbide (SiOC) thin films are important materials in industry, widely used for insulation, passivation, encapsulation, and gate dielectric layers. These films can be used in a variety of applications, such as in semiconductor device manufacturing, where they can serve as permanent dielectric films or sacrificial structures, like hard masks, etch stop layers, or in photolithography processes such as double patterning; in biomedical and dental applications, such as coatings for powders containing active pharmaceutical ingredients or vaccines, scaffolds, shunts, and meshes for implantable devices, tissue engineering scaffolds, lenses, drug delivery devices (such as syringes, vials, or catheters), medical devices, biosensors, bioelectronic devices, or bioanalytical devices; or as coatings in industrial applications, such as metal passivation or corrosion protection, encapsulation of sensitive devices or compounds (such as organic light-emitting diodes, catalysts, or perovskite solar cells), or film coatings. Traditional thermal methods for depositing silicon-based thin films, such as thermochemical vapor deposition (CVD) or atomic layer deposition (ALD), require high processing temperatures and strong oxidants such as ozone, which may damage parts of the substrate. In contrast, plasma-enhanced chemical vapor deposition (PECVD) or plasma-enhanced atomic layer deposition (PEALD) can operate at temperatures with significantly lower specific heat than CVD and ALD, even down to room temperature. However, plasma-based processes suffer from visibility issues, limit the conformal properties of the thin film, are unsuitable for substrates with complex geometries or high aspect ratios, and often result in plasma damage to the substrate, which limits the applications that can use plasma.

[0003] Furthermore, both thermal ozone and plasma-based processes remove a significant portion of the carbon from the film, which is undesirable in many applications. While the thermal deposition of silica and silicon carbide at low temperatures (<150 °C) using water as an oxidant has been reported, and these processes generally protect silicon-carbon bonds, the kinetics of these reactions, even with amine-catalyzed enhancement, remain too slow for practical industrial applications in most cases. Therefore, while it is known that ALD films can be deposited at low temperatures onto temperature-sensitive materials or devices, most reports only discuss ALD films such as alumina, titanium dioxide, or zinc oxide, which can be deposited at low temperatures using weakly oxidizing water as an oxidant. Reports of low-temperature silica or silicon carbide films either employ plasma-based processes unsuitable for many material or device geometries or use impractical, slow deposition processes. Given their excellent barrier properties, dielectric properties, biocompatibility, and ease of chemical functionalization, there is a strong industry demand for practical low-temperature thermal atomic layer deposition processes for SiO2 and SiOC films.

[0004] Low-temperature (<150 °C) plasma-based atomic layer deposition (ALD) of silicon-based thin films has been widely used in industry, with numerous detailed studies reported. In particular, plasma-based ALD of silicon dioxide thin films has been applied in advanced multi-layer patterning lithography processes, where an ALD silicon dioxide film is conformally coated onto a lithographically defined mandrel, followed by anisotropic etching to reveal two features formed by silicon dioxide deposited on the mandrel sidewalls. This process can be repeated to achieve quadruple or octave patterning, as is known in the art. Due to the poor thermal and plasma stability of the developed photoresist, it is common practice to first expose and develop the photoresist, then etch the pattern into a mandrel-forming layer more suitable for subsequent silicon dioxide ALD deposition and etching processes to form the mandrel. However, issues regarding the plasma stability and film conformability of the mandrel remain.

[0005] Furthermore, in the field of area selective deposition (ASD), there is a desire for a low-temperature thermal process for depositing silicon-based thin films (such as silicon dioxide or carbon-containing silicon dioxide (SiOC)), where the film is deposited only on specific regions of the patterned substrate. Plasma-based ASD strategies face challenges because the strong chemical reactivity of plasma can rapidly erode the chemical barrier agents used to suppress the growth of non-target regions on the patterned substrate.

[0006] U.S. Patent No. 11,139,163 describes an example of a plasma-based ASD process in which a SiOC film is selectively deposited on dielectric regions of a substrate, rather than metallic regions, using a three-step sequence of alkoxysilane precursor, hydrogen-containing plasma, and fluorine-based etching at a temperature of approximately 200 °C. Due to the relatively high temperature and the strong plasma and etching conditions, selective passivation of non-grown regions using small-molecule organics would be challenging and unreported, thus limiting the selection of non-grown surfaces to those inherently exhibiting non-grown behavior in this process. Furthermore, the use of plasma challenges conformality in high aspect ratio structures, limiting the types of device structures to which this invention can be applied. Another limitation of this disclosure is that the plasma or etching process may damage the substrate, further limiting which substrate regions can be exposed to the deposition process. Another limitation is the use of alkoxysilanes, whose oxygen atoms are the source of oxygen in the deposited SiOC film. Alkoxysilanes have lower reaction rates with SiOC, silicon dioxide, or silicon nitride substrates compared to aminosilane precursors more commonly used in PEALD. Although not reported, it can be inferred that the growth rate of the disclosed process is correspondingly low, and this problem is further exacerbated by the need for etching to remove unwanted nucleation and film growth on unblocked non-target areas. This step not only adds a third process to the cycle but also reduces the required SiOC film thickness in each etching cycle, thus expected to reduce the overall growth rate of the process.

[0007] Non-selective thermal deposition of silicon-based thin films using ozone as an oxidant has been extensively studied. However, ozone has several limitations. First, the deposition rate is temperature-sensitive, typically dropping below the practical limit of 0.5 nm / cycle below 100 °C. Furthermore, like oxygen plasma, ozone is a strong oxidant, and its indiscriminate reactivity poses challenges for both the formation and selective deposition of carbon-containing SiOC thin films.

[0008] Hirose et al. Thin Solid Films (519; 270-275 (2010)) discusses atomic layer deposition of silica using tris(dimethylamino)silane as the silane source and ozone as the oxidant. The authors demonstrate that although ozone readily oxidizes the dimethylamino group of the precursor at room temperature, the resulting film needs to be exposed to water vapor at 155 °C to 160 °C to regenerate the hydroxylated surface required for subsequent deposition cycles.

[0009] Lee et al. Ceramics International(43; 2095-2099 (2017)) Atomic layer deposition (ALD) was used to deposit silica films at temperatures as low as 100 °C by combining bis(isopropylamino)silane with ozone. However, from 150 °C to 100 °C, the deposition rate decreased significantly, from about 0.125 nm / cycle to about 0.050 nm / cycle, indicating that further reduction in temperature while maintaining a practical deposition rate of at least 0.050 nm / cycle is unlikely.

[0010] Hiller et al. Angew. Chem. Int. Ed. 47, 6177-6179 (2008) developed an autocatalytic method for growing silica films using (3-aminopropyl)triethoxysilane, employing a three-step sequence of silane precursor, water, and ozone. The advantage of this process is that the precursor does not contain Si-H bonds that would remain in the final film, thus increasing the etching rate. However, the growth rate was not ideal, decreasing from 0.06 nm / cycle at 150 °C to 0.035 nm / cycle at 120 °C (the lowest reported temperature). The reported optimal cycle time of 73.2 seconds was also higher than expected in practical applications. Furthermore, the autocatalytic precursor used in this work is prone to undesirable polymerization reactions, potentially contaminating or damaging the chambers, piping, or pumps of the deposition equipment.

[0011] Ahn et al. J. Vac. Sci. Technol. A 35, 01B131 (2017) investigated atomic layer deposition using tris(dimethylamino)silane and ozone in a temperature range from 400 °C to 200 °C, with deposition rates decreasing from about 0.6 nm / cycle at 400 °C to about 0.3 nm / cycle at 200 °C.

[0012] Reports of selective processes using ozone are even more limited. U.S. Patent Application Publication No. 2024 / 0047196 discloses a selective thermal atomic layer deposition (ALD) process for depositing a silicon-based dielectric layer on a dielectric surface (rather than a metal surface), utilizing a repeating three-step “ABC” sequence of barrier agent, silicon precursor, and oxidant. The relatively high temperature and strong ozone oxidation conditions in the disclosed example cause partial oxidation of the barrier layer, requiring reapplication of the barrier layer during each cycle. Furthermore, the disclosed process requires a metal oxidation step prior to the repeating “ABC” growth cycles, which may be disadvantageous in some applications. Moreover, because the barrier layer needs to be rebuilt for each cycle, this disclosure limits it to a “dielectric layer to dielectric layer” selective deposition process with a non-metallic growth surface; if the newly grown surface is chemically similar to any non-grown surface, barrier layer reconstruction cannot be achieved. Another limitation of this disclosure is that the disclosed process is limited to ten ALD cycles using a hydrocarbon-based barrier agent or thirty cycles using a perfluorinated barrier agent. Although the resulting film thickness was not reported, based on data from similar precursors provided by Lee et al. and Ahn et al., ten and thirty ALD cycles are expected to produce films with thicknesses of less than 1 nm and 3 nm, respectively, far below the industry-relevant target of 5 nm to 10 nm or more. Furthermore, the perfluorinated materials used are undesirable due to their environmental impact and the resulting regulatory issues. A further limitation of the disclosed example is that silicon-carbon bonds are incompatible with ozone oxidation, in which they are easily broken. Therefore, this disclosure is limited to substantially carbon-free films. Carbon-silicon-based films are highly desirable due to their lower dielectric constant compared to silicon dioxide.

[0013] There are relatively few studies on the use of hydrogen peroxide / aqueous solution as an oxidant in the formation of silicon-based thin films via atomic layer deposition. Burton et al. (… J. Phys. Chem. C Atomic layer deposition of silica using tris(dimethylamino)silane as the silane source and aqueous hydrogen peroxide solution as the oxidant in the temperature range of 150 °C to 500 °C was discussed in [Reference 113, 19, 8249-8257 (2009)]. The report showed that the growth rate of the silica film per cycle decreased significantly with temperature, dropping to 0.046 nm / cycle at 150 °C. Data at lower temperatures were not reported, nor was selectivity discussed. Due to the relatively high temperatures required for practical deposition rates, selectivity is expected to be difficult to achieve because chemical barrier agents typically used to suppress the growth of non-target areas on patterned substrates are unstable at high temperatures. Furthermore, the hydrogen peroxide / water used in this work may not be suitable for industrial applications in vapor deposition systems because water and hydrogen peroxide have different vapor pressures, and water consumption leads to faster concentration changes, causing process fluctuations. Additionally, the reported approximately 10 8 -10 9The high hydrogen peroxide utilization requirement of the Langmuir method may be a limitation to further implementation of this method. The Langmuir method, as defined herein, involves exposing the substrate to 10... -6 The pressure from torr lasts for 1 second.

[0014] Water has also been studied as an oxidant for forming silicon-based thin films via ALD. However, water has low reactivity with silane precursors, and even with catalysis by compounds such as ammonia or triethylamine, the cycle time is impractical for production. For example, Arl et al. ( RSC Adv. A study (10, 18073 (2020)) reported room-temperature silica deposition using SiCl4 as the silicon source, water as the oxidant, and ammonia as the catalyst. While a growth rate of 0.18 nm / cycle was achieved, the corresponding cycle time of 810 seconds was unsuitable for practical applications. Furthermore, significant chlorine contamination of the film rendered it unsuitable for certain applications.

[0015] In another example of a water-based ALD process for forming silicon-containing thin films, Yu et al. ( Chem. Mater The study (33, 902-909 (2021)) discussed the selective deposition of SiOC films on oxide substrates by using alkyl thiols as a metal barrier and alternating sequences of silane precursors bis(trichlorosilyl)methane and water to grow films incorporating carbon bridged in the silane precursors. While good selectivity was achieved, with films up to 10 nm thick selectively grown at a good growth rate of 0.148 nm / cycle, the reported cycle time of 1232 seconds was still unsuitable for practical applications. Furthermore, chlorine contamination caused by the chlorosilane precursors was also a problem for some applications.

[0016] U.S. Patent Application Publication No. 2022 / 0213597 discloses a method for silica deposition using tetraisocyanate silane as a precursor and a mixture of water and triethylamine as an oxidant system. While the growth per cycle is sufficient at 50 °C, reaching 0.138 nm / cycle, and the process is halogen-free and compatible with silicon-carbon bonds, the cycle time of >240 seconds is unacceptable for practical applications, and the long precursor exposure time of 120 seconds implies high precursor consumption.

[0017] Organic molecules have also been used as oxidants in SiOC thin film deposition. A process for depositing SiOC thin films using specific silicon precursors and oxygen-containing organic oxidants (such as glycols and diketones) is disclosed in U.S. Patent Nos. 11,186,909 and 11,447,865. A high temperature of at least 200 °C is required. Deposition rate data based on time or per cycle are not provided, but are expected to be slow. To obtain the film properties required for practical applications, the resulting film typically needs to be densified by a plasma-based process.

[0018] Among the currently known methods, ALD schemes using chlorosilanes and water to form SiOC or SiO2 films (regardless of whether amine catalysis is employed) all have cycle times exceeding 10 minutes, limiting their practicality. Similarly, previous attempts to form SiOC films using isocyanate silanes and water resulted in unacceptably long cycle times (exceeding 4 minutes).

[0019] The industry still has a strong need for a low-temperature thermal method to form SiO2 and SiOC thin films with deposition rates comparable to current high-temperature thermal CVD or plasma-based CVD or ALD processes. The desired approach is a purely thermal process for atomic-level deposition of silicon dioxide and SiOC thin films at low temperatures, with acceptable deposition rates and film properties, without the use of strong oxidants or plasmas that could damage the substrate or its features, strip or damage barrier or passivation layers, or remove most or almost all of the carbon from the SiOC film. Summary of the Invention

[0020] An aspect of the present invention relates to a method for depositing a silicon-oxygen-containing layer on a substrate, the method comprising: (a) Introducing the substrate into the reaction zone of the deposition chamber; (b) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (c) Performing a thermal atomic layer deposition process on a substrate by alternately exposing the substrate to at least one silicon-containing compound and low-water-content hydrogen peroxide to form a silicon-oxygen-containing layer on the substrate until the desired layer thickness is obtained.

[0021] A further aspect of the invention relates to a method for depositing a silicon-carbon layer on a substrate, the method comprising: (f) Introducing the substrate into the reaction zone of the deposition chamber; (g) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (h) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (i) Repeat step (h) until the desired layer thickness is obtained: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C2) 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental and is O, N(R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl or -C(R 73 (R) 74 )-C(R75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl or -Si(R) 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8 alkyl), straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and forms a ring with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R ... 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64 Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen bond or silicon-halogen bond, and at least one silicon-carbon bond.

[0022] Another aspect of the present invention relates to a method for selectively depositing a silicon-containing layer on a patterned substrate, the method comprising: (j) Introducing a patterned substrate into the reaction zone of the deposition chamber; (k) Heat or cool the reaction zone to approximately 0 °C to approximately 150 °C; (l) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to hydrogen peroxide with low water content and at least one silicon-containing compound having formula 1, 2, 3, 4 or 5 to form a silicon-containing layer on the substrate until the desired layer thickness is obtained; or (m) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to a substrate, optionally separated by a purge of the reaction zone, and optionally separated by exposure to low-water-content hydrogen peroxide; and (n) Repeat step (m) until the desired layer thickness is achieved; The method further includes: Before step (j): (j2) Perform one or more substrate passivation steps; and / or Before step (k): (k2) Perform one or more substrate passivation steps; Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C2) 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental and is O, N(R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl groups, or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl, or -Si(R 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and forms a ring with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R ... 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64 Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

[0023] Advantageous improvements to the invention may be implemented individually or in combination, as specified in the dependent claims.

[0024] In summary, the following embodiments are proposed as particularly preferred within the scope of this invention: Implementation Method 1: A method for depositing a silicon-oxygen-containing layer on a substrate, the method comprising: (a) Introducing the substrate into the reaction zone of the deposition chamber; (b) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (c) Performing a thermal atomic layer deposition process on a substrate by alternately exposing the substrate to at least one silicon-containing compound and low-water-content hydrogen peroxide to form a silicon- and oxygen-containing layer on the substrate until the desired layer thickness is obtained.

[0025] Implementation Method 2: According to the method of Implementation Method 1, the method further includes the following step (a): (a1) The substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0026] Implementation Method 3: The method according to Implementation Method 1 or 2 further includes, after step (a) and before step (b): (b1) The reaction zone is heated or cooled to about 0 °C to about 800 °C, and the substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0027] Embodiment 4: The method according to any one of Embodiments 1 to 3, wherein the at least one silicon-containing compound has Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R)27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds.

[0028] Embodiment 5: The method according to any one of Embodiments 1 to 4, wherein the at least one silicon-containing compound is tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, 1,3, 5-Tris(1-methylethyl)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disilane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane or tri(di-sec-butylamino)silane.

[0029] Implementation Method 6: According to the method of Implementation Method 5, the at least one silicon-containing compound is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane or tris(isopropylamino)silane.

[0030] Implementation method 7: The method according to any one of embodiments 1 to 6, wherein the temperature of the reaction zone in step (b) is below about 100 °C.

[0031] Implementation method 8: According to the method of implementation method 7, wherein the temperature of the reaction zone in step (b) is below about 50 °C.

[0032] Embodiment 9: The method according to any one of Embodiments 1 to 8, wherein the hydrogen peroxide contains less than about 30 percent by weight of water.

[0033] Implementation 10: The method according to Implementation 9, wherein the hydrogen peroxide contains less than about 20 percent by weight of water.

[0034] Embodiment 11: The method according to Embodiment 10, wherein the hydrogen peroxide contains less than about 10% by weight of water.

[0035] Implementation 12: The method according to any one of Implementations 1 to 11, wherein the deposition rate of the silicon-oxygen layer is greater than about 0.3 angstroms / cycle and the cycle time is less than about 120 seconds.

[0036] Implementation 13: The method according to Implementation 12, wherein the deposition rate of the silicon-oxygen layer is greater than about 0.5 angstroms / cycle and the cycle time is less than about 60 seconds.

[0037] Implementation Method 14: The method according to any one of Implementation Methods 1 to 13, wherein after step (c), the method further includes: (d) Heating or cooling the reaction zone to approximately 0°C to approximately 800°C; and (e) The substrate is subjected to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

[0038] Implementation method 15: The method according to implementation method 14 further includes the following after step (e); (o) Repeat steps (a) or (a1) to (e) until the desired layer thickness is achieved.

[0039] Embodiment 16: The method according to any one of Embodiments 1 to 15, wherein the substrate comprises a semiconductor device, an active pharmaceutical ingredient, a pharmaceutical product, a polymer, or a polymer film.

[0040] Embodiment 17: A method for depositing a silicon-carbon layer on a substrate, the method comprising: (f) Introducing the substrate into the reaction zone of the deposition chamber; (g) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (h) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (i) Repeat step (h) until the desired layer thickness is obtained: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34(R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C2) 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental, and is O or N (R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl or -Si(R) 54 (R) 55 (R) 56 ); R 54R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8 alkyl), straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and forms a ring with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R) 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 and R 64 Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

[0041] Implementation 18: The method according to Implementation 17, wherein, except for the final exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the surface of the available substrate, or are subsequently exposed to hydrogen peroxide with low water content.

[0042] Implementation 19: The method according to implementation 17 or 18 further includes the following before step (f): (f1) The substrate is subjected to at least one non-in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0043] Implementation Method 20: The method according to any one of Implementation Methods 17 to 19 further includes, after step (f) and before step (g): (g1) The reaction zone is heated or cooled to about 0 °C to about 800 °C, and the substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0044] Embodiment 21: The method according to any one of Embodiments 17 to 20, wherein at least one of the silicon-containing compounds of Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5 is tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di( Dimethylamino)silane, 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di-sec-butylaminosilane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tris(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disiloxane Alkane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane or tri(di-sec-butylamino)silane.

[0045] Embodiment 22: According to the method of Embodiment 21, at least one of the silicon-containing compounds having Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5 is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane or tris(isopropylamino)silane.

[0046] Embodiment 23: The method according to any one of Embodiments 17 to 22, wherein at least one of the silicon-containing compounds of Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10 is tris(dimethylamino)methylsilane, di(diethylamino)methylsilane, di(isopropylamino)methylsilane, dimethylamino(dimethoxy)methylsilane, tris(dimethylamino)(tert-butyl)silane, tris(dimethylamino)phenylsilane, or dimethylamino(dimethyl)cyclosilane. Hexylsilane, 2-(dimethylaminosilyl)bicyclo[2.2.1]heptane, tris(dimethylamino)decylsilane, N-methyl-aza-2,2,4-trimethylsilazopentane, N-trimethylsilyl-aza-4-methylsilazopentane, N-(n-butyl)-aza-silazopentane, N-ethyl-aza-4-methyl-2,2-dimethoxysilazopentane, 1,2,2,3-tetramethyl-1,3-diaza-2-silyl Heterocyclopentane, N-methyl-aza-4-methyl-2-methoxy-2-(n-butyl)silane, bis(dimethylaminomethylsilyl)methane, bis(tris(dimethylamino)silyl)methane, bis(bis(dimethylamino)methylsilyl)methane, 1,1-bis(tris(dimethylamino)silyl)ethane, bis(bis(dimethylamino)methylsilylamino)-(dimethylamino)methylsilane, (bis(dimethylamino)methylsilylamino)-bis(dimethylamino)silane 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trimethyl-2,4,6-trisylcyclohexane, 2,2,5,5-tetramethyl-1-aza-2,5-disiloxane, dimethylamino(trimethoxy)silane or N-trimethylsilyl-aza-siloxane Embodiment 24: According to the method of Embodiment 23, wherein at least one of the silicon-containing compounds of Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10 is tris(dimethylamino)methylsilane, bis(tris(dimethylamino)silyl)methane, N-methyl-aza-2,2,4-trimethylsilanecyclopentane or bis(dimethylaminomethylsilyl)methane.

[0047] Implementation Method 25: The method according to any one of Implementation Methods 17 to 24, wherein the temperature of the reaction zone in step (g) is below about 100°C.

[0048] Implementation Method 26: The method according to Implementation Method 25, wherein the temperature of the reaction zone in step (g) is below about 50°C.

[0049] Embodiment 27: The method according to any one of Embodiments 17 to 26, wherein the hydrogen peroxide contains less than about 30 percent by weight of water.

[0050] Implementation 28: The method according to Implementation 27, wherein the hydrogen peroxide contains less than about 20 percent by weight of water.

[0051] Implementation 29: The method according to Implementation 28, wherein the hydrogen peroxide contains less than about 10% by weight of water.

[0052] Implementation 30: The method according to any one of Implementations 17 to 29, wherein the deposition rate of the silicon-carbon layer is greater than about 0.3 angstroms / cycle and the cycle time is less than about 120 seconds.

[0053] Implementation 31: The method according to Implementation 30, wherein the deposition rate of the silicon-carbon layer is greater than about 0.5 angstroms / cycle and the cycle time is less than about 60 seconds.

[0054] Implementation Method 32: The method according to any one of Implementation Methods 17 to 31, wherein after step (i), the method further includes: (d) Heating or cooling the reaction zone to approximately 0°C to approximately 800°C; and (e) subject the substrate to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

[0055] Implementation method 33: The method according to implementation method 32 further includes the following step after step (e); (o) Repeat steps (f) or (f1) to (e) until the desired layer thickness is achieved.

[0056] Embodiment 34: The method according to any one of Embodiments 17 to 33, wherein the substrate comprises a semiconductor device, an active pharmaceutical ingredient, a pharmaceutical product, a polymer, or a polymer film.

[0057] Embodiment 35: A method for selectively depositing a silicon-containing layer on a patterned substrate, the method comprising: (j) Introducing a patterned substrate into the reaction zone of the deposition chamber; (k) Heat or cool the reaction zone to approximately 0°C to approximately 150°C; (l) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to hydrogen peroxide with low water content and at least one silicon-containing compound having formula 1, 2, 3, 4 or 5 to form a silicon-containing layer on the substrate until the desired layer thickness is obtained; or (m) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (n) Repeat step (m) until the desired layer thickness is achieved; The method further includes: Before step (j): (j2) Perform one or more substrate passivation steps; and / or Before step (k): (k2) Perform one or more substrate passivation steps; Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and cyclic with adjacent nitrogen atoms; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy, or -N(R 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl, or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and wherein at least half of the bonds to silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C2) 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental, and is O or N (R)53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl groups, or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl, or -Si(R 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8 alkyl), straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and cyclic with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R) 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

[0058] Implementation 36: The method according to Implementation 35, wherein, except for the final exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the surface of the available substrate, or are subsequently exposed to hydrogen peroxide with low water content.

[0059] Implementation method 37: The method according to implementation method 35 or 36 further includes, before or after step (j2): (j1) The patterned substrate is subjected to at least one non-in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

[0060] Implementation method 38: The method according to any one of implementation methods 35 to 37 further includes, before or after step (k2): (k1) The reaction zone is heated or cooled to about 0°C to about 800°C, and the patterned substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification, passivation or plasma treatment.

[0061] Implementation 39: The method according to any one of Implementations 35 to 38, wherein at least one passivation step (j2) or (k2) satisfies the following condition: (i) When the substrate comprises silicon dioxide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or germanium dioxide, the patterned substrate is exposed to a compound having Formula 11 or Formula 12 to selectively passivate regions of the substrate; or (ii) When the substrate comprises silicon nitride, titanium nitride, tantalum nitride, or germanium nitride, the patterned substrate is exposed to a compound containing aldehyde functional groups to selectively passivate regions of the substrate; or (iii) When the substrate comprises copper, cobalt, molybdenum, ruthenium, and / or tungsten, the patterned substrate is exposed to N-heterocyclic carbene or sulfur- or phosphorus-containing compounds to selectively passivate regions of the substrate; or (iv) When the substrate comprises silicon, germanium, copper, cobalt, molybdenum, ruthenium, or tungsten, the patterned substrate is exposed to a compound of Formula 13 to selectively passivate regions of the substrate; or (v) When the substrate comprises aluminum oxide, the patterned substrate is exposed to a compound of formula 11, 12, 14, or 15 to selectively passivate regions of the substrate: Where R 81 R 82 R 83 and R 84 Independently hydrogen, halogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R) 96 (R) 97 ), where R 96 and R 97 Independently hydrogen or (C1-C8) alkyl, and R 81 R 82 R 83 and R 84 At least one of them is a straight-chain or branched (C1-C8) alkyl group, and at least one is an N(R) alkyl group. 96 )R 97 ;R 85 and R 86 It is hydrogen, halogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R 96 (R) 97 ); R 88 R 89 R 90 and R 91 Independently hydrogen or (C1-C) 18 )alkyl, and R 88 R 89 R 90 Or R 91 At least one of them is hydrogen, and at least one is (C1-C) 18 ) alkyl; T is a straight-chain or branched (C1-C4) alkyl; R 92 R 93 R 94 and R 95It is hydrogen or (C1-C4) alkyl; wherein R 87 It is a hydrogen or a straight-chain or branched (C1-C4) alkyl group; and wherein n and m are 1, 2 or 3.

[0062] Embodiment 40: The method according to any one of Embodiments 35 to 39, wherein the silicon-containing compound having Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5 is tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)disil ... Silane, 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disiloxane Alkane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane or tri(di-sec-butylamino)silane.

[0063] Embodiment 41: According to the method of Embodiment 40, the silicon-containing compound having Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5 is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane or tris(isopropylamino)silane.

[0064] Embodiment 42: The method according to any one of Embodiments 35 to 41, wherein the silicon-containing compound having Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10 is tris(dimethylamino)methylsilane, di(diethylamino)methylsilane, di(isopropylamino)methylsilane, dimethylamino(dimethoxy)methylsilane, tris(dimethylamino)(tert-butyl)silane, tris(dimethylamino)phenylsilane, dimethylamino(dimethyl)cyclohexylsilane, 2-(dimethylaminosilyl)bicyclo[2.2.1]heptane, tris(dimethylamino)decylsilane, N-methyl-aza-2,2,4-trimethylsilazopentane, N-trimethylsilyl-aza-4-methylsilazopentane, N-(n-butyl)-aza-silazopentane, N-ethyl-aza-4-methyl-2,2-dimethoxysilazopentane, 1,2,2,3-tetramethyl-1,3-diaza-2-silazopentane N-Methyl-aza-4-methyl-2-methoxy-2-(n-butyl)silane, bis(dimethylaminomethylsilyl)methane, bis(tris(dimethylamino)silyl)methane, bis(bis(dimethylamino)methylsilyl)methane, 1,1-bis(tris(dimethylamino)silyl)ethane, bis(bis(dimethylamino)methylsilylamino)-(dimethylamino)methylsilane, (bis(dimethylamino)methylsilylamino)-bis(dimethylamino)methylsilane Silane, bis(bis(dimethylamino)silyl)methane, (bis(ethylamino)methylsilyl)bis(ethylamino)methylsilane, 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trimethyl-2,4,6-trisilacyclohexane, 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, dimethylamino(trimethoxy)silane, or N-trimethylsilyl-aza-sililacyclopentane.

[0065] Embodiment 43: According to the method of Embodiment 42, wherein the silicon-containing compound having Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10 is tris(dimethylamino)methylsilane, bis(tris(dimethylamino)silyl)methane, N-methyl-aza-2,2,4-trimethylsilanecyclopentane or bis(dimethylaminomethylsilyl)methane.

[0066] Implementation method 44: The method according to any one of implementation methods 35 to 43, wherein the temperature of the reaction zone in step (k) is below about 100°C.

[0067] Implementation 45: The method according to Implementation 44, wherein the temperature of the reaction zone in step (k) is below about 50°C.

[0068] Embodiment 46: The method according to any one of Embodiments 35 to 45, wherein the hydrogen peroxide contains less than about 30 percent by weight of water.

[0069] Embodiment 47: The method according to Embodiment 46, wherein the hydrogen peroxide contains less than about 20 percent by weight of water.

[0070] Embodiment 48: The method according to Embodiment 47, wherein the hydrogen peroxide contains less than about 10% by weight of water.

[0071] Implementation 49: The method according to any one of Implementations 35 to 48, wherein the deposition rate of the silicon-containing or silicon-containing carbon layer is greater than about 0.3 angstroms / cycle and the cycle time is less than about 120 seconds.

[0072] Implementation 50: The method according to Implementation 49, wherein the deposition rate of the silicon-containing or silicon-containing carbon layer is greater than about 0.5 angstroms / cycle and the cycle time is less than about 60 seconds.

[0073] Embodiment 51: The method according to any one of Embodiments 35 to 50, wherein the patterned substrate has a growth surface and a non-growth surface, and the selection ratio between the growth surface and the non-growth surface is at least about 2:1.

[0074] Implementation 52: According to the method of implementation 51, the selection ratio between the grown surface and the non-grown surface is at least about 5:1.

[0075] Implementation 53: According to the method of implementation 52, the selection ratio between the grown surface and the non-grown surface is at least about 10:1.

[0076] Implementation method 54: The method according to any one of embodiments 35 to 53, wherein after step (l) or (n), the method further includes: (d) Heat or cool the reaction zone to approximately 0°C to approximately 800°C; and (e) The substrate is subjected to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

[0077] Implementation 55: The method according to implementation 54 further includes the following step after step (e); (o) Repeat steps (j) or (j2) to (e) until the desired layer thickness is achieved.

[0078] Embodiment 56: The method according to any one of Embodiments 35 to 55, wherein the substrate comprises a semiconductor device, an active pharmaceutical ingredient, a drug, a polymer, or a polymer film.

[0079] Brief description of the attached figures The foregoing summary of the invention and the following detailed description of the invention will be better understood when read in conjunction with the accompanying drawings. The drawings illustrate currently preferred embodiments for the purpose of illustrating the invention. However, it should be understood that the invention is not limited to the precise arrangements and tools shown. In the drawings: Figure 1 It is a graph showing the deposition rate of a silicon dioxide thin film according to an embodiment of the present invention, and is accompanied by comparative deposition rate data.

[0080] Detailed description of the invention This invention addresses industry needs by providing a novel thermal method for low-temperature deposition of silicon dioxide and silicon carbide, paving the way for advancements in a broad spectrum of electronic and semiconductor technologies. Furthermore, the disclosed process is applicable to the deposition of silicon dioxide or silicon carbide on a variety of temperature-sensitive substrates, such as polymer films, pharmaceutical compounds, or devices with temperature-sensitive components. This technique utilizes a thermal ALD process consisting of alternating exposure of the substrate to one or more silicon-containing precursors and low-water-content hydrogen peroxide. While previous work has reported the use of hydrogen peroxide / water mixtures as oxidants for SiO2 deposition, previous work focused on high-temperature regions where deposition rates decreased with decreasing temperature, and a minimum deposition rate was reported at 150 °C; no further data were reported below this temperature.

[0081] Surprisingly, it has now been discovered that low-temperature deposition (<150°C) of silicon dioxide can be achieved through the correct combination of precursor, hydrogen peroxide source, and deposition conditions, with the deposition rate increasing as the temperature decreases. As described in more detail below, film deposition at industrially relevant rates (up to 0.1 nm / cycle) and cycle times of less than one minute can be achieved at temperatures as low as 23°C. The low temperature of the process described herein, along with the absence of strong oxidants such as ozone or oxygen plasma, allows for controlled carbon introduction into the film by utilizing a second silicon precursor containing a carbon-containing portion (which is incorporated into the resulting silicon carbide (SiOC) film in a precise manner determined by the precursor sequence and pulse timing established in the ALD process). Unlike previous attempts to form SiOC films using ALD with chlorosilanes and water, the process described in this invention does not involve halogens, which typically remain in the film and severely degrade performance and reliability.

[0082] In addition to forming captive thin films such as SiO2 or SiOC, the microelectronics industry continues to require selective deposition processes in which thin films are deposited only on the target "growth" regions of a patterned substrate. The mild conditions and rapid deposition rates of the processes described in this paper, combined with appropriate passivation schemes for non-target "non-growth" regions of the patterned substrate, allow for a variety of selective processes that differentiate between different oxides, nitrides, and metals.

[0083] The term "patterned substrate" is well known in the art and refers to a substrate in which vias, pillars, channels, and trenches are formed by etching and / or other processes known in the art. It should also be understood that a "patterned substrate" can consist of regions or areas of different elemental or chemical compositions, such as substrates having discrete metallic and non-metallic regions, substrates having discrete hydrogen-containing and hydrogen-free layers on conductive and semiconductor regions, and / or substrates having discrete conductor and insulator regions, said regions having hydroxyl-free and hydroxyl-containing surfaces, respectively.

[0084] Unless otherwise stated, any numerical value should be understood to be modified by the term "about" in all cases. Therefore, numerical values ​​typically include ±10% of the stated value. For example, a temperature description such as "10 °C" or "about 10 °C" includes 9 °C and 11 °C and all temperatures in between.

[0085] All numerical ranges expressed in this invention explicitly encompass all possible subranges, all individual numerical values ​​within that range, including integers within such ranges, as well as fractions and decimals, unless the context clearly indicates otherwise. For example, the temperature range from 0°C to approximately 150°C includes 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, and 150°C, as well as all intermediate temperatures and ranges. These temperatures can all be referred to as "low temperatures".

[0086] The term "thin film" is well known in the art and can include films with thicknesses ranging from a few angstroms to a few micrometers. More specifically, the term "thin film" can be understood as referring to a film with a thickness of less than about 1,000 nm, preferably between about 0.3 nm and about 100 nm, more preferably between about 1 nm and about 30 nm, and even more preferably between about 3 nm and about 20 nm. For the purposes of this invention, the terms "layer," "film," and "thin film" are synonymous.

[0087] In some embodiments, low-water-content hydrogen peroxide is used as an oxidant for forming silicon dioxide or silicon carbide films. Low-water-content hydrogen peroxide can be delivered in a variety of ways, including steam extraction, bubbling, or direct liquid injection. The low-water-content hydrogen peroxide described herein preferably contains less than about 30% by weight of water, more preferably less than about 20% by weight of water, and even more preferably less than about 10% by weight of water. While not limiting, the low-water-content hydrogen peroxide source can be a hydrogen peroxide / water liquid mixture, such as a mixture containing at least about 70% by weight of hydrogen peroxide in water, or a hydrogen peroxide / water mixture adsorbed onto a solid. Currently preferred low-water-content hydrogen peroxide sources for use in the applications of this invention are BRUTE hydrogen peroxide (RASIRC, San Diego, CA), which comprises high-purity (>95%) hydrogen peroxide adsorbed onto a proprietary solid material encapsulated in a custom delivery container. A further advantage of the method described herein is the very low consumption of low-water-content hydrogen peroxide. Compared to the use of a 50% aqueous hydrogen peroxide solution reported by Burton et al., the consumption is significantly lower. 8 -10 9 Compared to Langmuir's hydrogen peroxide exposure, the method described in this paper requires only about 10 per deposition cycle. 6 -10 7 Langmuir's hydrogen peroxide reduces the cost of materials and processing and mitigates the possibility of unwanted reactions or oxidation.

[0088] According to the aspects described herein, the use of a low-water-content hydrogen peroxide source enables high deposition rates to be achieved at temperatures below 150°C, as demonstrated in Comparative Examples 2 and 3. The film growth rate in the disclosed process is inversely proportional to increasing temperature. The preferred temperature range for the process described herein is from about 0°C to about 150°C, a more preferred temperature range is from about 0°C to about 75°C, and the most preferred temperature range is from about 0°C to about 50°C, encompassing all intermediate temperatures and ranges.

[0089] The first method A first aspect of the invention relates to a low-temperature thermal process for atomic layer deposition of silicon-oxygen thin films, the process using a selected silicon-based precursor and low-water-content hydrogen peroxide as an oxidant at temperatures below 150°C. The process includes the following steps, which will be described in more detail below: (a) Introducing the substrate into the reaction zone of the deposition chamber; (b) Heating or cooling the reaction zone to approximately 0°C to approximately 150°C; and (c) Performing a thermal atomic layer deposition process on a substrate by alternately exposing the substrate to at least one silicon-containing compound and low-water-content hydrogen peroxide to form a silicon-oxygen-containing layer on the substrate until the desired layer thickness is obtained.

[0090] In some embodiments, the method further includes, prior to step (a): (a1) The substrate is subjected to at least one non-in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0091] In some embodiments, the method further includes, after step (a) and before step (b): (b1) The reaction zone is heated or cooled to about 0°C to about 800°C, and the substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0092] Steps (a1) and (b1) are optional processes that can be used to prepare the substrate for the atomic layer deposition process in step (c). Steps (a1) and (b1) may include one or more processes known in the art, such as annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, or plasma treatment of the substrate. These processes may be performed independently before the substrate is placed into the atomic layer deposition tool or reactor, referred to as in-situ (step (a1)), or performed inside the atomic layer deposition reactor, referred to as in-situ (step (b1)). The temperature of any preparation step (a1) or step (b1) may be selected independently of the temperature of the atomic layer deposition process in step (c), and is not limited to the temperature range disclosed in step (b).

[0093] Step (c) is an atomic layer deposition process comprising exposing a substrate to at least one silicon-containing precursor, preferably but not limited to a precursor having formula 1, formula 2, formula 3, formula 4 and / or formula 5, for about 0.01 s to about 60 s, preferably about 0.1 s to about 20 s; optionally purging the reactor with an inert gas such as nitrogen, helium or argon for about 0 to about 120 s, preferably about 0 to about 30 s; exposing the substrate to a gas stream containing hydrogen peroxide with low water content for about 1 s to 120 s, preferably about 5 s to about 60 s; and optionally purging the reactor with an inert gas such as nitrogen, helium or argon for about 0 s to about 120 s, preferably about 0 to about 30 s.

[0094] In another preferred embodiment, step (c) includes exposing the substrate to a silicon-containing precursor having Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5 for about 1 to 10 s; optionally purging the reactor with an inert gas such as nitrogen, helium or argon for about 0 s to about 20 s; exposing the substrate to a gas stream containing hydrogen peroxide with low water content for about 5 s to about 30 s; and optionally purging the reactor with an inert gas such as nitrogen, helium or argon for about 0 s to about 20 s.

[0095] Suitable silicon precursors have formulas 1, 2, 3, 4, or 5: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 In equations 1-5, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy, or -N(R 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds.

[0096] Specific examples of compounds having formulas 1, 2, 3, 4, and 5 include tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, 1,3,5-tris(1-methyl)silane, and 1,3,5-tris(1-methyl)silane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,3,5-tris(1-methyl)silane, 1,4,6,9-tetramethylamino)dimethoxysilane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,5-tris(1-methyl)silane, 1,4,6,9-tetramethylamino)dimethoxy ... Ethyl)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disilane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, and tri(di-sec-butylamino)silane, as shown below. In a preferred embodiment, the temperature within the reaction zone in step (b) is below about 100°C or below about 50°C. In a preferred embodiment, as described in more detail below, the deposition rate of the silicon-oxide layer is greater than about 0.3 Å / cycle or greater than about 0.5 Å / cycle, and the cycle time is less than about 120 seconds or less than about 60 seconds.

[0097] The deposition rate of a silica thin film deposited using the process of the first aspect of the present invention and with tris(dimethylamino)silane as a precursor is shown in the figure. Figure 1 The study also provides comparative deposition rate information published in the literature ("Comparative Study of AF2-MoP7 Dielectric ALD Using Hydrogen Peroxide: Anhydrous H2O2, H2O2 / H2O Mixture and H2O in Growth and Film Properties," Daniel Alvarez). people? The 19th International Conference on Atomic Layer Deposition (RASIRC) (2019), and Burton people? ( J. Phys. Chem. C , 113, 19, 8249-8257 (2009)). At temperatures below 75 °C, an increase in deposition rate was observed when using hydrogen peroxide with low water content, but no increase in deposition rate was observed when using hydrogen peroxide with high water content (30% hydrogen peroxide in water) under the same conditions.

[0098] The second method A second aspect of the invention relates to a low-temperature thermal process for atomic layer deposition of silicon-carbon thin films, which uses a selected silicon-based precursor and low-water-content hydrogen peroxide as an oxidant at temperatures below 150 °C. The process for depositing a silicon-carbon layer on a substrate includes: (f) Introducing the substrate into the reaction zone of the deposition chamber; (g) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (h) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (i) Repeat step (h) until the desired layer thickness is obtained: In some embodiments, the method further includes the following steps prior to step (f): (f1) The substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0099] In some embodiments, the method further includes, after step (f) and before step (g): (g1) Heat or cool the reaction zone to about 0 °C to about 800 °C and subject the substrate to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

[0100] Steps (f1) and (g1) are optional processes that can be used to prepare the substrate for the atomic layer deposition process in steps (h) and (i). Steps (f1) and (g1) may include one or more processes known in the art, such as annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, or plasma treatment of the substrate. These processes may be performed independently before the substrate is placed into the atomic layer deposition tool or reactor, referred to as in-situ (step (f1)), or performed inside the atomic layer deposition reactor, referred to as in-situ (step (g1)). The temperature of any preparation step (f1) or step (g1) may be selected independently of the temperature of the atomic layer deposition process defined in steps (h) and (i), and is not limited to the temperature range disclosed in step (g).

[0101] In some embodiments of step (h), except for the final exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the usable substrate surface, or are subsequently exposed to hydrogen peroxide with low water content. In some embodiments of step (h), each exposure of the substrate to the two or more silicon-containing compounds covers only a portion of the usable substrate surface, or is subsequently exposed to hydrogen peroxide with low water content.

[0102] Steps (h) and (i) include an atomic layer deposition process comprising exposing a substrate to hydrogen peroxide with low water content, at least one silicon-containing precursor having formula 1, 2, 3, 4, or 5, and at least one precursor having silicon-carbon bonds and having formula 6, 7, 8, 9, or 10. At least two of the precursors may be simultaneously exposed for about 0.01 s to about 60 s, more preferably about 0.1 s to about 30 s, or most preferably about 1 s to about 10 s. Alternatively, at least two of the precursors may be exposed sequentially, each precursor for about 0.005 s to about 30 s, more preferably about 0.01 s to about 15 s, or most preferably about 0.1 s to about 10 s, optionally separated by purging with an inert gas such as nitrogen, helium, or argon for about 0 s to about 120 s, such that, except for the last exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the usable substrate surface, or the substrate may subsequently be additionally exposed to low-water-content hydrogen peroxide for about 1 s to about 120 s, preferably about 5 s to about 60 s, and most preferably about 5 s to about 30 s. Details of using subsaturated doses of silicon-containing precursors to cover only a portion of the usable substrate, thereby allowing for subsequent silicon-containing precursor reactions in the process, are discussed below. As an alternative to using subsaturated doses of silicon-containing precursors, any exposure of any precursor in the process can be followed by exposure to low-water-content hydrogen peroxide, which generates a chemically active surface on which the next precursor in the process can react. In other words, the sequence, conditions, and duration of exposing the substrate to low-water-content hydrogen peroxide, as well as to silicon-containing precursors having formulas 1, 2, 3, 4, and / or 5, and precursors having formulas 6, 7, 8, 9, and / or 10, are highly flexible and can be optimized through routine experiments.

[0103] After two or more silicon precursors are delivered to the substrate surface, the atomic layer deposition process continues: optionally, the reactor is purged with an inert gas such as nitrogen, helium, or argon for about 0 s to about 120 s, preferably about 0 s to about 30 s, and most preferably about 0 s to about 20 s; the substrate is exposed to a gas stream containing low-water-content hydrogen peroxide for about 1 s to about 120 s, preferably about 5 s to about 60 s, and most preferably about 5 s to about 30 s; and optionally, the reactor is purged with an inert gas such as nitrogen, helium, or argon for about 0 s to about 120 s, preferably about 0 s to about 30 s, and most preferably about 0 s to about 20 s. Switching between simultaneous and sequential delivery of silicon precursors in a single deposition process is also within the scope of this invention. The deposition steps are repeated until the desired layer or film thickness is obtained.

[0104] Suitable silicon precursors of the second aspect of the invention have formulas 1, 2, 3, 4, or 5, as described above, including specific examples of these compounds, and silicon-carbon bond-containing precursors have formulas 6, 7, 8, 9, and 10: Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 In these formulas, R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C2) 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental and is O or N (R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl groups, or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl, or -Si(R 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8 alkyl), straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and cyclic with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R) 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64 Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

[0105] Specific examples of compounds having formulas 6, 7, 8, 9, and 10 include tris(dimethylamino)methylsilane, di(diethylamino)methylsilane, di(isopropylamino)methylsilane, dimethylamino(dimethoxy)methylsilane, tris(dimethylamino)(tert-butyl)silane, tris(dimethylamino)phenylsilane, dimethylamino(dimethyl)cyclohexylsilane, and 2-(dimethylaminosilyl)bicyclo[2.2.1]heptane. Tris(dimethylamino)decylsilane, N-methyl-aza-2,2,4-trimethylsilazopentane, N-trimethylsilyl-aza-4-methylsilazopentane, N-(n-butyl)-aza-silazopentane, N-ethyl-aza-4-methyl-2,2-dimethoxysilazopentane, 1,2,2,3-tetramethyl-1,3-diaza-2-silazopentane, N-methyl-aza-4-methyl-2- Methoxy-2-(n-Butyl)silane, bis(dimethylaminomethylsilyl)methane, bis(tris(dimethylamino)silyl)methane, bis(bis(dimethylamino)methylsilyl)methane, 1,1-bis(tris(dimethylamino)silyl)ethane, bis(bis(dimethylamino)methylsilylamino)-(dimethylamino)methylsilane, (bis(dimethylamino)methylsilylamino)-bis(dimethylamino)methylsilane, bis( ...-bis(dimethylamino)-bis(dimethylamino) (amino)silyl)methane, (bis(ethylamino)methylsilyl)bis(ethylamino)methylsilane, 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trimethyl-2,4,6-trisilacyclohexane, 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, dimethylamino(trimethoxy)silane, and N-trimethylsilyl-aza-sililacyclopentane, as shown below. In a preferred embodiment, the temperature within the reaction zone in step (g) is below about 100°C or below about 50°C. In a preferred embodiment, as described in more detail below, the deposition rate of the silicon-carbon layer is greater than about 0.3 Å / cycle or greater than about 0.5 Å / cycle, and the cycle time is less than about 120 seconds or less than about 60 seconds.

[0106] The third method A third aspect of the invention relates to a selective thermal process for depositing atomic layers of silicon-containing or silicon-carbon-containing thin films on a patterned substrate using any of the above-described deposition processes. The low-temperature and mild oxidation conditions of the disclosed deposition processes are suitable for a variety of substrate passivation schemes, as described in the ASD procedures disclosed below.

[0107] Therefore, according to the aspects described above, the third method is a method for selectively depositing a silicon-containing layer on a patterned substrate, the method comprising: (j1) Perform at least one non-in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment on the patterned substrate; (j2) Optionally perform one or more substrate passivation steps; (j) Introducing a patterned substrate into the reaction zone of the deposition chamber; (k1) Optionally, the reaction zone is heated or cooled to about 0 °C to about 800 °C, and the substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment. (k2) Optionally perform one or more passivation steps; (k) Heat or cool the reaction zone to approximately 0 °C to approximately 150 °C; (l) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to hydrogen peroxide with low water content and at least one silicon-containing compound having formula 1, 2, 3, 4 or 5 to form a silicon-containing layer on the substrate until the desired layer thickness is obtained; or (m) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds is selected from Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5, and at least one of the two or more silicon-containing compounds is selected from Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10; wherein at least two of the at least two silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to a substrate, optionally separated by purge of the reaction zone, and optionally separated by exposure to low-water-content hydrogen peroxide; and (n) Repeat step (m) until the desired layer thickness is achieved; At least one passivation step (j2) or step (k2) is performed.

[0108] Therefore, the method can also be considered as including at least one of steps (j), (k), (l), (m), and (n), as well as (j2) and (k2). Step (j1) may be performed before or after step (j2), and step (k1) may be performed before or after step (k2).

[0109] In a preferred embodiment, except for the final exposure, all exposures of the substrate to two or more silicon-containing compounds in step (m) cover only a portion of the usable substrate surface, or are subsequently exposed to low-water-content hydrogen peroxide. The final exposure of the substrate to two or more silicon-containing compounds in step (m) may cover the entire substrate surface, or only a portion of the substrate surface.

[0110] Steps (m) and (n) comprise an atomic layer deposition process comprising exposing a substrate to hydrogen peroxide with low water content, at least one silicon-containing precursor having formula 1, 2, 3, 4, or 5, and at least one precursor having silicon-carbon bonds and having formula 6, 7, 8, 9, or 10. At least two of the precursors may be simultaneously exposed for about 0.01 s to about 60 s, more preferably about 0.1 s to about 30 s, or most preferably about 1 s to about 10 s. Alternatively, at least two of the precursors may be exposed sequentially, each precursor for about 0.005 s to about 30 s, more preferably about 0.01 s to about 15 s, or most preferably about 0.1 s to about 10 s, optionally separated by purging with an inert gas such as nitrogen, helium, or argon for about 0 s to about 120 s, such that, except for the last exposure, all exposures of the substrate to two or more silicon-containing compounds cover only a portion of the usable substrate surface, or the substrate is subsequently additionally exposed to low-water-content hydrogen peroxide for about 1 s to about 120 s, preferably about 5 s to about 60 s, and most preferably about 5 s to about 30 s. Details of using subsaturated doses of silicon-containing precursors to cover only a portion of the usable substrate, thereby allowing subsequent silicon-containing precursor reactions in the process, are discussed below. As an alternative to using subsaturated doses of silicon-containing precursors, any exposure of any precursor in the process can be followed by exposure to low-water-content hydrogen peroxide, which creates a chemically active surface to which the next precursor in the process can react. In other words, the sequence, conditions, and duration of exposure of the substrate to low-water-content hydrogen peroxide, as well as to silicon-containing precursors having formulas 1, 2, 3, 4, and / or 5, and to precursors having formulas 6, 7, 8, 9, and / or 10, are highly flexible and can be optimized through routine experiments.

[0111] In a preferred embodiment, at least one passivation step (j2) and / or step (k2) satisfies one of the following criteria: (i) When the substrate comprises silicon dioxide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or germanium dioxide, the patterned substrate is exposed to a region of the substrate having a compound of Formula 11 or Formula 12 to selectively passivate the substrate; or (ii) When the substrate comprises silicon nitride, titanium nitride, tantalum nitride, or germanium nitride, the patterned substrate is exposed to a compound containing aldehyde functional groups to selectively passivate regions of the substrate; or (iii) When the substrate contains copper, cobalt, molybdenum, ruthenium, and / or tungsten, the patterned substrate is exposed to N-heterocyclic carbene or sulfur- or phosphorus-containing compounds to selectively passivate regions of the substrate; or (iv) When the substrate comprises silicon, germanium, copper, cobalt, molybdenum, ruthenium, or tungsten, the patterned substrate is exposed to the compound of Formula 13 to selectively passivate regions of the substrate; or (v) When the substrate contains aluminum oxide, the patterned substrate is exposed to a compound of formula 11, formula 12, formula 14 or formula 15 to selectively passivate regions of the substrate. In Equation 11-15, R 81 R 82 R 83 and R 84 Independently hydrogen, halogen, straight-chain or branched (C1-C) 18 )alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R 96 (R) 97 ), where R 96 and R 97 Independently hydrogen or (C1-C) 18 )alkyl, and R 81 R 82 R 83 and R 84 At least one of them is a straight chain or a branched chain (C1-C) 18 )alkyl, at least one of which is N(R) 96 )R 97 ;R 85 and R 86 Hydrogen, halogen, straight-chain or branched (C1-C) 18 )alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R 96 (R) 97 ); R 88 R 89 R 90 and R 91 Independently hydrogen or (C1-C) 18 )alkyl, and R 88 R 89 R 90 Or R 91 At least one of them is hydrogen, and at least one is (C1-C) 18 ) alkyl; T is a straight-chain or branched (C1-C4) alkyl; R 92 R 93 R 94 and R 95 It is hydrogen or (C1-C4) alkyl; wherein R 87It is a hydrogen or a straight-chain or branched (C1-C4) alkyl group; and wherein n and m are 1, 2 or 3.

[0112] Compounds having formulas 1 to 10 have been previously described. In a preferred embodiment, the temperature of the reaction zone in step (k) is below about 100°C or below about 50°C. In a preferred embodiment, as described in more detail below, the deposition rate of the silicon-containing layer and / or the silicon-carbon-containing layer is greater than about 0.3 Å / cycle or greater than about 0.5 Å / cycle, and the cycle time is less than about 120 seconds or less than about 60 seconds.

[0113] The first method, the second method, and the third method In some embodiments of the first, second, and third aspects of the present invention, the method may further include the following additional steps after steps (c), (i), (l), or (n): (d) Heat or cool the reaction zone to approximately 0°C to approximately 800°C; and (e) Perform at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, or plasma treatment on the substrate. Step (e) may optionally include a passivation step. In this case, the passivation step shall meet the same criteria as steps (j2) and (k2).

[0114] In this case, the method may further include repeating steps (a) or (a1) to (e) until the desired layer thickness is reached, repeating steps (f) or (f1) to (e) until the desired layer thickness is reached, or repeating steps (j) or (j2) to (e) until the desired layer thickness is reached.

[0115] In some embodiments of the first, second, and third aspects of the invention, the deposition step is performed at a temperature of about 0°C to about 150°C, more preferably about 0°C to about 100°C, most preferably about 0°C to about 60°C, and at all intermediate temperatures. The preferred temperature for the pretreatment step depends on the nature of the step being performed and can be determined by those skilled in the art through conventional optimization.

[0116] As used herein, the term "substrate" or "substrate surface" refers to the base material on which modifications or additions are made. Examples of substrate surfaces relevant to semiconductor device fabrication include semiconductors such as silicon, germanium, or gallium arsenide; metals such as copper, cobalt, ruthenium, molybdenum, tungsten, or alloys thereof; oxides such as silicon dioxide, silicon carbide, titanium dioxide, hafnium dioxide, or aluminum oxide; or nitrides such as silicon nitride, silicon carbonitride, aluminum nitride, titanium nitride, or tantalum nitride.

[0117] Further examples of substrates include polymers or polymer films, metals, glass, inorganic powders, organic powders, metal powders, or powders containing active ingredients, such as vaccines, enzymes, active pharmaceutical ingredients, pharmaceuticals, catalysts, curing agents, anodes, cathodes, or electrolytic materials; natural materials such as wood, fibers, or paper; tissue-engineered scaffolds or membranes made of biological or synthetic materials; or reactive or temperature-sensitive materials, such as biomolecules, organic light-emitting compounds, phosphors, catalysts, perovskites, or two-dimensional nanosheets, such as graphene, molybdenum disulfide, tungsten disulfide, or MXenes. As used herein, the term substrate can refer to simple substrates, such as wafers, self-supporting films, sheets, wires, tubes, fibers, or powders; complex three-dimensional substrates, such as jewelry, lenses, vials, fabrics, supported catalysts, nanotubes, membranes, fabrics, or tissue scaffolds; or integrated devices, such as semiconductor chips, semiconductor wafers, semiconductor panels, solar panels, displays, filters, immobilized catalyst beds, microelectromechanical systems, batteries, or medical devices.

[0118] As used in this article, a semiconductor device is an electronic component that relies on the electronic properties of semiconductor materials to perform its function. A semiconductor wafer is any substrate used to manufacture semiconductor devices.

[0119] An active pharmaceutical ingredient, a drug product, or a pharmaceutical substance can refer to any substance or mixture of substances intended to be included in a final pharmaceutical product as a bioactive ingredient (or "active substance") and intended to provide pharmacological activity or other direct effects.

[0120] A polymer or polymer film can refer to any solid particles, granules, fibers, foams, or films made of polymeric materials, whether as a single object or as part of a larger device. While not limited thereto, suitable polymeric materials include polyethylene, polypropylene, polyethylene terephthalate, polystyrene, natural rubber, polyvinyl chloride, polyester, polyurethane, polytetrafluoroethylene, polycarbonate, polymethyl methacrylate, polyacrylonitrile, and polydimethylsiloxane.

[0121] Substrate surfaces can be processed or altered in a variety of ways, including pretreatment processes such as annealing, polishing, etching, hydroxylation, oxidation, reduction, passivation, compound modification, or plasma treatment. Furthermore, new layers of other materials can be deposited onto the substrate surface. Importantly, as used herein, the term "substrate surface" is flexible and can refer to the surface of the original substrate or any newly added layer. Moreover, substrate surfaces can be substantially planar or contain complex three-dimensional structures such as vias, trenches, pillars, or holes. The specific materials and processes used will determine the composition and structure of the final substrate surface.

[0122] As used herein, an "active," "usable," or "chemically active" region on the substrate surface is a region having a chemical functionality capable of chemically reacting with the disclosed silicon-containing precursor, low-water-content hydrogen peroxide, or the chemical passivating agent of step (j2) or (k2). While not limited thereto, examples of such chemical functionality include hydroxyl, alkoxy, hydride, amino, alkylamino, halogen, alkylaluminum, thiol, phosphine, and alkylphosphine.

[0123] In steps (h) and (m), two or more silicon-containing precursors—at least one of which must contain silicon-carbon bonds (such as preferred compounds having formulas 6 to 10) and at least one of which does not contain silicon-carbon bonds (such as preferred compounds having formulas 1 to 5)—may be sequentially exposed to the substrate surface in any order, such that all exposures of the substrate to the two or more silicon-containing compounds, except for the last exposure, only cover a portion of the available substrate surface. The last exposure of the substrate to the two or more silicon-containing compounds in step (h) or step (m) may cover the entire substrate surface or only a portion of the substrate surface. As defined herein, "coverage" means chemical reaction with chemical bonds on the substrate surface that are capable of reacting with the silicon-containing precursors. Therefore, the first silicon-containing precursor may not react with all available chemical bonds on the substrate surface, and only the last silicon-containing precursor may react with all available chemical bonds on the substrate surface. Another description of the method is that, except for the last silicon-containing precursor, the exposure dose of all silicon-containing precursors is subsaturated, while the exposure dose of the last silicon-containing precursor may be saturated or subsaturated.

[0124] As an alternative to steps (h) and (m), two or more silicon-containing precursors—at least one of which must contain silicon-carbon bonds (such as preferred compounds having formulas 6 to 10) and at least one of which does not contain silicon-carbon bonds (such as preferred compounds having formulas 1 to 5)—may be sequentially exposed to the substrate surface, interspersed with exposure to low-water-content hydrogen peroxide. In this case, the precursors other than the last one in the process may completely cover the entire surface or only partially cover the entire substrate surface, with intermediate exposure to low-water-content hydrogen peroxide forming an active surface with suitable chemical bonds to which the precursors in subsequent processes can react.

[0125] By implementing steps (h) and (m), two or more different precursors can be formed on the substrate surface to form a mixed layer. It should be understood that the deposition rate and proportion of silicon-containing precursors in the resulting film can be controlled by adjusting the precursor dosage during precursor exposure to the substrate, the duration of inert gas purging during precursor exposure, interspersing exposure of the substrate to low-water-content hydrogen peroxide in the process, or the order of exposure of two or more silicon-containing precursors, and can be determined by those skilled in the art through conventional optimization. Furthermore, implementing steps (h) and (m) within a single process using different methods is within the scope of the invention, for example, simultaneously exposing the substrate to two silicon-containing precursors and sequentially exposing it to a third.

[0126] As used herein, "silicon dioxide" refers to a film whose atomic composition (excluding hydrogen) is at least about 25% silicon and about 60% oxygen, and at most about 2% carbon and at most about 5% nitrogen; "silicon carbide" refers to a film whose atomic composition (excluding hydrogen) is at least about 90% silicon, oxygen, and carbon in total, at least about 2% carbon, and at most about 5% nitrogen. These atomic percentages are typically measured by X-ray photoelectron spectroscopy (XPS). Note that hydrogen is not included in these definitions because it cannot be measured by XPS.

[0127] In some embodiments, the process for depositing the thin films of the present invention may be described as a thermal "atomic layer deposition" or "thermal ALD" process. While not limiting, the atomic layer deposition process includes alternating exposure of a substrate to one or more chemical precursors that react with the substrate surface, and a second chemical substance that reacts with said one or more precursors to form a film, optionally purging the reaction zone with an inert gas to prevent gas-phase interactions between the chemical precursors and the second chemical substance. The alternating exposure of the precursors and the second compound can be achieved by alternating the movement of the precursors and the second compound into and out of the substrate-containing reaction zone (time-based ALD), or by alternating the movement of the substrate into different reaction zones, wherein at least one reaction zone contains one or more chemical precursors and at least one reaction zone contains the second compound (space-based ALD). The duration of substrate exposure to the precursor or compound is referred to as a "pulse" and is typically from milliseconds to tens of seconds, as defined herein with respect to specific steps of the process of the present invention.

[0128] In some embodiments, the process described herein may be a "region-selective" or "selective" deposition process. A selective deposition process involves using a patterned substrate composed of two or more different constituent regions, such that the film thickness deposited by the deposition process on one or more regions of the patterned substrate (referred to as "growth regions" or "growth areas") is greater than the film thickness deposited on one or more other regions of the patterned substrate (referred to as "non-growth regions" or "non-growth areas"). As defined herein, a "selectivity ratio" refers to the ratio of film thicknesses deposited on any pair of regions or portions of the patterned substrate in the same process. In embodiments of the invention, the selectivity ratio between the growth surface and the non-growth surface is at least about 2:1, at least about 5:1, or at least about 10:1.

[0129] In some embodiments, the region-selective process described herein involves passivating one or more substrate regions to suppress film growth during a silicon-containing thin film deposition process. Passivation can be achieved by a variety of means known in the art, such as exposure to a compound that selectively reacts with a target region of the substrate, blocking contact between the silicon-containing chemical precursor and the chemically active sites on the substrate surface, thereby delaying film growth in that region. Such passivation can occur in a different deposition system than that used to deposit the silicon-containing thin film (referred to as in situ) or in the same deposition system or tool (referred to as in situ), as described in steps (j2) and (k2). Furthermore, passivation can be repeated during the thin film deposition process, up to once per atomic layer deposition cycle, forming an "ABC" atomic layer deposition cycle. Passivation can also be repeated only after a portion of the atomic layer deposition cycles, often referred to as a "supercycle." For example, depending on the specific process requirements, passivation can be repeated after every five or ten cycles to maintain sufficient selectivity between the substrate growth regions and non-growth regions. Both "ABC" and the supercycle process can be achieved by appropriate combinations of deposition processes (c), (h)+(i)), (l) or (m)+(n)) with steps (d)+(e)).

[0130] The compounds suitable for passivating substrate regions depend on the chemical or material composition of the target region. Due to the low temperature and mild oxidation conditions described herein, a variety of passivation schemes known in the art are compatible with the disclosed deposition conditions. Although not limiting, suitable passivation processes may include: reactions of oxides (such as silicon dioxide, silicon carbide, silicon carbonitride, germanium dioxide) with aminosilanes, cyclic azirnes, alkoxysilanes, or halosilanes; reactions of nitrides (such as silicon nitride, titanium nitride, tantalum nitride, or aluminum nitride) with aldehydes; reactions of metals (such as copper, cobalt, tungsten, ruthenium, or molybdenum) with sulfur- or phosphorus-containing molecules (such as alkyl thiols, trialkylphosphine, benzimidazonium N-heterocyclic carbene, or imidazonium N-heterocyclic carbene); reactions of metals (such as copper, cobalt, tungsten, ruthenium, or molybdenum) and semiconductors (such as silicon, germanium, silicon-germanium alloys, and gallium arsenide) with silanes containing Si-H bonds (such as octylsilane or dodecylsilane); or reactions of alumina surfaces with diketones (such as acetylacetone). It should be noted that steps (j2) and (k2) may include more than one of the above passivation processes to suppress growth on more than one region of the substrate surface.

[0131] According to one aspect of the invention, the deposition rate of the deposition step is greater than 0.3 Å / cycle, and the cycle time is less than 120 seconds. According to a further aspect of the invention, the deposition rate is greater than 0.5 Å / cycle, and the cycle time is less than 60 seconds. According to a further aspect of the invention, the deposition rate is greater than 0.6 Å / cycle at 30°C and greater than 0.25 Å / cycle at 100°C. Therefore, by using hydrogen peroxide with low water content, ideal deposition rates greater than 0.3 Å / cycle, greater than 0.5 Å / cycle, or even higher, can be achieved, while the cycle time is very short, for example, less than 120 seconds, less than 60 seconds, or even shorter. Furthermore, these advantageous deposition rates and cycle times are achieved at low temperatures. For the purposes of this invention, cycle time can be understood as the total exposure time of all silicon precursors, hydrogen peroxide with low water content, and the time spent purging during the process. For example, in a first embodiment, cycle time refers to the time of step (c) divided by the number of exposures to a silicon-containing compound (e.g., a compound having formula 1, 2, 3, 4, or 5). In the second embodiment, the cycle time refers to the time of step (h). In the third embodiment, the cycle time refers to the time of step (l) divided by the number of times the compound having formula 1, formula 2, formula 3, formula 4 or formula 5 is exposed, or the time of step (m).

[0132] A variety of pre-deposition processes can be applied to the substrate to remove contaminants, planarize or chemically modify the surface, or alter the chemical, mechanical, or electrical properties of one or more regions of the substrate. While not limiting, these processes may include substrate annealing, cleaning, wet or dry etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification, passivation, or plasma treatment, and may include in-situ processes (such as steps (a1), (f1), or (j1)) performed in tools different from the disclosed silicon-containing thin film deposition process; or in-situ processes (such as steps (b1), (g1), or (k1)) performed in tools identical to the silicon-containing thin film deposition process. These pre-deposition processes may be performed at ambient temperature, below ambient temperature (such as about 10°C or about 0°C), or elevated temperature (such as about 100°C, about 200°C, about 400°C, or about 800°C), depending on the specific process. Similarly, pre-deposition processes may be performed in ambient atmosphere, oxidizing or reducing atmosphere, vacuum, or inert gas, depending on the specific process. The process conditions for pretreatment (such as temperature, pressure, and atmospheric composition) can be selected independently of the conditions for silicon deposition processes.

[0133] Accordingly, the same set of processes (i.e., steps (d) and (e)) may be performed after deposition or during the deposition process to alter the properties of one or more components of the thin film or substrate, or to prepare the substrate for subsequent processes, which may include repeating any of the processes disclosed herein or performing a "supercycle". These processes may include non-in-situ processes performed in tools different from the disclosed silicon-containing thin film deposition process, or in-situ processes performed in tools identical to the silicon-containing thin film deposition process. These processes may be performed at ambient temperature, below ambient temperature (e.g., about 10°C or about 0°C), or elevated temperature (e.g., about 100°C, about 200°C, about 400°C, or about 800°C), as appropriate for the specific process. Similarly, these processes may be performed in ambient atmosphere, oxidizing or reducing atmosphere, vacuum, or inert gas, as appropriate for the specific process. The process conditions (e.g., temperature, pressure, and atmospheric composition) of the post-processing can be selected independently of the conditions of the silicon-containing deposition process.

[0134] Thermal annealing involves heating a substrate in an inert (nitrogen, rare gases, carbon dioxide), oxidizing (oxygen, air, ozone, hydrogen peroxide, nitrous oxide), or reducing (hydrogen, ammonia, hydrocarbon) atmosphere at pressures from about 0.01 torr to about 1000 torr, temperatures from about 20°C to about 800°C, and times from about one second to about twelve hours. Thermal annealing can be assisted by electromagnetic radiation. This type of photo-annealing process utilizes various forms of light, such as microwaves, infrared, visible light, ultraviolet light, X-rays, or gamma rays, which can be appropriately tuned to excite chemical bonds within one or more layers of the substrate. Similarly, thermal annealing can also be assisted by an electron beam, the energy and power of which can be appropriately tuned to excite chemical bonds within one or more layers of the substrate.

[0135] Steps (a1), (b1), (f1), (g1), (j1), and (k1) are optional processes that may be performed to prepare the substrate for the atomic layer deposition process of steps (c), (h and i), (l), or (m and n). Steps (a1), (b1), (f1), (g1), (j1), and (k1) may include one or more processes known in the art, such as substrate annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, or plasma treatment. These processes may be performed independently before the substrate is placed into the atomic layer deposition tool, referred to as in-situ (steps (a1), (f1), or (j1)); or independently within the atomic layer deposition reactor, referred to as in-situ (steps (b1), (g1), or (k1)). The temperatures of any of the preparation steps (a1), (b1), (f1), (g1), (j1), and (k1) may be selected independently of each other, or independently of the temperature of the atomic layer deposition process defined in steps (c), (h and i), (l), or (m and n), and are not limited to the temperature ranges disclosed in steps (c), (h and i), (l), or (m and n).

[0136] Steps (c) and (l) include a thermal atomic layer deposition process, said process comprising exposing a substrate to at least one silicon-containing precursor having formula 1, 2, 3, 4, or 5 for about 0.01 s to about 60 s, optionally purging the reactor with an inert gas (such as nitrogen, helium, or argon) for 0 s to about 120 s, exposing the substrate to a gas stream containing low-water-content hydrogen peroxide for about 1 s to about 120 s, and optionally purging the reactor with an inert gas (such as nitrogen, helium, or argon) for 0 s to about 120 s; or preferably comprising exposing the substrate to a silicon-containing precursor having formula 1, 2, 3, 4, or 5 for about 0.1 s to about 20 s, optionally purging the reactor with an inert gas (such as nitrogen, helium, or argon) for 0 s to about 30 s, and exposing the substrate to a gas stream containing low-water-content hydrogen peroxide for about 5 s to about 60 s. The process involves exposing the substrate to a silicon-containing precursor having formula 1, 2, 3, 4 or 5 for about 1 to about 10 s, optionally purging the reactor with an inert gas (such as nitrogen, helium or argon) for about 0 to about 20 s, exposing the substrate to a gas stream containing low-water-content hydrogen peroxide for about 5 to about 30 s, and optionally purging the reactor with an inert gas (such as nitrogen, helium or argon) for about 0 to about 20 s.

[0137] The difference between steps (h and i) and (m and n) and steps (c) and (l) is that, during the atomic layer deposition cycle, two or more silicon-containing chemical precursors are delivered to the substrate, at least one of which is a precursor of formula 1, 2, 3, 4, or 5 without Si-C bonds, and at least one of which is a precursor of formula 6, 7, 8, 9, or 10 containing Si-C bonds. These precursors may be delivered simultaneously or sequentially, as described in steps (h and i) and (m and n). If the silicon-containing chemical precursors are delivered sequentially, the amount of any precursor, except the last one in the procedure, must be insufficient to completely saturate the available chemically active groups on the substrate interacting with the precursor, so that the second and any subsequent precursors can react with the remaining available chemically active groups on the surface. The feeding of two or more silicon-containing chemical precursors (whether simultaneously or sequentially) can be controlled by a variety of means known in the art, such as feeding time, controlling precursor vapor pressure by adjusting precursor temperature, precursor container design, pumping rate, carrier gas flow control, flow restrictor orifice plates, and throttle valves.

[0138] When the substrate is a patterned substrate having a growth surface and a non-growth surface, the selection ratio between the growth surface and the non-growth surface in the embodiments of the present invention is at least about 2:1, at least about 5:1 or at least about 10:1.

[0139] The invention will now be described in conjunction with the following non-limiting embodiments.

[0140] Example 1: Low-temperature deposition of silica at 23 °C using hydrogen peroxide with low water content and aminosilane A silicon wafer sample with 1000 nm thermally grown silica was placed in a reaction chamber at 23°C. The sample was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by 25 ALD cycles, sequentially exposed to tris(dimethylamino)silane (7 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by a 5-second nitrogen purging. Film growth of 1.0 Å was observed every 37 seconds using in-situ ellipsometric measurements. X-ray photoelectron spectroscopy (XPS) confirmed the film composition as silica with less than 1% carbon and less than 1% nitrogen. The substrate exposure to hydrogen peroxide was determined to be no greater than 3.35 x 10⁻⁶ per atomic layer deposition cycle. -6 Langmuir.

[0141] Example 2: Low-temperature deposition of silica using hydrogen peroxide with low water content and chloroaminosilane at 30 °C A silicon wafer sample with 1.7 nm of natural silica was placed in a reaction chamber at 30°C. The sample was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by 500 ALD cycles, sequentially exposed to tris(dimethylamino)chlorosilane (5 s) and low-water-content hydrogen peroxide delivered by the RASIRC BRUTE hydrogen peroxide delivery system (20 s), separated by a 5-second nitrogen purging. Thin film growth of 0.31 Å was observed every 35 seconds of cycling via in-situ ellipsometric measurements.

[0142] Example 3 (Comparative): Low-temperature deposition of silica using 30% hydrogen peroxide aqueous solution and aminosilane at 30°C A silicon wafer sample with 1000 nm thermally grown silica was placed in a reaction chamber at 30°C. The sample was exposed to nitrogen plasma for one minute to remove exogenous contamination, followed by 100 ALD cycles, sequentially exposed to tris(dimethylamino)silane (5 seconds) and a 30% aqueous hydrogen peroxide solution delivered by a bubbler (20 seconds), separated by a 5-second nitrogen purging. In-situ ellipsometry measurements showed a film growth of 0.004 Å per 35-second cycle. This example demonstrates the importance of using hydrogen peroxide with low water content, as the solution containing 30% hydrogen peroxide (70% water) produced almost no film growth at 30°C.

[0143] Example 4: Low-temperature deposition of silica using hydrogen peroxide with low water content and aminosilane at 30°C A silicon wafer slice with 1.7 nm of natural silica was placed in a reaction chamber at 30°C. The slice was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by 50 ALD cycles of sequential exposure to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by the RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by nitrogen purging for 10 seconds and 5 seconds, respectively. Thin film growth of 0.88 Å was observed every 38 seconds using in-situ elliptic polarization.

[0144] Comparative Example 5 (Contrast): Silica was deposited at low temperatures using hydrogen peroxide with low water content and water, respectively. A silicon wafer slice with 1.7 nm of natural silica was placed in a reaction chamber at 30°C. The slice was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by 550 ALD cycles of sequential exposure to tris(dimethylamino)silane (3 seconds), low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), and water (5 seconds), separated by nitrogen purging for 5 seconds, 5 seconds, and 0 seconds, respectively. Film growth of 0.77 Å was observed every 38 seconds using in-situ elliptic polarization. Therefore, the pulsed introduction of water before the silane was observed to interfere with silane adsorption, reducing the growth rate by 12% compared to Example 4, further demonstrating the need for low-water-content hydrogen peroxide.

[0145] Example 6: Low-temperature deposition of silica using hydrogen peroxide with low water content and aminosilane at 30°C. passivation of silicon oxide substrate A silicon wafer slice with 1000 nm thermally grown silica was placed in a reaction chamber at 30°C. The slice was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by exposure to a 10-second pulse of N-methyl-aza-2,2,4-trimethylsilazine. An immediate 0.38 nm thick passivation layer was observed to grow. Subsequently, 75 ALD cycles were performed, sequentially exposing the wafer to tris(dimethylamino)silane (5 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by a 15-second nitrogen purging. An additional 0.19 nm of film growth within the 75 cycles was determined by in-situ ellipsometry and confirmed by XPS. This example demonstrates that silica is a non-grown surface.

[0146] Example 7: Cobalt substrate during low-temperature deposition of silica using low-water-content hydrogen peroxide and aminosilane at 30°C The bottom was not passivated. A silicon wafer slice with a 50 nm cobalt sputtered surface layer was placed in a reaction chamber at 30°C. The slice was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by exposure to a 10-second pulse of N-methyl-aza-2,2,4-trimethylsilanecyclopentane. Subsequently, 75 ALD cycles were performed, sequentially exposing the slice to tris(dimethylamino)silane (5 seconds) and low-water-content hydrogen peroxide delivered by the RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by a 15-second nitrogen purging. X-ray photoelectron spectroscopy (XPS) confirmed the formation of a thin film approximately four nanometers thick, composed of silicon dioxide with a carbon content of less than 1% and a nitrogen content of less than 1%, resulting in a selection ratio of approximately 21 for Example 7 relative to Example 6.

[0147] Example 8: The effect of oxygen on low-temperature deposition of silica using low-water-content hydrogen peroxide and aminosilane at 30°C. passivation of aluminum oxide substrate A silicon wafer slice with 100 nm alumina deposited by physical vapor deposition was placed in a reaction chamber at 30°C. The slice was exposed to nitrogen plasma for one minute and hydrogen peroxide for 30 seconds to remove exogenous contamination, followed by exposure to a 10-second pulse of N-methyl-aza-2,2,4-trimethylsilane. Immediate growth of a 0.40 nm thick passivation layer was observed. Subsequently, 150 ALD cycles were performed, sequentially exposing the wafer to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by 10-second and 5-second nitrogen purgings, respectively. An additional 2.3 nm film growth was observed within the 150 cycles, as determined by in-situ ellipsometry, with no growth observed in the first 86 cycles. This example demonstrates the effect of alumina (Al₂O₃) on the growth of the silicon wafer. x The surface is a non-growing surface.

[0148] Example 9: Hydrogen final concentration during low-temperature deposition of silica using low-water-content hydrogen peroxide and aminosilane at 30°C The silicon substrate was not passivated. A silicon wafer slice with a 1.7 nm native oxide layer was etched with a 100:1 HF buffer solution for 5 minutes, rinsed with water, and dried with nitrogen. The slice was then placed in a reaction chamber at 30°C and maintained at that temperature for 90 minutes to remove surface-adsorbed moisture. The slice was then exposed to a 10-second pulse of N-methyl-aza-2,2,4-trimethylsilane, and a passivation layer less than one angstrom thick was observed to grow. Subsequently, 150 ALD cycles were performed, sequentially exposing the wafer to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by 10-second and 5-second nitrogen purgings, respectively. In-situ ellipsometry determined that the additional film growth within the 150 cycles was 8.7 nm, and within the first 86 cycles it was 5.3 nm, with growth beginning from the first cycle. This example demonstrates Si(H) as the growth surface. Compared to Example 8, the selection ratio after 150 cycles is approximately 3.8, and after 86 cycles it exceeds 100.

[0149] Example 10: Nitriding of silica at low temperature using hydrogen peroxide with low water content and aminosilane at 30°C The silicon substrate was not passivated. A silicon wafer slice with a 100 nm thick SiN layer prepared by physical vapor deposition was etched with a 100:1 HF buffer solution for 5 minutes, rinsed with water, and dried with nitrogen. The slice was placed in a reaction chamber at 30°C and maintained at that temperature for 90 minutes to remove surface-adsorbed moisture. The slice was then exposed to a 10-second pulse of N-methyl-aza-2,2,4-trimethylsilane, and a passivation layer of approximately 1 angstrom thickness was observed to grow. Subsequently, 50 ALD cycles were performed, sequentially exposing the slice to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by 10-second and 5-second nitrogen purgings, respectively. The additional film growth within 50 cycles was determined by in-situ elliptic polarization, with growth beginning from the fifth cycle. This example demonstrates that silicon nitride can be used as a growth surface. The selectivity after 50 cycles is greater than 100 compared to Example 8.

[0150] Example 11: Precipitation of acetaminophen powder using low-moisture hydrogen peroxide and aminosilane at 30°C silicon dioxide Acetaminophen powder was placed in an aluminum dish within a 30°C reaction chamber. The powder was exposed to 100 ALD cycles, sequentially to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by a 5-second nitrogen purging. The powder was then removed from the reaction chamber and mixed. The deposition and mixing process was then repeated twice more, for a total of 300 ALD cycles. An approximately 18.5 nm silica coating was obtained by in-situ ellipsometry on test silicon wafer slices. The presence of 1.1 atomic percent silicon on the acetaminophen powder was confirmed by energy-dispersive X-ray (EDX) spectroscopy (SEM). Further liquid chromatography analysis of the acetaminophen powder revealed a purity greater than 98%.

[0151] Example 12: Deposition of PET polymer film using low-water-content hydrogen peroxide and aminosilane at 30°C silicon dioxide A self-supported polyethylene terephthalate (PET) film was placed in a reaction chamber at 30°C. The film was exposed to 300 ALD cycles, followed by sequential exposure to tris(dimethylamino)silane (3 seconds) and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 seconds), separated by a 5-second nitrogen purging. An approximately 18.5 nm silica coating was obtained by in-situ ellipticization of test silicon wafer slices. The presence of 0.69 atomic percent silicon on the PET was confirmed by energy-dispersive X-ray (EDX) spectroscopy with scanning electron microscopy (SEM) and XPS.

[0152] Example 13: Low-temperature deposition of silicon carbide using low-water-content hydrogen peroxide and two aminosilanes at 30°C A silicon wafer slice with 1000 nm thermally grown silica was placed in a reaction chamber at 30°C. The slice was exposed to oxygen plasma for one minute to remove exogenous contamination, followed by 300 ALD cycles, sequentially exposed to tris(dimethylamino)silane (1 s), tris(dimethylamino)silane (5 s), and low-water-content hydrogen peroxide delivered by a RASIRC BRUTE hydrogen peroxide delivery system (20 s), separated by a 5-second nitrogen purging. Thin film growth of 0.37 Å was observed every 41 seconds using in-situ elliptic polarization. X-ray photoelectron spectroscopy (XPS) confirmed the film composition as oxysilicon carbide containing 7.1% carbon and 1.7% nitrogen. It should be noted that the cycle shown in this example used a precursor of Formula 6 (subsaturated), followed by a precursor of Formula 1 (saturated), and then low-water-content hydrogen peroxide, with each step separated by a purging. The short pulse duration of the Formula 6 compound left space on the substrate surface for the reaction of the Formula 1 compound. Therefore, when hydrogen peroxide is introduced, both precursors are present, forming a mixed layer. Since hydrogen peroxide has difficulty cleaving methyl groups, most or all of them are retained in the film.

[0153] Therefore, it is understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the invention as defined by the appended claims.

Claims

1. A method for depositing a silicon-oxygen-containing layer on a substrate, the method comprising: (a) Introducing the substrate into the reaction zone of the deposition chamber; (b) Heat or cool the reaction zone to approximately 0 °C to approximately 150 °C; as well as (c) Performing a thermal atomic layer deposition process on a substrate by alternately exposing the substrate to at least one silicon-containing compound and low-water-content hydrogen peroxide to form a silicon-oxygen-containing layer on the substrate until the desired layer thickness is obtained.

2. The method according to claim 1, further comprising, prior to step (a): (a1) The substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

3. The method according to claim 1 or 2, further comprising, after step (a) and before step (b): (b1) The reaction zone is heated or cooled to about 0 °C to about 800 °C, and the substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

4. The method according to any one of claims 1 to 3, characterized in that, The at least one silicon-containing compound has a formula of 1, 2, 3, 4 or 5: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl, or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds.

5. The method according to any one of claims 1 to 4, characterized in that, The at least one silicon-containing compound is tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, 1,3,5-tris(1-methylethyl)-1 3,5-Triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disilane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane or tri(di-sec-butylamino)silane.

6. The method according to claim 5, characterized in that, The at least one silicon-containing compound is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane, or tris(isopropylamino)silane.

7. The method according to any one of claims 1 to 6, characterized in that, The temperature of the reaction zone in step (b) is below approximately 100 °C.

8. The method according to claim 7, characterized in that, The temperature of the reaction zone in step (b) is below approximately 50 °C.

9. The method according to any one of claims 1 to 8, characterized in that, The hydrogen peroxide contains less than about 30 percent water by weight.

10. The method according to claim 9, characterized in that, The hydrogen peroxide contains less than about 20 percent water by weight.

11. The method according to claim 10, characterized in that, The hydrogen peroxide contains less than about 10 percent water by weight.

12. The method according to any one of claims 1 to 11, characterized in that, The deposition rate of the silicon-oxygen layer is greater than about 0.3 angstroms per cycle, and the cycle time is less than about 120 seconds.

13. The method according to claim 12, characterized in that, The deposition rate of the silicon-oxygen layer is greater than about 0.5 angstroms per cycle, and the cycle time is less than about 60 seconds.

14. The method according to any one of claims 1 to 13, wherein after step (c), the method further comprises: (d) Heat or cool the reaction zone to approximately 0 °C to approximately 800 °C; as well as (e) The substrate is subjected to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

15. The method of claim 14, further comprising, after step (e): (p) Repeat steps (a) or (a1) to (e) until the desired layer thickness is achieved.

16. The method according to any one of claims 1 to 15, characterized in that, The substrate includes semiconductor devices, active pharmaceutical ingredients, pharmaceutical products, polymers, or polymer films.

17. A method for depositing a silicon-carbon layer on a substrate, the method comprising: (f) Introducing the substrate into the reaction zone of the deposition chamber; (g) Heating or cooling the reaction zone to approximately 0 °C to approximately 150 °C; and (h) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (ii) Repeat step (h) until the desired layer thickness is obtained: Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental and is O or N (R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl or -Si(R) 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8 alkyl), straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and forms a ring with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R) 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; wherein the precursor compound comprises at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

18. The method according to claim 17, characterized in that, Except for the final exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the available substrate surface, or are subsequently exposed to hydrogen peroxide with low water content.

19. The method according to claim 17 or 18, further comprising, prior to step (f): (f1) The substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

20. The method according to any one of claims 17 to 19, further comprising, after step (f) and before step (g): (g1) Heat or cool the reaction zone to about 0 °C to about 800 °C and subject the substrate to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification or plasma treatment.

21. The method according to any one of claims 17 to 20, characterized in that, At least one of the silicon-containing compounds having formula 1, formula 2, formula 3, formula 4 or formula 5 is tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, 1,3,5-tris( 1-Methylethyl)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disilane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silanes, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane or tri(di-sec-butylamino)silane.

22. The method according to claim 21, characterized in that, At least one of the silicon-containing compounds having formula 1, formula 2, formula 3, formula 4 or formula 5 is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane or tris(isopropylamino)silane.

23. The method according to any one of claims 17 to 22, characterized in that, At least one of the silicon-containing compounds of formula 6, 7, 8, 9, or 10 is tris(dimethylamino)methylsilane, di(diethylamino)methylsilane, di(isopropylamino)methylsilane, dimethylamino(dimethoxy)methylsilane, tris(dimethylamino)(tert-butyl)silane, tris(dimethylamino)phenylsilane, dimethylamino(dimethyl)cyclohexylsilane, or 2-(dimethylaminosilyl)bicyclo[2.2.1] Heptane, Tris(dimethylamino)decylsilane, N-methyl-aza-2,2,4-trimethylsilazopentane, N-trimethylsilyl-aza-4-methylsilazopentane, N-(n-butyl)-aza-silazopentane, N-ethyl-aza-4-methyl-2,2-dimethoxysilazopentane, 1,2,2,3-tetramethyl-1,3-diaza-2-silazopentane, N-methyl-aza-4-methyl -2-Methoxy-2-(n-Butyl)silane, bis(dimethylaminomethylsilyl)methane, bis(tris(dimethylamino)silyl)methane, bis(bis(dimethylamino)methylsilyl)methane, 1,1-bis(tris(dimethylamino)silyl)ethane, bis(bis(dimethylamino)methylsilylamino)-(dimethylamino)methylsilane, (bis(dimethylamino)methylsilylamino)-bis(dimethylamino)methylsilane, bis(bis... (Dimethylamino)silyl)methane, (bis(ethylamino)methylsilyl)bis(ethylamino)methylsilane, and 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trimethyl-2,4,6-trisilacyclohexane, 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, dimethylamino(trimethoxy)silane, or N-trimethylsilyl-aza-sililacyclopentane.

24. The method according to claim 23, characterized in that, At least one of the silicon-containing compounds having formula 6, formula 7, formula 8, formula 9 or formula 10 is tris(dimethylamino)methylsilane, bis(tris(dimethylamino)silyl)methane, N-methyl-aza-2,2,4-trimethylsilazopentane or bis(dimethylaminomethylsilyl)methane.

25. The method according to any one of claims 17 to 24, characterized in that, The temperature of the reaction zone in step (g) is below approximately 100 °C.

26. The method according to claim 25, characterized in that, The temperature of the reaction zone in step (g) is below approximately 50 °C.

27. The method according to any one of claims 17 to 26, characterized in that, The hydrogen peroxide contains less than about 30 percent water by weight.

28. The method according to claim 27, characterized in that, The hydrogen peroxide contains less than about 20 percent water by weight.

29. The method according to claim 28, characterized in that, The hydrogen peroxide contains less than about 10 percent water by weight.

30. The method according to any one of claims 17 to 29, characterized in that, The deposition rate of the silicon-carbon layer is greater than about 0.3 angstroms per cycle, and the cycle time is less than about 120 seconds.

31. The method according to claim 30, characterized in that, The deposition rate of the silicon-carbon layer is greater than about 0.5 angstroms per cycle, and the cycle time is less than about 60 seconds.

32. The method according to any one of claims 17 to 31, characterized in that, Following step (i), the method further includes: (d) Heating or cooling the reaction zone to approximately 0 °C to approximately 800 °C; and (e) The substrate is subjected to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

33. The method of claim 32, further comprising, after step (e); (o) Repeat steps (f) or (f1) to (e) until the desired layer thickness is achieved.

34. The method according to any one of claims 17 to 33, characterized in that, The substrate includes semiconductor devices, active pharmaceutical ingredients, pharmaceutical products, polymers, or polymer films.

35. A method for selectively depositing a silicon-containing layer on a patterned substrate, the method comprising: (j) Introducing a patterned substrate into the reaction zone of the deposition chamber; (k) Heat or cool the reaction zone to approximately 0 °C to approximately 150 °C; (l) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to hydrogen peroxide with low water content and at least one silicon-containing compound having formula 1, formula 2, formula 3, formula 4 or formula 5 to form a silicon-containing layer on the substrate until the desired layer thickness is obtained. or (m) A thermal atomic layer deposition process is performed on a substrate by alternately exposing the substrate to two or more silicon-containing compounds and low-water-content hydrogen peroxide to form a silicon-containing carbon layer on the substrate; wherein at least one of the two or more silicon-containing compounds has a formula 1, 2, 3, 4 or 5, and at least one of the two or more silicon-containing compounds has a formula 6, 7, 8, 9 or 10; wherein at least two of the two or more silicon-containing compounds are: Simultaneously transported to the substrate; or The mixture is sequentially conveyed to the substrate, optionally separated by purge of the reaction zone, optionally separated by exposure to low-water-content hydrogen peroxide, and (n) Repeat step (m) until the desired layer thickness is achieved; The method further includes: Before step (j): (j2) Perform one or more substrate passivation steps; and / or Before step (k): (k2) Perform one or more substrate passivation steps; Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Among them, R1, R2, R3, R4, R5, R6, R 26 R 27 R 29 and R 30 Independently selected from hydrogen, halogen, OR7 or N(R8)(R9); X is O or N(R9). 10 ); Y and Z are -C(R) 20 (R) 21 ), -C(R 20 (R) 21 )-C(R 22 (R) 23 )-、-C(R 20 (R) 21 )-C(R 22 (R) 23 )-C(R 24 (R) 25 )-or-Si(R 26 (R) 27 )-N(R 28 )-Si(R 29 )R( 30 Y and Z are optionally bidentate and form a ring with the adjacent nitrogen atom; R7 is a straight-chain or branched (C1-C8) alkyl group, or -Si(R 11 (R) 12 (R) 13 ), R 11 R 12 and R 13 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C8) alkoxy or -N(R) 14 (R) 15 ), R 14 and R 15 Independently hydrogen or straight-chain or branched (C1-C8) alkyl; R8, R9, R 10 R 16 R 17 R 18 R 19 and R 28 Independently hydrogen, straight-chain or branched (C1-C8) alkyl or Si(R) 31 (R) 32 (R) 33 ), R 31 R 32 and R 33 It is hydrogen, (C1-C8)alkyl or N(R) 34 (R) 35 ), R 34 and R 35 It is hydrogen or (C1-C8) alkyl; R 20 R 21 R 22 R 23 R 24 and R 25 It is hydrogen, vinyl, allyl, or straight-chain or branched (C1-C4) alkyl; and at least half of the bonds with silicon atoms contain Si-N bonds or silicon-halogen bonds; Formula 6, Formula 7, Formula 8, Formula 9, Formula 10 Where R 36 R 37 R 38 R 39 R 40 R 41 R 42 R 43 R 44 R 45 R 46 R 47 R 79 and R 80 Independently selected from hydrogen, halogen, straight-chain or branched (C1-C2) 18 )alkyl, straight-chain or branched (C1-C 18 )alkoxy, vinyl, allyl, butenyl, phenyl, tolyl, cyclohexyl, cyclooctyl or norbornyl, or N(R 51 (R) 52 V is optionally bidental and is O, N(R) 53 ), C(R 73 (R) 74 ), straight-chain or branched (C1-C8) alkyl groups, or -C(R 73 (R) 74 )-C(R 75 (R) 76 )-, where C 73 C 74 C 75 and C 76 It is a hydrogen or straight-chain or branched (C1-C8) alkyl group; R 49 R 50 R 51 R 52 and R 53 It is hydrogen, straight-chain or branched (C1-C8) alkyl, or -Si(R 54 (R) 55 (R) 56 ); R 54 R 55 and R 56 Independently selected from hydrogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or -N(R) 57 (R) 58 ); R 57 and R 58 Independently hydrogen or (C1-C8) alkyl; R 48 It is a hydrogen or straight-chain or branched (C1-C8) hydrocarbon; W is optionally bidentate and forms a ring with adjacent nitrogen, silicon and / or carbon atoms, and is a straight-chain or branched (C1-C8) alkyl, C(R ... 59 (R) 60 ), -C(R 59 (R) 60 )-C(R 61 (R) 62 )-、-C(R 59 (R) 60 )-C(R 61 (R) 62 )-C(R 63 (R) 64 )-or-Si(R 65 (R) 66 )-N(R 67 )-Si(R 68 (R) 69 )-;R 59 R 60 R 61 R 62 R 63 R 64 Independently hydrogen, straight-chain or branched (C1-C8) alkyl; R 65 R 66 R 68 and R 69 Hydrogen, halogen, (C1-C8) alkyl, O(R) 70 ) or N(R 71 (R) 72 ); R 70 It is a straight-chain or branched (C1-C8) alkyl group; U is a C(R) alkyl group. 77 (R) 78 ) or Si(R 79 )Si(R 80 ); R 67 R 71 R 72 R 77 and R 78 It is independently hydrogen or a straight-chain or branched (C1-C8) alkyl group; and said precursor compound contains at least one silicon-nitrogen or silicon-halogen bond and at least one silicon-carbon bond.

36. The method according to claim 35, characterized in that, Except for the final exposure, all exposures of the substrate to the two or more silicon-containing compounds cover only a portion of the available substrate surface, or are subsequently exposed to hydrogen peroxide with low water content.

37. The method according to claim 35 or 36, further comprising, before or after step (j2): (j1) Perform at least one non-in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment on the patterned substrate.

38. The method according to any one of claims 35 to 37, further comprising, before or after step (k2): (k1) The reaction zone is heated or cooled to about 0 °C to about 800 °C, and the patterned substrate is subjected to at least one in-situ annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment, chemical modification, passivation or plasma treatment.

39. The method according to any one of claims 35 to 38, characterized in that, At least one passivation step (j2) or (k2) satisfies the following criteria: (vi) When the substrate comprises silicon dioxide, silicon carbide, silicon oxynitride, silicon carbonitride or germanium dioxide, the patterned substrate is exposed to a compound having formula 11 or formula 12 to selectively passivate regions of the substrate. or (vii) When the substrate comprises silicon nitride, titanium nitride, tantalum nitride or germanium nitride, the patterned substrate is exposed to a compound containing aldehyde functional groups to selectively passivate regions of the substrate. or (viii) When the substrate comprises copper, cobalt, molybdenum, ruthenium and / or tungsten, the patterned substrate is exposed to N-heterocyclic carbene or sulfur- or phosphorus-containing compounds to selectively passivate regions of the substrate; or (ix) When the substrate comprises silicon, germanium, copper, cobalt, molybdenum, ruthenium or tungsten, the patterned substrate is exposed to a compound of Formula 13 to selectively passivate regions of the substrate; or (x) When the substrate comprises aluminum oxide, the patterned substrate is exposed to a compound of formula 11, formula 12, formula 14, or formula 15 to selectively passivate regions of the substrate: Where R 81 R 82 R 83 and R 84 Independently hydrogen, halogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R) 96 (R) 97 ), where R 96 and R 97 Independently hydrogen or (C1-C8) alkyl, and R 81 R 82 R 83 and R 84 At least one of them is a straight-chain or branched (C1-C8) alkyl group, and at least one is an N(R) alkyl group. 96 )R 97 ;R 85 and R 86 It is hydrogen, halogen, straight-chain or branched (C1-C8) alkyl, straight-chain or branched (C1-C8) alkoxy, or N(R 96 (R) 97 ); R 88 R 89 R 90 and R 91 Independently hydrogen or (C1-C) 18 )alkyl, and R 88 R 89 R 90 Or R 91 At least one of them is hydrogen, and at least one is (C1-C) 18 ) alkyl; T is a straight-chain or branched (C1-C4) alkyl; R 92 R 93 R 94 and R 95 It is hydrogen or (C1-C4) alkyl; wherein R 87 It is a hydrogen or a straight-chain or branched (C1-C4) alkyl group; and wherein n and m are 1, 2 or 3.

40. The method according to any one of claims 35 to 39, characterized in that, The silicon-containing compounds having formula 1, formula 2, formula 3, formula 4 or formula 5 are tris(dimethylamino)silane, tetra(dimethylamino)silane, 1,4,6,9-tetramethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 2,2-dimethoxy-1,3-dimethyl-1,3-diaza-2-silazacyclopentane, trisilylamine, di(diethylamino)silane, di(isopropylamino)silane, 1,2,4,6,8,9-hexamethyl-1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, 1,3,5-tris(1-methyl)silane, and 1,3,5-tris(1-methyl)silane, 1,4,6,9-tetramethoxysilane, 1,3,5-tris(1-methyl)silane, 1,4,6,9-tetramethoxysilane, 1,4,6,9-tetraaza-5-silazaspiro[4.4]nonane, penta(dimethylamino)disilane, di(tert-butylamino)silane, di(dimethylamino)dimethoxysilane, di(dimethylamino)silane, and 1,3,5-tris(1-methyl)silane, 1,4,6,9-tetramethoxysilane, 1,4,6,9-tetramethoxysilane, 1,4,6,9-tetramethoxysilane, 1,4,6,9-tetramethoxysilane, 1,4,6,9-tetramethoxysilane, 1,4,6, (By)-1,3,5-triaza-2,4,6-trisilacyclohexane, hexa(ethylamino)disilane, di(sec-butylamino)silane, hexa(dimethylamino)disiloxane, bis(bis(dimethylamino)silylamino)(dimethylamino)silane, hexa(dimethylamino)silazane, tetrachlorosilane, tri(dimethylamino)chlorosilane, 1,2-bis(dimethylamino)disilane, hexa(ethylamino)disilane, tri(ethylamino)silane, tri(isopropylamino)silane, tri(n-propylamino)silane, tri(tert-butylamino)silane, tri(n-butylamino)silane, tri(sec-butylamino)silane, tri(diethylamino)silane, tri(diisopropylamino)silane, tri(di-n-propylamino)silane, tri(di-tert-butylamino)silane, tri(di-n-butylamino)silane, or tri(di-sec-butylamino)silane.

41. The method according to claim 40, characterized in that, The silicon-containing compound having formula 1, formula 2, formula 3, formula 4 or formula 5 is tris(dimethylamino)silane, tris(dimethylamino)chlorosilane, tris(diethylamino)silane, tris(ethylamino)silane, or tris(isopropylamino)silane.

42. The method according to any one of claims 35 to 41, characterized in that, The silicon-containing compound having formula 6, formula 7, formula 8, formula 9 or formula 10 is tris(dimethylamino)methylsilane, di(diethylamino)methylsilane, di(isopropylamino)methylsilane, dimethylamino(dimethoxy)methylsilane, tris(dimethylamino)(tert-butyl)silane, tris(dimethylamino)phenylsilane, dimethylamino(dimethyl)cyclohexylsilane, 2-(dimethylaminosilyl)bicyclo[2.2.1]heptane, Tris(dimethylamino)decylsilane, N-methyl-aza-2,2,4-trimethylsilazopentane, N-trimethylsilyl-aza-4-methylsilazopentane, N-(n-butyl)-aza-silazopentane, N-ethyl-aza-4-methyl-2,2-dimethoxysilazopentane, 1,2,2,3-tetramethyl-1,3-diaza-2-silazopentane, N-methyl-aza-4-methyl-2- Methoxy-2-(n-Butyl)silane, bis(dimethylaminomethylsilyl)methane, bis(tris(dimethylamino)silyl)methane, bis(bis(dimethylamino)methylsilyl)methane, 1,1-bis(tris(dimethylamino)silyl)ethane, bis(bis(dimethylamino)methylsilylamino)-(dimethylamino)methylsilane, (bis(dimethylamino)methylsilylamino)-bis(dimethylamino)methylsilane, bis(bis( Dimethylamino)silyl)methane, (bis(ethylamino)methylsilyl)bis(ethylamino)methylsilane, and 1,3,5-tris(1-methylethyl)-1,3,5-triaza-2,4,6-trimethyl-2,4,6-trisilacyclohexane, 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, dimethylamino(trimethoxy)silane, or N-trimethylsilyl-aza-sililacyclopentane.

43. The method according to claim 42, characterized in that, The silicon-containing compound having formula 6, formula 7, formula 8, formula 9 or formula 10 is tris(dimethylamino)methylsilane, bis(tris(dimethylamino)silyl)methane, N-methyl-aza-2,2,4-trimethylsilazopentane or bis(dimethylaminomethylsilyl)methane.

44. The method according to any one of claims 35 to 43, characterized in that, The temperature of the reaction zone in step (k) is below approximately 100 °C.

45. The method according to claim 44, characterized in that, The temperature of the reaction zone in step (k) is below approximately 50 °C.

46. ​​The method according to any one of claims 35 to 45, characterized in that, The hydrogen peroxide contains less than about 30 percent water by weight.

47. The method according to claim 46, characterized in that, The hydrogen peroxide contains less than about 20 percent water by weight.

48. The method according to claim 47, characterized in that, The hydrogen peroxide contains less than about 10 percent water by weight.

49. The method according to any one of claims 35 to 48, characterized in that, The deposition rate of the silicon-containing layer or silicon-carbon-containing layer is greater than about 0.3 angstroms per cycle, and the cycle time is less than about 120 seconds.

50. The method according to claim 49, characterized in that, The deposition rate of the silicon-containing layer or silicon-carbon-containing layer is greater than about 0.5 angstroms per cycle, and the cycle time is less than about 60 seconds.

51. The method according to any one of claims 35 to 50, characterized in that, The patterned substrate has a growth surface and a non-growth surface, and the selection ratio between the growth surface and the non-growth surface is at least about 2:

1.

52. The method according to claim 51, characterized in that, The selection ratio between the grown surface and the non-grown surface is at least about 5:

1.

53. The method according to claim 52, characterized in that, The selection ratio between the grown surface and the non-grown surface is at least about 10:

1.

54. The method according to any one of claims 35 to 53, characterized in that, After step (l) or (n), the method further includes: (d) Heating or cooling the reaction zone to approximately 0°C to approximately 800°C; and (e) The substrate is subjected to at least one in-situ passivation, annealing, cleaning, etching, polishing, oxidation, reduction, photolysis, ultraviolet (UV) / ozone treatment or plasma treatment.

55. The method of claim 54, further comprising, after step (e); (o) Repeat steps (j) or (j2) to (e) until the desired layer thickness is achieved.

56. The method according to any one of claims 35 to 55, characterized in that, The substrate includes semiconductor devices, active pharmaceutical ingredients, pharmaceutical products, polymers, or polymer films.

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