Precursors and methods for preparing silicon-containing films

Abstract

To provide improved organosilicon precursors and processes for the formation of silicon-containing films, in the manufacture of microelectronic devices, particularly in processes utilizing low-temperature vapor deposition techniques that are used for the formation of silicon nitride, silicon dioxide, and silicon oxynitride films.SOLUTION: The present invention provides a method for depositing a silicon-containing film on a surface of a microelectronic device, which comprises introducing at least one compound of Formula (I) to the surface in a reaction chamber under vapor deposition conditions (where, R1 is independently selected from hydrogen, C1-C4 alkyl, or halogen atoms selected from Cl, Br, and I).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Generally, the present invention relates to methods and precursors for the deposition of silicon-containing films on microelectronic device surfaces. [Background technology]

[0002] In semiconductor manufacturing, silicon nitride (Si3N4), silicon oxynitride (SiO x N y Thin (e.g., <1000 nanometers thick) passivation layers of chemically inert dielectric materials such as silicon carbide (SiC), silicon carbide nitride (SiCN), and silicon oxynitride (SiCO) and / or silicon dioxide (SiO2) are widely used in microelectronic device construction to serve as structural elements in multilayer devices such as sidewall spacer elements, diffusion masks, oxidation barriers, trench isolation coatings, intermetal dielectric materials, passivation layers, insulators, and etch stop layers.

[0003] Deposition of silicon-containing films by chemical vapor deposition techniques is a very attractive methodology for forming such films. CVD processes involving low deposition temperatures, e.g., temperatures below about 550°C, are particularly desirable, but require the availability of suitable silicon precursor compounds for such purposes. In some cases, higher deposition temperatures can be considered if the thermal budget of the integrated circuit allows. In these cases, particularly when high-quality silicon dioxide films are desired, temperatures >450°C can be utilized to achieve the desired properties of the dielectric film. In situations where very high-quality films are required and a high thermal budget can be tolerated, source materials that are stable to high temperatures are preferred, as they enable saturated ALD pulses that provide uniform process coverage across high-aspect-ratio structures.

[0004] Silicon nitride (SiN) has been used for source and drain spacers (S / D spacers) for FinFET and gate-all-around (GAA) structures due to its high wet etch and O2 ashing resistance. Unfortunately, SiN has a high dielectric constant (k) of approximately 7.5. To reduce the k and maintain excellent wet etch and ashing resistance during post-deposition processing, carbon- and nitrogen-doped SiO2 (SiCON) spacers have been developed. Currently, the best wet etch and ashing resistant SiCON dielectrics have k values ​​of approximately 4.0. Next-generation devices require wet etch and ashing resistant dielectrics with k values ​​of <3.5.

[0005] Furthermore, there remains a need for improved organosilicon precursors and processes for the formation of silicon-containing films in the manufacture of microelectronic devices, particularly in processes that utilize low-temperature deposition techniques utilized in the formation of silicon nitride, silicon dioxide, and silicon oxynitride films. In particular, there is a need for liquid silicon precursors that have good thermal stability during storage and vapor phase transport, high volatility, and reactivity with substrate surfaces. Summary of the Invention

[0006] The present invention relates generally to the formation of silicon-containing films in the manufacture of semiconductor devices, and more particularly to compositions and methods for forming such silicon-containing films, such as films comprising silicon, silicon nitride, silicon oxynitride, silicon dioxide, silicon carbide, carbon-doped silicon nitride, or carbon-doped silicon oxynitride films, in certain cases at relatively low temperatures.

[0007] The compounds of formula (I) described herein are useful as precursor compounds in the formation of such a variety of silicon-containing films. Advantageously, the precursors of the present invention can be used under low-temperature vapor deposition conditions to form high-quality nitride films, while also being able to be used to form high-quality, high-growth-rate silicon dioxide films at relatively high temperatures. This versatility thus demonstrates the flexibility of the precursors of formula (I). In one embodiment, compounds of formula (I), such as bis(dimethylsilyl)dimethylhydrazine, can also provide higher silicon dioxide film deposition rates compared to traditional silicon precursors. Similarly, compounds of formula (I) can be utilized to prepare silicon nitride films at higher growth rates. (See Figure 5 below.) SiN and SiCN films were deposited under similar conditions in the presence of N2 and NH3 co-reactants. Vapor deposition conditions and processes including chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), plasma-enhanced ALD-like processes, or ALD processes using oxygen-containing reactants, nitrogen-containing reactants, or combinations thereof, can be utilized with these precursor compounds to form silicon-containing films. [Brief explanation of the drawings]

[0008] [Figure 1] Figure 1 depicts a depiction of SiO2 growth rate in Angstroms per cycle versus pulse time in seconds using bis(dimethylsilyl)dimethylhydrazine (Formula (I) below, where each R1 is methyl) and ozone as the oxidizing co-reactant gas at three temperatures: 500°C, 550°C, and 600°C. An ALD saturation curve was observed at substrate temperatures <600°C, indicating saturated ALD behavior at lower temperatures. A high SiO2 growth rate of >2.5 Å / cycle was observed at 550°C. [Figure 2]FIG. 2 is a graph of atomic percentage measured by X-ray photoelectron spectroscopy (XPS) as a function of etch time in seconds (depth profiling) for pure SiO films deposited by a process similar to that described in FIG. 1. After removing the environmental cap layer on the film, neither N nor C is observed. The relative ratio of Si:O content reflects the composition of the SiO film. [Figure 3] FIG. 2 illustrates the deposition of SiO films with >92% conformal step coverage achieved by the precursor chemistry and process described in FIG. 1 on SiN / SiO / Si trench structures with an aspect ratio of 18:1. [Figure 4] Figure 1 shows a comparison of the wet etch rates of films deposited from bis(dimethylsilyl)dimethylhydrazine (BDMSDMH) and bis(t-butylamino)silane (BTBAS) at various substrate temperatures. Wet etching was performed in a 200:1 aqueous HF solution. The wet etch rate in this case represents an approximately >60% improvement for films deposited from the bis(dimethylsilyl)dimethylhydrazine precursor when compared to films from BTBAS. The wet etch rate is also compared to the wet etch rate of thermal oxide (SiO2). [Figure 5] Figure 1 shows the growth rate per cycle as a function of silicon pulse time under the influence of N plasma exposure for a silicon nitride deposition process using bis(dimethylsilyl)dimethylhydrazine as the precursor at 250°C, a plasma power of 200 Watts, and a nitrogen flow rate of 300 sccm. The cycle sequence utilized was (i) precursor with pulse length plotted on the x-axis, (ii) a 20-second purge, (iii) nitrogen plasma for 15 seconds (squares) or 20 seconds (circles), followed by (iv) a 20-second purge. [Figure 6] FIG. 6 shows the effect of nitrogen plasma power (200 watts or 300 watts) on growth rate per cycle using different pulse times of bis(dimethylsilyl)dimethylhydrazine as precursor under similar reactor and plasma deposition conditions as described in FIG. 5 with a plasma exposure time of 15 seconds. DETAILED DESCRIPTION OF THE INVENTION

[0009] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0010] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (e.g., having the same function or result). In many instances, the term "about" may include numbers that are rounded to the nearest significant figure.

[0011] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0012] In a first aspect, the present invention provides a compound of formula (I): TIFF0007825656000001.tif46170 (in the formula, each R 1 are independently selected from hydrogen, C1-C4 alkyl, or a halogen atom selected from Cl, Br, and I. In one embodiment, each R 1 is methyl.

[0013] The compounds of formula (I) are useful as precursors for depositing silicon-containing films on the surface of microelectronic devices. In certain embodiments, the films also contain nitrogen and / or oxygen and / or carbon.

[0014] Thus, in a second aspect, the present invention provides a method for depositing a silicon-containing film on a surface of a microelectronic device, the method comprising introducing at least one compound of formula (I) to said surface in a reaction chamber under vapor deposition conditions. Compounds of formula (I) can be prepared according to the following reaction scheme.

[0015] Step 1: TIFF0007825656000002.tif30170 In step 1, a chlorosilane is reacted with dimethylhydrazine to give a silylhydrazide intermediate and a hydrazine hydrochloride by-product.

[0016] Step 2: TIFF0007825656000003.tif30170 As shown in step 2 above, hydrazide dimethylsilane (or some other hydrazides (R 1 The 2-silane can be reacted with n-butyllithium or some other reactive alkali metal C1-C6 alkane optionally containing a nitrogen atom. Other potential reactants include methyllithium, t-butyllithium, lithium diisopropylamide, methylpotassium, n-butylpotassium, etc. to give the novel intermediate (II), as shown below: TIFF0007825656000004.tif38170 (in the formula, each R 1 are independently selected from hydrogen, C1-C4 alkyl, or a halogen atom selected from Cl, Br, and I; R 2 is selected from lithium or potassium. ) is obtained, which in turn is useful for the synthesis of compounds of formula (I). Compounds of formula (II) are then reacted with, for example, chlorodimethylsilane in this scheme. Thus, in a third aspect of the present invention, there is provided compounds of formula (II) above.

[0017] Thus, in a fourth aspect of the present invention, there is provided a compound of formula (I): TIFF0007825656000005.tif43170 (in the formula, each R 1 are independently selected from hydrogen, C1-C4 alkyl, or a halogen atom selected from Cl, Br, and I, comprising: A.Formula: The compound in TIFF0007825656000006.tif33170 is represented by the formula MR3 (wherein M is lithium or potassium, and R 3 is a C1-C6 alkyl group optionally containing a nitrogen atom, to produce a compound of formula (II): TIFF0007825656000007.tif39170 (in the formula, each R 1 are independently selected from hydrogen, C1-C4 alkyl, or a halide atom selected from Cl, Br, and I; R 2 is selected from lithium or potassium, and thereafter B. Reacting a compound of formula (II) with the formula: TIFF0007825656000008.tif28170, wherein X is a halogen; A method is provided which includes:

[0018] As used herein, the term silicon-containing film refers to films such as silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbonitride, silicon oxycarbonitride, low-k thin silicon-containing films, and the like.

[0019] In certain embodiments, vapor deposition conditions include reaction conditions known as chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition. In the case of pulsed chemical vapor deposition, a series of alternating pulses of precursor compounds and co-reactants, with or without intermediate (inert gas) purge steps, can be utilized to build film thickness to a desired endpoint.

[0020] Compounds of formula (I) are capable of low-temperature CVD and / or ALD formation of silicon-containing films. Such compounds exhibit high volatility and chemical reactivity, yet are stable to thermal decomposition at temperatures associated with precursor volatilization or vaporization, allowing for consistent and repeatable delivery of the resulting precursor vapor to a deposition zone or reaction chamber.

[0021] In certain embodiments, the pulse time of the precursor compounds (i.e., the duration of precursor exposure to the substrate) ranges from about 0.1 to about 30 seconds. In other embodiments, the pulse time of the co-reactant ranges from about 0.1 to about 30 seconds.

[0022] In one embodiment, the vapor deposition conditions include a temperature of about 50°C to about 750°C. In another embodiment, the vapor deposition conditions include a temperature of about 200°C to about 650°C. In another embodiment, the deposition conditions include a temperature of about 500°C to 550°C.

[0023] In one embodiment, the vapor pressure conditions include a pressure of about 0.5 to about 1000 Torr.

[0024] The compounds described above can be used to form high-purity thin silicon-containing films by any suitable deposition technique, such as CVD, digital (pulsed) CVD, ALD, and pulsed plasma deposition (PEALD). Such deposition processes can be used to form silicon-containing films on microelectronic devices using deposition temperatures of about 250°C to about 550°C, forming films having thicknesses of about 20 angstroms to about 2000 angstroms.

[0025] In the methods of the present invention, the compounds can be reacted with the desired microelectronic device substrate in any suitable manner, for example, in a single wafer CVD, ALD and / or PECVD or PEALD chamber, or in a furnace containing multiple wafers.

[0026] Alternatively, the method of the present invention can be carried out as an ALD or ALD-like process. As used herein, the term "ALD or ALD-like" refers to processes such as (i) reactants including the silicon precursor compound of formula (I) and an oxidizing and / or reducing gas are sequentially introduced into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, or (ii) reactants including the silicon precursor compound of formula (I) and an oxidizing and / or reducing gas are sequentially exposed to a substrate or microelectronic device surface by moving or rotating the substrate through different sections of the reactor, each section being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0027] In one aspect, the present invention relates to a plasma-enhanced atomic layer deposition (PEALD) process for depositing low wet etch rates using a precursor of formula (I) described herein in conjunction with a hydrogen plasma or a nitrogen plasma. Nitrogen plasma is useful for forming silicon nitride films when used in conjunction with the precursor compound of formula (I).

[0028] Thus, in another embodiment, the deposition process described above may further include a step involving exposing the film to a reducing gas. In particular embodiments of the present invention, the reducing gas is comprised of a gas selected from H, hydrazine (NH), methylhydrazine, t-butylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, alkylamines, pyridine, and NH.

[0029] In another embodiment, the deposition process may further include a step involving exposing the precursor to an oxidizing gas, such as O2, O3, N2O, water vapor, alcohol, or oxygen plasma, to form a silicon dioxide film. 1 When is halo, oxidizing agents such as water and alcohols can be used along with bases such as pyridine, alkylamines, N,N'-dimethylformamide, and ammonia. In certain embodiments, the oxidizing gas further comprises an inert gas such as argon, helium, nitrogen, or a combination thereof. In other embodiments, the oxidizing gas further comprises nitrogen, nitrous oxide, or ammonia, which can react with the precursor of Formula (I) under plasma conditions to form a silicon oxynitride film.

[0030] In general, the desired film produced using the precursor compounds of formula (I) can be tailored by the selection of each compound and reaction conditions, along with the use of a reducing or oxidizing co-reactant. See, for example, Scheme 1 below: TIFF0007825656000009.tif57170

[0031] Bis(dimethylsilyl)dimethylhydrazine (each R 1In the case of formula (I) where is methyl, the resulting SiO2 film exhibited a growth rate of 1.3 Å / cycle at 450°C and very fast surface saturation in the oxygen plasma process.

[0032] In one embodiment, an oxidizing gas, such as ozone (O), is utilized in the deposition process to provide a rapidly growing silicon dioxide film. In one embodiment, the temperature is about 500°C to 600°C. Growth rates of 1.9 to about 5.8 Å / cycle were observed for the ozone process. Furthermore, the wet etch rate of the resulting SiO2 films showed improvement over comparative films utilizing BTBAS (bis(t-butylamino)silane) as the silicon precursor.

[0033] For silicon dioxide films, exemplary pulsing regimes include: (i) injection of a precursor of formula (I) for 0.1 to 30 seconds, followed by (ii) purging with an inert gas for 1 to 30 seconds, followed by (iii) injection of ozone at a flow rate of 50-500 sccm (standard cubic centimeters per minute) for approximately 0.1-30 seconds, followed by (iv) Purging with an inert gas for 1 to 30 seconds (1 cycle). Steps (i) to (iv) can then be repeated until a film of the desired thickness is obtained.

[0034] Thus, in another embodiment, the present invention provides a method for preparing a silicon dioxide film, wherein the vapor deposition conditions include a temperature of about 150° C. to about 650° C.; (i) a step of injecting a precursor of formula (I) for 0.1 to 30 seconds, followed by (ii) a purging step using an inert gas for 1 to 30 seconds, followed by: (iii) injecting ozone at a flow rate of 50-500 sccm for about 0.1-30 seconds, followed by: (iv) purging with an inert gas for 1 to 30 seconds, and repeating steps (i) to (iv) until a film of the desired thickness is obtained. and a pulsing sequence including:

[0035] In one embodiment, a nitrogen plasma is used in the deposition process to provide a silicon nitride film. In one embodiment, the temperature is about 200° C. to 300° C. In the case of bis(dimethylsilyl)dimethylhydrazine, a nitrogen plasma is used with a power of 200 watts to 300 watts and a flow rate of 100 to 300 sccm of N2 to provide the silicon nitride.

[0036] For silicon nitride membranes, exemplary pulsing regimes include: (i) injecting a precursor of formula (I) for 0.1 to 30 seconds, followed by (ii) Purging with inert gas for 1 to 30 seconds, followed by (iii) nitrogen plasma injection using N2 at a flow rate of 50-500 sccm and a power of about 50 watts to 1000 watts for 0.1-30 seconds, followed by (iv) Optionally, purge with an inert gas for 1 to 30 seconds after plasma exposure (1 cycle). Steps (i) to (iv) can then be repeated until a film of the desired thickness is obtained.

[0037] Thus, in another embodiment, in preparing silicon nitride films, vapor deposition conditions include a temperature of about 150° C. to about 300° C., a pressure of about 0.1 to about 5 Torr, and (i) injection of a precursor of formula (I) for 0.1 to 30 seconds, followed by (ii) Purging with an inert gas for 1 to 30 seconds, followed by (iii) injection of nitrogen plasma using N2 at a flow rate of 50-500 sccm and a power of about 50 watts to 500 watts for 0.1-30 seconds, followed by (iv) optional purging with an inert gas for 1 to 30 seconds after plasma exposure, and repeating steps (i) to (iv) until a film of the desired thickness is obtained. and a pulsing sequence including:

[0038] During the use of the precursor compound of formula (I), the incorporation of carbon and nitrogen into such films is a natural consequence of the composition of such compounds, and the process conditions can be adjusted to promote the incorporation or elimination of these elements. Furthermore, if the incorporation of carbon is desired, for example, carbon in the form of methane, ethane, ethylene or acetylene can be utilized to further introduce carbon content into the silicon-containing film, thereby producing silicon carbide, silicon carbonitride or silicon carboxide.

[0039] The deposition methods disclosed herein can involve one or more purge gases. Purge gases used to purge unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon, nitrogen, helium, neon, hydrogen, and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and any by-products that may remain in the reactor. Note that gases, such as nitrogen, are inert and act as purges when not activated by the plasma, but are co-reactants when activated by the plasma.

[0040] Each step of supplying the silicon precursor compound, oxidizing gas, reducing gas, and / or other precursors, source gases, and / or reagents can be performed by varying the sequence for supplying them and / or by varying the stoichiometry of the resulting dielectric film.

[0041] Energy is added to the silicon precursor compound of formula (I) and at least one of an oxidizing gas, a reducing gas, or a combination thereof to induce a reaction and form a silicon-containing film on a microelectronic device substrate. Such energy can be provided by, but is not limited to, heat, pulsed heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In other embodiments, a DC bias can be maintained between the plasma and the substrate. In embodiments in which deposition involves plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated "remote" from the reaction zone and the substrate and fed into the reactor.

[0042] As used herein, the term "microelectronic device" corresponds to a semiconductor substrate fabricated for use in microelectronic, integrated circuit, or computer chip applications, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS). It should be understood that the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that contains negative-channel metal-oxide-semiconductor (nMOS) and / or positive-channel metal-oxide-semiconductor (pMOS) transistors and that ultimately becomes a microelectronic device or microelectronic assembly. Such microelectronic devices include at least one substrate that can be selected from, for example, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, antireflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, and porous inorganic materials, metals such as copper, aluminum, cobalt, tungsten, molybdenum, ruthenium, and iridium, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, WN, WC, MoC, or MoN. The films are compatible with various subsequent processing steps, such as, for example, chemical mechanical planarization (CMP) and anisotropic etching steps.

[0043] The present invention can be further described by the following examples of specific embodiments thereof, although it will be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise specified. [Example]

[0044] Example 1 - Synthesis of Dimethylhydrazidedimethylsilane To an ice-cooled solution of N,N'-dimethylhydrazine (88.93 g, 1.48 mol) in n-pentane (350 g, 4.85 mol), a solution of chlorodimethylsilane (70 g, 0.74 mol) in n-pentane (70 g, 0.97 mol) was added dropwise and stirred at below -10 °C. After the addition of the chlorodimethylsilane solution, the reaction mixture was stirred at room temperature for 5 h. The resulting white slurry was filtered and washed with n-pentane (125 g). After removing the volatiles, the resulting crude product was purified by simple distillation at 50 °C and 240 Torr to give the title compound as a colorless liquid (62.50 g, 71.4%).

[0045] Example 2 - Synthesis of bis(dimethylsilyl)dimethylhydrazine A solution of n-butyllithium in n-hexane (203 mL, 2.5 mol) was added dropwise to a solution of dimethylhydrazide-dimethylsilane (60 g, 0.507 mol) in n-hexane (210 g, 2.44 mol) at -20 °C. After the addition of the n-butyllithium solution, the reaction mixture was stirred at room temperature for 2 hours and then cooled to 10 °C. A solution of chlorodimethylsilane in n-hexane was added dropwise to the reaction mixture, which was then stirred at room temperature for 5 hours. The resulting white slurry was filtered and washed with n-hexane (90 g). After removing the volatiles, the resulting crude product was purified by simple distillation at 80 °C and 80 Torr to give the final product as a colorless liquid (78.71 g, 63.5%).

[0046] Example 3 - Deposition of Silicon Dioxide Film Silicon oxide films were deposited using bis(dimethylsilyl)dimethylhydrazine vapor as the silicon precursor. Bis(dimethylsilyl)dimethylhydrazine was placed in a bubbler at room temperature. Silicon oxide films were deposited on silicon wafers using an ozone co-reactant at wafer temperatures of 500-600°C using a double showerhead ALD reactor. The reactor pressure was controlled between 0.5 and 1.5 Torr. Silicon oxide films were formed using the following pulse sequence: a 28-second silicon precursor pulse, a 20-second Ar purge, a 25-second ozone pulse, and a 20-second Ar purge. This sequence was repeated 160 times to obtain a film thickness of 400 Å. The deposition rate saturated at approximately 2.5 Å / cycle at 550°C, with no carbon or chlorine impurities present in the film. The wet etch rate of the film was 51.4 Å / min using a 0.2% HF dilute solution.

[0047] Example 4 - Deposition of Silicon Nitride Films Silicon nitride films were deposited using bis(dimethylsilyl)dimethylhydrazine as the silicon precursor material. The BDMSDMH bubbler was maintained at room temperature (approximately 23 °C), and the reactor pressure was controlled between 0.5 and 1.5 Torr. The following pulse sequence was used to form silicon nitride films: a 28-second silicon precursor pulse, a 20-second Ar purge, a 15- or 20-second direct nitrogen plasma with a 13.56 MHz frequency pulse at 200 or 300 W, and a 20-second Ar purge. This sequence was repeated 170 times, resulting in a film thickness of 200 Å. This process was free of carbon and chlorine impurities in the film and saturated at approximately 1.16 Å / cycle at 300 °C.

[0048] The invention has been described in detail with particular reference to certain embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

[0049] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Many advantages of the present disclosure, which are covered by this document, have been set forth in the foregoing description. It will be understood, however, that the present disclosure is in many respects merely illustrative. Changes may be made in details, particularly in matters relating to the shape, size, and arrangement of parts, without exceeding the scope of the present disclosure. The scope of the present disclosure is, of course, defined in the language in which the appended claims are expressed.

Claims

1. 1. A method for depositing a silicon-containing film on a surface of a microelectronic device, comprising: Formula (I): (In the formula, each R １ is hydrogen or C １ ~C ４ alkyl, with the proviso that all R １ and (II) is not hydrogen, under vapor deposition conditions to said surface in a reaction chamber.

2. The method of claim 1 , wherein the silicon-containing film is silicon dioxide.

3. The method of claim 1 , wherein the silicon-containing film is silicon nitride.

4. 10. The method of claim 1, wherein the vapor deposition conditions are selected from chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), a plasma-enhanced ALD-like process, or an ALD process using an oxygen-containing reactant, a nitrogen-containing reactant, or a combination thereof.

5. The vapor deposition conditions are a temperature of 150°C to 650°C; (i) injection of a precursor of formula (I) for 0.1 to 30 seconds, followed by (ii) a purging step with an inert gas for 1 to 30 seconds, followed by: (iii) injecting ozone at a flow rate of 50-500 sccm for 0.1-30 seconds, followed by: (iv) purging with an inert gas for 1 to 30 seconds, and repeating steps (i) to (iv) until a film of the desired thickness is obtained. and a pulsing sequence including The method of claim 1 , comprising:

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