Silicon hydrazide precursor compounds

Abstract

To provide compositions and methods for forming silicon-containing films at relatively low temperatures.SOLUTION: The invention provides a compound of the formula (I) in the figure. In the formula, R1 and R2 are independently selected from C1-C4 alkyl, phenyl, substituted phenyl and C4-C6 cycloalkyl, or can be taken together with the nitrogen atom to which they are bound to form a C3-C5 nitrogen-containing ring; R3 and R4 are independently selected from hydrogen and C1-C4 alkyl, or are taken together with the Si atom to which they are bound to form a C3-C5 silicon-containing ring; R5 and R6 are independently selected from hydrogen and C1-C4 alkyl; and Q may be chloro, bromo, or iodo.SELECTED DRAWING: None

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., less than 1000 nanometers thick) passive layers of chemically inert dielectric materials such as silicon carbide (SiC), silicon carbon nitride (SiCN) and silicon carbon oxide (SiCO) and / or silicon dioxide (SiO2) are widely used in microelectronic device construction to function as structural elements of 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 method for forming such films. CVD processes involving low deposition temperatures, e.g., temperatures below about 450°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, temperatures above 450°C can be utilized to achieve the desired dielectric film.

[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. However, SiN has a high dielectric constant (k) of about 7.5. To reduce the dielectric constant and maintain good etch and ashing resistance during post-deposition processing, carbon and nitrogen doped SiO2 (SiCON) spacers have been developed. Currently, the best etch and ashing resistant SiCON dielectrics have k values ​​of about 4.0. Next generation devices require etch and ashing resistant dielectrics with k values ​​below 3.5.

[0005] Furthermore, there remains a need for improved organosilicon precursors and processes for forming silicon-containing films in the manufacture of microelectronic devices, particularly in processes utilizing low temperature deposition techniques for forming silicon nitride, silicon dioxide, and silicon oxynitride films.In particular, there is a need for liquid silicon precursors that have good thermal stability, 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 specifically to compositions and methods for forming such silicon-containing films, such as films comprising silicon, silicon nitride, silicon oxynitride, silicon dioxide, carbon-doped silicon nitride or silicon oxide, or carbon-doped silicon oxynitride films, at relatively low temperatures.

[0007] The compounds of formula (I) described herein are useful as precursor compounds in the formation of such various silicon-containing films.Vapor deposition conditions and processes can be used with these precursor compounds to form silicon-containing films, 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 with oxygen-containing reactants, nitrogen-containing reactants, or combinations thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context 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.

[0009] 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 cases, the term "about" can include numbers that are rounded to the nearest significant figure.

[0010] Numeric 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).

[0011] In a first aspect, the present invention provides a compound of formula (I): TIFF0007661455000001.tif29170 (in the formula, R 1 and R 2 are independently selected from C1-C4 alkyl, phenyl, substituted phenyl, or C4-C6 cycloalkyl, or can be taken together with the nitrogen atom to which they are attached to form a C3-C5 nitrogen-containing ring; R 3 and R 4 are independently selected from hydrogen or C1-C4 alkyl, or together with the Si atom to which they are attached form a C3-C5 silicon-containing ring, and R 5 and R 6 is independently selected from hydrogen or C1-C4 alkyl; Q is chloro, bromo, iodo or a group of the formula TIFF0007661455000002.tif46170, and x is 0 or 1, and (i) y is 0, with the proviso that when y is 0, Q is of the formula other than the base TIFF0007661455000003.tif21170, or (ii) if x is 1, then y is 1.

[0012] As used herein, the term "substituted phenyl" refers to a phenyl group containing one or two C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, C1-C4 alkanoyloxy, C1-C4 alkanoylamino, halogen, carboxy, nitro, hydroxy, C1-C4 alkylene--OH, C1-C4 alkylene--CO2R7, --OC1-C4 alkylene--OH, or --OC1-C4 alkylene--CO2R7 (wherein R7 is a C1-C6 alkyl group) as substituents.

[0013] In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each of is independently selected from methyl, ethyl, or isopropyl.

[0014] In another embodiment, the compound of formula (I) has the formula: TIFF0007661455000004.tif30170.

[0015] In another embodiment, the compound of formula (I) has the formula: Selected from TIFF0007661455000005.tif133170.

[0016] In another embodiment, the present invention provides a compound of formula: TIFF0007661455000006.tif35170 [wherein Q is chloro, bromo or iodo, or a group of the formula TIFF0007661455000007.tif22170 (in the formula, R 1 and R 2are independently selected from C1-C4 alkyl, phenyl, substituted phenyl, or C4-C6 cycloalkyl, or can be taken together with the two nitrogen atoms to which they are attached to form a C3-C5 nitrogen-containing ring. The present invention provides a compound having the formula:

[0017] In certain embodiments, Q is chloro.

[0018] In another embodiment, the present invention provides a compound of formula TIFF0007661455000008.tif30170 (in the formula, R 1 and R 2 is independently selected from C1-C4 alkyl, phenyl, substituted phenyl, or C4-C6 cycloalkyl, n is 1, 2, or 3, and R 4 is selected from hydrogen, chloro, bromo or iodo, or is represented by the formula (selected from the group TIFF0007661455000009.tif48170) The present invention provides a compound having the formula:

[0019] In certain embodiments, R 1 and R 2 is independently selected from methyl, ethyl, and isopropyl. In other embodiments, n is 1.

[0020] In another embodiment, the present invention provides a compound of formula: The present invention provides a compound of formula (I) having the formula TIFF0007661455000010.tif87170.

[0021] In certain embodiments, the compound of formula (I) has less than 100 ppm, 50 ppm, or less than 10 ppm chlorine contamination.

[0022] The compounds of formula (I) are useful as precursors for the deposition of silicon-containing films on the surface of microelectronic devices. In certain embodiments, the films also contain nitrogen and / or oxygen and / or carbon.

[0023] Thus, in a second aspect, the present invention provides a method for forming 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.

[0024] As used herein, silicon-containing films refer to films such as silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbonitride, silicon oxycarbonitride, low-k thin silicon-containing films, high-k gate silicate films, and low temperature silicon epitaxial films.

[0025] 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.

[0026] In certain embodiments, the pulse time of the precursor compounds (i.e., duration of precursor exposure to the substrate) ranges from about 1 to 10 seconds. If a purge step is utilized, the duration is about 1 to 4 seconds or 1 to 2 seconds. In other embodiments, the pulse time of the co-reactant ranges from 1 to 60 seconds. In other embodiments, the pulse time of the co-reactant ranges from about 5 to about 10 seconds.

[0027] In one embodiment, the vapor deposition conditions include a temperature between about 350° C. and about 750° C. and a pressure between about 1 and about 1000 Torr. In another embodiment, the vapor deposition conditions include a temperature between about 350° C. and about 650° C.

[0028] The above compounds 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 processes. Such deposition processes can be used to form silicon-containing films on microelectronic devices using deposition temperatures of about 350° to about 550° C. to form films having thicknesses of about 20 angstroms to about 2000 angstroms.

[0029] In the processes 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.

[0030] Alternatively, the process 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 a process in which (i) each reactant comprising the silicon precursor compound of formula (I) and oxidizing and / or reducing gas is introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, or (ii) each reactant comprising the silicon precursor compound of formula (I) and oxidizing and / or reducing gas is exposed to the substrate or microelectronic device surface by moving or rotating the substrate to different sections of the reactor, and each section is separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0031] In one aspect, the present invention relates to a plasma enhanced atomic layer deposition (PEALD) process for depositing low wet etch rate and O2 ashing resistant low-k thin films using the precursors of formula (I) described herein with hydrogen plasma or nitrogen plasma. Nitrogen plasma can be useful for forming silicon nitride films using compounds of formula (I).

[0032] In general, the desired film produced using the precursor compounds of formula (I) can be tailored by the selection of each compound in combination with the use of a reducing or oxidizing co-reactant. See, for example, Scheme 1 below, which shows how the precursors of formula (I) can be used in a deposition process. TIFF0007661455000011.tif52170

[0033] Thus, in another embodiment, the deposition process described above may further include a step comprising exposing the film to a reducing gas. In a particular embodiment of the present invention, the reducing gas is comprised of a gas selected from H2, hydrazine (N2H4), methylhydrazine, t-butylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and NH3.

[0034] 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, but are stable to thermal decomposition at temperatures involved in precursor volatilization or vaporization, allowing consistent and repeatable transport of the resulting precursor vapor to deposition zones or reaction chambers.The chemical reactivity of compounds of formula (I) allows film growth at low temperatures where traditional silicon precursor materials, such as TEOS, are inert and therefore exhibit little or no deposition behavior.

[0035] In another embodiment, the deposition process may further include a step including exposing the precursor to an oxidizing gas, such as O2, O3, N2O, water vapor, alcohol, or oxygen plasma. In a particular embodiment, the oxidizing gas further comprises an inert gas, such as argon, helium, nitrogen, or a combination thereof. In another embodiment, the oxidizing gas further comprises nitrogen, which can react with the precursor of formula (I) under plasma conditions to form a silicon oxynitride film.

[0036] Although the precursor compound of formula (I) is used, the incorporation of carbon and nitrogen into such films is a natural consequence of the composition of such compounds.Furthermore, carbon in the form of, for example, methane, ethane, ethylene or acetylene can be utilized to further introduce carbon content into the silicon-containing film, thereby producing silicon carbide.

[0037] The deposition methods disclosed herein can include 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, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0038] Each step of supplying the silicon precursor compound, the oxidizing gas, the reducing gas, and / or other precursors, source gases, and / or reagents may be performed by varying the order for supplying them and / or by varying the stoichiometry of the resulting dielectric film.

[0039] 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 methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where 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" to the reaction zone and the substrate and fed into the reactor.

[0040] As used herein, the term "microelectronic device" corresponds to semiconductor substrates, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), fabricated for use in microelectronic, integrated circuit, or computer chip applications. 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 will ultimately become a microelectronic device or microelectronic assembly. Such microelectronic devices may be, for example, silicon, SiO2, Si3N4, or other semiconductor substrates. 、 The at least one substrate may be selected from OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, porous inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The films are compatible with a variety of subsequent processing steps, such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.

[0041] Particular compounds of formula (I) are those of the formula: Such compounds can be prepared by starting from TIFF0007661455000012.tif44170 and reacting it with a variety of amine and azide compounds.

[0042] Other compounds of formula (I) can be prepared starting with cyclotrimethylenedichlorosilane as the primary reactant with various amine and azide compounds according to the flow diagram below. TIFF0007661455000013.tif23170

[0043] The present invention can be further illustrated by the following examples of specific embodiments thereof, however, 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 specifically stated. EXAMPLES

[0044] Example 1 TIFF0007661455000014.tif51170CTMDCS (cyclotrimethylenedichlorosilane) (1 g, 7.08 mmol) was placed in a 20 mL glass vial. Pentane (2 mL) was added followed by TEA (triethylamine) (1.3 g, 12.8 mmol). To the resulting cloudy solution was added UDMH (unsymmetric dimethylhydrazine) (1.1 g, 16.6 mmol) dropwise. A vigorous exothermic reaction ensued and a thick precipitate formed immediately. The solid was extracted with 10 mL of diethyl ether and the combined extracts were filtered and the volatiles removed under reduced pressure to give a pale yellow oil, ca. 0.5 g, 80% purity.

[0045] The crude product was analyzed by NMR. 29Si NMR analysis showed a single major silicon species and the product was confirmed by 13C and 1H NMR. The overall purity of the crude product was about 80%. The product could be further purified by short path distillation to obtain high purity semiconductor grade material. NMR analysis: 1 H NMR(C6D6): δ1.58(t,4H,CH2), 1.90(m,2H,CH2),2.27(s,12H,NN(CH3)2); 13 C{1H}NMR(C6D6):δ 13.6(CH2),22.7(CH2),52.5(CH3); 29 Si NMR(C6D6): δ-11.49

[0046] Example 2 TIFF0007661455000015.tif41170In a 1 L three-necked round bottom flask equipped with a magnetic stir bar, a thermocouple adapter and temperature reading, 1,3-dichloro-tetramethyl-disiloxane (10 g, 49.2 mmol) was dissolved in pentane (200 mL) (T1=24.1° C.). To the clear solution, TEA (11 g, 108 mmol) was added. A slightly cloudy reaction mixture was formed (T1=25.3° C.). To the resulting reaction mixture, UDMH (6.5 g, 108 mmol) was added as a solution in diethyl ether (5 mL). The UDMH solution was added dropwise over 10 min (approximately 1 mL / min). Immediate fuming was observed and a dense precipitate formed in the headspace. 5 min after addition, a large amount of precipitate was observed. The reaction mixture was left for an additional 2 h before being filtered through a coarse filter. The salt was washed twice with 50 mL of hexane. The combined washes were subjected to vacuum distillation to remove volatiles at room temperature to 1.2 Torr. The resulting cloudy viscous oil was filtered and analyzed by 1H, 13C and 29Si NMR. Yield 7.2 g, approximately 90% purity. Yield 58% crude. No further purification was attempted, but further purification by distillation can provide electronic grade material. NMR analysis: 1 H NMR(C6D6): δ0.25(s,12H,Si- CH3 ), 2.21(bs,2H,N H ),2.29(s,12H,NN( CH3 )2); 13 C{1H}NMR(C6D6):δ-0.74(Si-CH3),52.4(N-CH3); 29Si NMR(C6D6): δ-16.16

[0047] Example 3 CTMDCS (1 g, 7.08 mmol) was placed in a 20 mL glass vial. Pentane (2 mL) was added followed by TEA (1.3 g, 12.8 mmol). To the resulting cloudy solution was added UDMH (1.1 g, 16.6 mmol) dropwise. A vigorous exothermic reaction ensued and a thick precipitate formed immediately. The solid was extracted with 10 mL of diethyl ether and the combined extracts were filtered and the volatiles removed under reduced pressure to give approximately 0.5 g of a pale yellow oil, 80% pure.

[0048] The crude product was analyzed by NMR. 29 Si NMR analysis showed a single major silicon species. 13 C and 1 Confirmed by H NMR, overall purity is about 80%. NMR analysis: 1 H NMR(C6D6): δ1.58(t,4H,CH2),1.90(m,2H,CH2),2.27(s,12H,NN(CH3)2); 13 C{ 1 H}NMR(C6D6):δ 13.6(CH2),22.7(CH2),52.5(CH3); 29 Si NMR(C6D6): δ-11.49

[0049] Example 4 - Synthesis of 2-(2-chloro-1,1,2,2-tetramethyldisilan-1-yl)-1,1-dimethylhydrazine TIFF0007661455000016.tif34170A 10 L reactor equipped with a mechanical overhead stirrer, thermocouple probe, temperature readout and nitrogen gas inlet adapter, solvent supply lines (3 / 8'' PTFE tubing), another 3 / 8'' PTFE tubing for reagent loading and filtration was dried and purged with nitrogen. A 5 L filter funnel was leaked to 80 mT and purged with nitrogen overnight.

[0050] Cl2Me4Si2 (100 g, 534 mmol) and TEA (114 g) were combined in a 1 L flask inside a glove box. Some fuming occurred and the solution became slightly cloudy. A solution of UDMH (64.2 g, 81.2 mL) in diethyl ether (approximately 220 mL) was prepared in a 500 mL liquid addition funnel. The reactor was charged with 2.5 L of hexane and cooled to -4°C. The chiller was set at -10°C. The mixture of Cl2Me4Si2 and TEA (neat) was charged under nitrogen flow using a 3 / 8'' PTFE tube. An additional amount of hexane (approximately 500 mL) was added. The mixture was stirred under nitrogen. An addition funnel containing UDMH in ether (310 mL solution) was attached to the reactor under nitrogen flow. The UDMH solution was added dropwise over 45 minutes at a rate of approximately 6.8 mL / min. The reaction mixture was stirred at room temperature overnight while maintaining the reaction temperature below 0° C., and then filtered through a 5 L fritted filter funnel. The solid was washed twice with hexane (500 mL) and the solvent was removed under reduced pressure to 4.8 Torr at −21.1° C. The resulting colorless oil was transferred to a three-neck round-bottom flask for further purification. The title compound was identified as the major intermediate by 1H NMR, 13C NMR, and 29Si NMR. NMR analysis: 1 H NMR(C6D6): δ 0.22 (s, 6H, Si- CH3 ), 0.49(s,6H,Si- CH3 ), 1.89(bs,1H,N H ), 2.12(s,6H,NN (CH3) 2); 13 C{1H}NMR(C6D6):δ-1.8,2.7(Si-CH3),52.4(N-CH3); 29 Si NMR(C6D6): δ-9.1, 19.4.

[0051] Example 5 TIFF0007661455000017.tif37170 The partially substituted intermediate (2-(2-chloro-1,1,2,2-tetramethyldisilan-1-yl)-1,1-dimethylhydrazine) (0.21 g, 1 mmol) (synthesized in Example 4) could be further reacted with a stoichiometric amount of diethylamine (0.73 g, 1 mmol) in the presence of triethylamine (0.101 g, 1 mmol) in hexane (20 mL). The resulting slurry is filtered and the volatiles are removed under reduced pressure to give the title compound. The product could be further purified by distillation.

[0052] Example 6 - PEALD Silicon Nitride Deposition using Ar / N2 Plasma (Predicted) Silicon-containing films are deposited using the silicon precursor of formula (I) and Ar / N2 plasma as co-reactant gases under the process conditions set forth in the table below. TIFF0007661455000018.tif42170

[0053] Example 7 - PEALD silicon oxide deposition using Ar / O2 plasma Using the process conditions set forth in the table below, silicon-containing films could be deposited using the silicon precursor of formula (I) and Ar / O2 plasma as co-reactants. TIFF0007661455000019.tif42170

[0054] Example 8 - CVD Deposition Vaporization of the compound of formula (I) and introduction into the CVD chamber can be accomplished by gentle heating to 40°C at 40 Torr. The precursors can be dispersed through a circular showerhead to provide uniform delivery to the heated substrate. A mixture of nitrogen, oxygen (O2) and nitrous oxide (N2O) is expected to co-react with the substrate containing metal, silicon and silicon nitride regions, and a film of SiCOx is deposited at 450°C for 10 minutes. This precursor and process is expected to deposit uniform, highly conformal coatings on structured substrates with desirable dielectric properties and excellent wet etch resistance. The film is expected to show a slight increase in wet etch resistance after ashing in an O2 plasma for 30 seconds.

[0055] Example 9 - PECVD Deposition Vaporization of compound 1 of formula (I) and introduction into the PE-CVD chamber could be achieved with gentle heating at 35°C and 1 Torr. The precursor could be dispersed through a circular showerhead to provide uniform release directly into the argon plasma (250 watts). A mixture of nitrogen and ammonia (NH3) co-reactants could also be introduced into the plasma, which is expected to result in gas-phase dissociation of the precursor and deposition of a SiCNx film onto the heated substrate (300°C). The substrate is expected to consist of high aspect ratio patterns of metal and dielectric features, and the deposited film is expected to exhibit acceptable conformity to the features. This precursor and process is expected to deposit compositionally uniform films across the patterned substrate and exhibit acceptable wet etch resistance both before and after plasma ashing in O2.

[0056] 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.

Claims

1. A compound of formula (I) (In the formula, R １ and R ２ is independently １ -C ４ Alkyl, phenyl, substituted phenyl or C ４ -C ６ cycloalkyl, or together with the nitrogen atom to which they are attached, C ３ -C ５ A nitrogen-containing ring can be formed, R ３ and R ４ are independently hydrogen or C １ -C ４ alkyl, or together with the Si atom to which they are attached, C ３ -C ５ Forms a silicon-containing ring and R ５ and R ６ are independently hydrogen or C １ -C ４ alkyl, Q is bromo, iodo or a group of the formula and x is 0 or 1, and (i) y is 0, or (ii) y is 1.

2. A method for forming a silicon-containing film on a surface of a microelectronic device, comprising depositing, under vapor deposition conditions, on said surface in a reaction chamber at least one compound of formula (I). wherein R 1 and R 2 are independently selected from C 1 -C 4 alkyl, phenyl, substituted phenyl, or C 4 -C 6 cycloalkyl, or can be taken together with the nitrogen atom to which they are attached to form a C 3 -C 5 nitrogen-containing ring; R 3 and R 4 are independently selected from hydrogen or C 1 -C 4 alkyl, or can be taken together with the Si atom to which they are attached to form a C 3 -C 5 silicon-containing ring; and R 5 and R 6 are independently selected from hydrogen or C 1 -C 4 alkyl; Q is bromo, iodo or a group of the formula and x is 0 or 1, and (i) y is 0, or (ii) y is 1. The method includes introducing

3. 3. The method of claim 2, 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), plasma enhanced ALD-like process, or an ALD process.

4. 3. The method of claim 2, wherein the silicon-containing film is selected from silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbonitride, silicon oxycarbonitride, low-k silicon-containing thin films, high-k gate silicate films, and low-temperature silicon epitaxial films.

5. 3. The method of claim 2, wherein the surface is selected from silicon dioxide, silicon nitride, aluminum oxide, aluminum nitride, aluminum, tungsten, copper, cobalt, molybdenum, ruthenium, silicon wafer, or combinations thereof.

6. The method of claim 2 , wherein the surface is silicon dioxide.

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