Composition for high temperature atomic layer deposition of high quality silicon oxide thin films

Abstract

An atomic layer deposition (ALD) process for forming silicon oxide at a temperature > 600 DEG C is disclosed. The silicon precursor used has the formula: I. R1R2mSi (NR3R4) n, wherein R1, R2 and R3 are each independently selected from a linear or branched C1 to C10 alkyl group and a C6 to C10 aryl group; r4 is selected from the group consisting of hydrogen, linear or branched C1 to C10 alkyl groups and C6 to C10 aryl groups, C3 to C10 alkylsilyl groups; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; m is 0 to 2; n is 1 to 3; and m + n = 3.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 201980073496.6, application date October 3, 2019, and invention name “Composition for high temperature atomic layer deposition of high-quality silicon oxide films”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. Provisional Patent Application No. 62 / 741,126, filed on October 4, 2018, the entire contents of which are incorporated herein by reference. Background of the Invention

[0005] Compositions and methods for forming silicon oxide films are described herein. More specifically, compositions and methods for forming silicon oxide films at one or more deposition temperatures of about 600° C. or higher and using an atomic layer deposition (ALD) process are described herein.

[0006] Thermal oxidation is a process commonly used in semiconductor applications to deposit high purity and highly conformal silicon oxide films, such as silicon dioxide (SiO2). However, the thermal oxidation process has a very low deposition rate, for example, less than 100 Å at 700°C. This makes it unsuitable for high-volume manufacturing processes (see, for example, Wolf, S., “Silicon Processing for the VLSI Era Vol. 1—Process Technology”, Lattice Press, CA, 1986).

[0007] Atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) are processes for depositing conformal films of silicon dioxide (SiO2) at low temperatures (<500°C). In the ALD and PEALD processes, precursors and reactive gases (e.g., oxygen or ozone) are pulsed separately in a certain number of cycles to form a monolayer of silicon dioxide (SiO2) in each cycle. However, silicon dioxide (SiO2) deposited at low temperatures using these processes may contain levels of impurities that are harmful to semiconductor applications, such as carbon (C), nitrogen (N), hydrogen (H), or a combination of these. To address this issue, one possible solution is to increase the deposition temperature, such as 500°C or higher. However, at these higher temperatures, conventional precursors used by the semiconductor industry tend to self-react, thermally decompose, and deposit in a chemical vapor deposition (CVD) mode rather than an ALD mode. Compared to ALD deposition, CVD mode deposition has reduced conformality, especially in high aspect ratio structures in semiconductor applications. In addition, CVD mode deposition has less control over the thickness of the film or material than ALD mode deposition.

[0008] JP2010275602 and JP2010225663 disclose forming a silicon-containing thin film such as silicon oxide by a CVD process using a raw material at a temperature range of 300-500°C. The raw material is an organic silicon compound represented by the following formula: (a) HSi(CH3)(R 1 )(NR 2 R 3 ), where R 1 Represents NR 4 R 5 or 1C-5C alkyl; R 2 and R 4 Each represents a 1C-5C alkyl group or a hydrogen atom; and R 3 and R 5 represents 1C-5C alkyl; or (b) HSiCl(NR 1 R 2 )(NR 3 R 4 ), where R 1 and R 3 independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; and R 2 and R 4 and independently represent an alkyl group having 1 to 4 carbon atoms. The organosilicon compound contains an H-Si bond.

[0009] US Patent No. 7,084,076 ("the '076 patent") discloses a halogenated siloxane, such as hexachlorodisiloxane (HCDSO), in combination with pyridine as a catalyst for ALD deposition at less than 500°C to form silicon dioxide.

[0010] U.S. Patent No. 6,992,019 ("the '019 patent") discloses a catalyst-assisted ALD method for forming a silicon dioxide layer having excellent properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using an aliphatic tertiary amine as a catalyst component, or a combination of both, and associated purge methods and sequencing. The precursor used is hexachlorodisilane. The deposition temperature is between 25-150°C.

[0011] U.S. Patent Nos. 9,460,912 and 10,242,864 ("the '912 and '864 patents") disclose compositions and atomic layer deposition (ALD) methods for forming films containing silicon oxide at one or more deposition temperatures of about 500 degrees Celsius. In one aspect, the compositions and methods use one or more silicon precursors selected from compounds having the following formulas I, II, and combinations thereof: R 1 R 2 m Si(NR3 R 4 ) n X p I and R 1 R 2 m Si(OR 3 ) n (OR 4 ) q X p II.

[0012] There is a need to develop a method for forming high quality, low impurity, highly conformal silicon oxide films using an ALD process or an ALD-like process (such as, but not limited to, a CVD process) instead of a thermal-based deposition process. In addition, it is desirable to develop high temperature deposition (e.g., deposition at one or more temperatures of 600° C.) in an ALD or ALD-like process to improve one or more film properties, such as purity and / or density. SUMMARY OF THE INVENTION

[0014] Described herein is a method for depositing silicon oxide materials or films in an ALD or ALD-like process at high temperatures, for example, at one or more temperatures of 600° C. or higher.

[0015] One disclosed embodiment is a method for depositing a silicon oxide film onto a substrate, comprising the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor into the reactor, wherein the at least one silicon precursor has a structure represented by Formula I:

[0016] R 1 R 2 m Si(NR 3 R 4 ) n (I)

[0017] Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl; R 4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, and C3 to C 10alkylsilyl; m is 0 to 2; and n is 1 to 3, wherein m+n=3; c. purging the reactor with a purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with a purge gas, wherein steps b to e are repeated until a desired thickness of silicon oxide is deposited, and wherein the method is carried out at one or more temperatures in the range of 600 to 800°C and one or more pressures in the range of 50 millitorr (mT) to 760 Torr.

[0018] In another embodiment, a method for depositing a silicon oxide film is disclosed, comprising the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor into the reactor, wherein the at least one silicon precursor has a structure represented by Formula I:

[0019] R 1 R 2 m Si(NR 3 R 4 ) n (I)

[0020] Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl; R 4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, and C3 to C 10 alkylsilyl; m is 0 to 2; and n is 1 to 3, wherein m+n=3; c. purging the reactor with a purge gas; d. introducing an oxygen source into the reactor; e. purging the reactor with a purge gas; f. introducing water vapor or an OH source into the reactor; and g. purging the reactor with a purge gas, wherein steps b to g are repeated until the desired thickness is deposited, and wherein the process temperature ranges from 600 to 800°C and the pressure in the reactor ranges from 50mT to 760 Torr.

[0021] The silicon oxide film disclosed herein and prepared by any of the above methods has a 1.0e -9 A / cm 2 or lower leakage current, or 1.0e at 4MV / cm -9 A / cm 2 or lower leakage current, or 1.0e at 6MV / cm -8 A / cm 2 or lower leakage current.

[0022] Other features and advantages of the present invention will become apparent from the following more detailed description of the preferred embodiments in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. The embodiments and features of the present invention may be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Figure 2 is the leakage current curve of silicon oxide films deposited with DMATMS with >50 ppm chloride impurities at 650°C and 700°C, respectively. The film leakage current is greater than 1.0e at 2MW / cm -9 A / cm 2 , greater than 1.0e at 4MV / cm -9 A / cm 2 , greater than 1.0e at 6MV / cm -8 A / cm 2 .

[0025] Figure 2 Figure 2 is the leakage current curve of silicon oxide films deposited with DMATMS with 2 ppm chloride impurities at 650°C and 700°C, respectively. The leakage current of the 700°C film is less than 1.0e at 2MW / cm -9 A / cm 2 , below 1.0e at 4MV / cm -9 A / cm 2 , below 1.0e at 6MV / cm -8 A / cm 2 . DETAILED DESCRIPTION OF THE INVENTION

[0027] Described herein are compositions and methods related to forming a silicon oxide-containing film, such as a silicon oxynitride film, a stoichiometric or non-stoichiometric silicon oxide film, a silicon oxide film, or a combination thereof, in an ALD or ALD-like process (such as, but not limited to, a cyclic chemical vapor deposition process (CCVD)) using one or more temperatures of 600° C. or higher, preferably 700° C. or higher, and most preferably 720° C. or higher. The high temperature deposition (e.g., one or more deposition temperatures in the range of about 600 to 800° C.) methods described herein provide films or materials that exhibit at least one or more of the following advantages: a density of about 2.1 g / cm 3 or greater, low chemical impurities, high conformality in thermal atomic layer deposition, PEALD processes, or PEALD-like processes, the ability to adjust the carbon content of the resulting film; and / or an etch rate of 5 angstroms per second for the film when measured in 0.5 wt% dilute HF For carbon-doped silicon oxide films, in addition to other properties (such as but not limited to a density of about 1.8 g / cm 3 or greater or about 2.0 g / cm 3or greater), more than 1% carbon is required to adjust the etching rate in 0.5wt% dilute HF to less than Importantly, the leakage current of the deposited silicon oxide is 1.0e at 2MW / cm -9 A / cm 2 or lower, or 1.0e at 4MV / cm -9 A / cm 2 or lower, or 1.0e at 6MV / cm -8 A / cm 2 or lower.

[0028] Typical ALD processes in the prior art directly use an oxygen source or an oxidant such as oxygen, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide or ozone source to form SiO2 at a process temperature ranging from 25 to 500°C. The deposition steps include:

[0029] a. providing a substrate in a reactor;

[0030] b. introducing a silicon precursor into the reactor,

[0031] c. purging the reactor with a purge gas;

[0032] d. introducing an oxygen source into the reactor; and

[0033] e. Purge the reactor with purge gas.

[0034] In such prior art methods, steps b to e are repeated until the desired film thickness is deposited.

[0035] It is believed that high temperature processes, i.e. above 600°C, produce better film quality in terms of film purity and density. The ALD process provides good film step coverage, however, typical organosilicon precursors used in ALD or PEALD can only deposit films in the ALD mode within a temperature range that is typically below 500°C. When the temperature is above this range, the precursor undergoes thermal decomposition, which results in gas phase reactions or continuous substrate surface reactions, which changes the deposition process to a CVD mode instead of the desired ALD mode.

[0036] Without wishing to be bound by a particular theory, for ALD or ALD-like deposition processes at one or more temperatures greater than 600° C., the silicon precursor molecules described herein have at least one anchoring functional group that reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon material. The anchoring functional group may be selected from an amino group, such as a dimethylamino group or a diethylamino group. The silicon precursor should also have a passive functionality because it is chemically stable to prevent further surface reactions, thereby resulting in a self-limiting process. The passivating functional group is selected from different alkyl groups such as methyl, ethyl, phenyl, preferably methyl. The remaining groups on the surface can then be oxidized to form Si-O-Si connections and hydroxyl groups. In addition, a hydroxyl source (e.g., H2O or water plasma) can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle, as shown in Scheme 1 below.

[0037]

[0038] In one embodiment, at least one silicon precursor described herein is a compound having the following Formula I:

[0039] R 1 R 2 m Si(NR 3 R 4 ) n (I)

[0040] Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl; R 4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, C3 to C 10 Alkylsilyl; wherein R 3 and R 4 connected to form a cyclic ring structure or R 3 and R 4 m is 0 to 2; n is 1 to 3; and m+n=3; and wherein the silicon precursor is substantially free of one or more impurities selected from halides, metal ions, metals, and combinations thereof.

[0041] Examples of precursors having Formula I include, but are not limited to, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, tert-butylaminotriethylsilane, isopropylaminotriethylsilane, diisopropylaminotriethylsilane, pyrrolidinyltriethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidinyltrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, tert-butylaminodimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, Dimethylsilane, pyrrolidinyldimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, tert-butylaminodiethylsilane, isopropylaminodiethylsilane, diisopropylaminodiethylsilane, pyrrolidonyldiethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, dipyrrolidinyldimethylsilane, bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)dimethylsilane 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 2,6-dimethylaminobenzene trimethylsilane, 1-methylpiperazinyltrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, and mixtures thereof.

[0042] The precursor having the structure of Formula I has an anchoring functional group selected from an amine group and an alkoxy group, and has a functionally passivated alkyl group, which is preferably a methyl group. Without intending to be bound by a particular theory, it is believed that the Si-Me group is stable at temperatures above 600°C and provides a passivating functional group to prevent further surface reactions, thereby resulting in a self-limiting ALD or ALD-like process.

[0043] In the above formula and throughout the specification, the term "alkyl" means a straight or branched functional group having 1 to 10, 3 to 10, or 1 to 6 carbon atoms. Exemplary straight chain alkyls include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Exemplary branched alkyls include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl may have one or more functional groups attached thereto, such as, but not limited to, alkoxy, dialkylamino, or a combination thereof. In other embodiments, the alkyl does not have one or more functional groups attached thereto. The alkyl may be saturated or alternatively unsaturated.

[0044] In the above formula and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 3 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0045] In the above formula and throughout the specification, the term "amino" refers to an alkyl or aromatic group (e.g., NR as defined above) attached to a nitrogen atom. 3 R 4 ) and may have 1 to 12 or 1 to 6 carbon atoms. Exemplary amino groups include, but are not limited to, dimethylamino, diethylamino, tert-butylamino, cyclohexylamino, piperidino, alkyl-substituted piperidino (e.g., 2,6-dimethylpiperidino), pyrrolidinyl, alkyl-substituted pyrrolidinyl (e.g., 2,5-dimethylpyrrolidinyl), pyrrolyl, alkyl-substituted pyrrolyl, imidazolyl, and alkyl-substituted imidazolyl.

[0046] In the above formula and throughout the specification, the term "unsaturated" as used herein means that the functional group, substituent, ring or bridge has one or more carbon double bonds or triple bonds. Examples of unsaturated rings can be, but are not limited to, aromatic rings, such as benzene rings. The term "saturated" means that the functional group, substituent, ring or bridge does not have one or more double bonds or triple bonds.

[0047] In the above formula and throughout the specification, the term "alkylsilyl" refers to a linear or branched functional group having 3 to 10. Exemplary alkylsilyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, dimethylsilyl, diethylsilyl, and dimethylethylsilyl.

[0048] In certain embodiments, the substituent R in Formula I 3 and R 4 Can be linked together to form a ring structure. As will be appreciated by the skilled artisan, in which R 3 and R 4 When connected together to form a ring, R 3 Contains the R 4 In these embodiments, the ring structure can be saturated, for example, a cyclic alkyl ring, or unsaturated, for example, an aryl ring. In addition, in these embodiments, the ring structure can also be substituted or substituted. Exemplary cyclic ring groups include, but are not limited to, pyrrolidinyl, piperidino, and 2,6-dimethylpiperidino. However, in other embodiments, the substituent R 3 and R 4 Not connected.

[0049] The precursor of formula I can be prepared according to the following reaction formula (1):

[0050]

[0051] The reaction in reaction formula (1) can be carried out with an organic solvent (e.g., in the presence of an organic solvent) or without an organic solvent (e.g., in the absence of an organic solvent). In embodiments in which an organic solvent is used, examples of suitable organic solvents include, but are not limited to, hydrocarbons, such as hexane, octane, toluene, and ethers such as diethyl ether and tetrahydrofuran (THF). In these or other embodiments, if a solvent is used, the reaction temperature is in the range of about -70°C to the boiling point of the solvent used. The resulting silicon precursor compound can be purified, for example, by vacuum distillation, after removing all by-products and any solvent (if present).

[0052] Substantially free of halide compositions according to the present invention can be obtained by (1) reducing or eliminating chloride sources during chemical synthesis, and / or (2) implementing an effective purification process to remove chloride from the crude product so that the final purified product is substantially free of chloride. Chloride sources can be reduced during the synthesis process by using reagents that do not contain halides (e.g., chlorosilanes, bromosilanes or iodosilanes), thereby avoiding the production of halide-containing by-products. In addition, the aforementioned reagents should be substantially free of chloride impurities so that the resulting crude product is substantially free of chloride impurities. In a similar manner, the synthesis should not use halide-based solvents, catalysts or solvents containing unacceptably high levels of halide contamination. The crude product can also be treated by various purification methods so that the final product is substantially free of halides, such as chlorides. Such methods have been well described in the prior art and can include, but are not limited to, purification processes such as distillation or adsorption. Distillation is generally used to separate impurities from the desired product by utilizing differences in boiling points. Adsorption can also be used to utilize the different adsorption characteristics of the components to achieve separation so that the final product is substantially free of halides. Adsorbents, such as commercially available MgO-Al2O3 blends, can be used to remove halides, such as chlorides.

[0053] Reaction formula (1) is an exemplary synthetic route for preparing silicon precursor compounds of formula I, which involves the reaction between halotrialkylsilane and primary or secondary amine as described in the literature. As disclosed in the prior art, other synthetic routes, such as reaction formula (2) or (3), can also be used to prepare these silicon precursor compounds of formula I.

[0054]

[0055] The catalyst used in the method of the present invention is a catalyst that promotes the formation of silicon-nitrogen bonds, i.e., a dehydrogenative coupling catalyst. Exemplary catalysts that can be used in the methods described herein include, but are not limited to, the following: alkaline earth metal catalysts; halogen-free main group, transition metal, lanthanide and actinide catalysts; and halogen-containing main group, transition metal, lanthanide and actinide catalysts.

[0056] Exemplary alkaline earth metal catalysts include, but are not limited to, the following: Mg[N(SiMe3)2]2, To M MgMe[To M = tris(4,4-dimethyl-2-oxazolinyl)phenylboronic acid], To M Mg-H, To M Mg-NR2 (R = H, alkyl, aryl), Ca[N(SiMe3)2]2, [(dipp-nacnac)CaX(THF)]2 (dipp-nacnac = CH[(CMe)(2,6- iPr2-C6H3N)]2; X = H, alkyl, carbosilyl, organic amino), Ca(CH2Ph)2, Ca(C3H5)2, Ca(α-Me3Si-2-(Me2N)-benzyl)2(THF)2, Ca(9-(Me3Si)-fluorenyl)(α-Me3Si-2-(Me2N)-benzyl)(THF), [(Me3TACD)3Ca3(μ 3 -H)2] + (Me3TACD=Me3

[12] aneN4), Ca(η 2 -Ph2CNPh)(hmpa)3 (hmpa = hexamethylphosphoramide), Sr[N(SiMe3)2]2 and other M 2+ Alkaline earth metal-amide, -imine, -alkyl, -hydride and -carbosilyl complexes (M = Ca, Mg, Sr, Ba).

[0057] Exemplary halogen-free, main group, transition metal, lanthanide and actinide catalysts include, but are not limited to, the following: 1,3-di-isopropyl-4,5-dimethylimidazol-2-yl, 2,2'-bipyridine, o-phenanthroline, B(C6F5)3, BR3 (R = linear, branched or cyclic C1 to C 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 Alkoxy), AlR3 (R = linear, branched or cyclic C1 to C 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 alkoxy), (C5H5)2TiR2 (R = alkyl, H, alkoxy, organic amino, carbosilyl), (C5H5)2Ti(OAr)2[Ar = (2,6-( i Pr)2C6H3)], (C5H5)2Ti(SiHRR')PMe3 (wherein R, R' are each independently selected from H, Me, Ph), TiMe2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphino)ethane), bis(phenyl)chromium(0), Cr(CO)6, Mn2(CO) 12 、Fe(CO)5、Fe3(CO) 12 、(C5H5)Fe(CO)2Me、Co2(CO)8、nickel(II) acetate、nickel(II) acetylacetonate、Ni(cyclooctadiene)2、[(dippe)Ni(μ-H)]2(dippe=1,2-bis(diisopropylphosphino)ethane)、(R-indenyl)Ni(PR'3)Me(R=1- iPr, 1-SiMe3, 1,3-(SiMe3)2; R'=Me, Ph), [{Ni(η-CH2:CHSiMe2)2O}2{μ-(η-CH2:CHSiMe2)2O}], copper(I) acetate, CuH, [tri(4,4-dimethyl-2-oxazolinyl)phenylboronic acid]ZnH, (C5H5)2ZrR2 (R=alkyl, H, alkoxy, organic amino, carbosilyl), Ru3(CO) 12 、[(Et3P)Ru(2,6-diisopropylbenzenethiophenol)][B[3,5-(CF3)2C6H3]4]、[(C5Me5)Ru(R3P) x (NCMe) 3-x ] + (wherein R is selected from a linear, branched or cyclic C1 to C 10 Alkyl and C5 to C 10 Aryl; x = 0, 1, 2, 3), Rh6 (CO) 16 , tris(triphenylphosphine)rhodium(I) carbonyl hydride, Rh2H2(CO)2(dppm)2(dppm=bis(diphenylphosphino)methane), Rh2(μ-SiRH)2(CO)2(dppm)2(R=Ph, Et, C6H 13 )、Pd / C、tris(dibenzylideneacetone)dipalladium(0)、tetrakis(triphenylphosphine)palladium(0)、palladium(II) acetate、(C5H5)2SmH、(C5Me5)2SmH、(THF)2Yb[N(SiMe3)2]2、(NHC)Yb(N(SiMe3)2)2[NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-yl subunit)]、Yb(η 2 -Ph2CNPh)(hmpa)3(hmpa=hexamethylphosphoramide), W(CO)6, Re2(CO) 10 、Os3(CO) 12 、Ir4(CO) 12 , (acetylacetonato) dicarbonyliridium(I), Ir(Me)2(C5Me5)L(L=PMe3, PPh3), [Ir(cyclooctadiene)OMe]2, PtO2 (Adams catalyst), platinum on carbon (Pt / C), ruthenium on carbon (Ru / C), palladium on carbon, nickel on carbon, osmium on carbon, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst), bis(tri-tert-butylphosphine)platinum(0), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4] and other halide-free M n+Compound (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

[0058] Exemplary halogen-containing, main group, transition metal, lanthanide and actinide catalysts include, but are not limited to, the following: BX3 (X = F, Cl, Br, I), BF3.OEt2, AlX3 (X = F, Cl, Br, I), (C5H5)2TiX2 (X = F, Cl), [Mn(CO)4Br]2, NiCl2, (C5H5)2ZrX2 (X = F, Cl), PdCl2, PdI2, CuCl, CuI, CuF2, CuCl2, Cu Br2, Cu(PPh3)3Cl, ZnCl2, [(C6H6)RuX2]2 (X = Cl, Br, I), (Ph3P)3RhCl (Wilkinson catalyst), [RhCl(cyclooctadiene)]2, di-μ-chloro-tetracarbonyldirhodium (I), bis(triphenylphosphine)rhodium (I) phosgene, NdI2, SmI2, DyI2, (POCOP)IrHCl (POCOP = 2,6-(R2PO)2C6H3; R = i Pr, n Bu, Me), H2PtCl6·nH2O (Speier catalyst), PtCl2, Pt(PPh3)2Cl2 and other halogen-containing M n+ Compound (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

[0059] The silicon precursor compound of formula I according to the present invention and the composition containing the silicon precursor compound of formula I according to the present invention are preferably substantially free of halide ions. As used herein, the term "substantially free" refers to less than 5 ppm (by weight) as measured by ion chromatography (IC), preferably less than 3 ppm as measured by ion chromatography (IC), and more preferably less than 1 ppm as measured by ion chromatography (IC), and most preferably 0 ppm as measured by ion chromatography (IC). It is believed that a significant level of chloride in the final product may be detrimental to device performance, such as higher leakage current. The silicon precursor compound of formula I is also preferably substantially free of metal ions or metal impurities, such as Li + 、Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ , volatile metal complexes. As used herein, the term "substantially free" in relation to Li, Al, Fe, Ni, Cr means less than 5 ppm (by weight) as measured by ICP-MS, preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm. In some embodiments, the silicon precursor compound having Formula I does not contain metal ions, for example, Li + 、Al 3+ , Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ As used herein, the term "free of" refers to Li, Al, Fe, Ni, Cr, noble metals such as Ru or Pt (ruthenium (Ru) or platinum (Pt) from the catalyst used in the synthesis), which means less than 1 ppm (by weight) measured by ICP-MS, preferably less than 0.1 ppm measured by ICP-MS, and more preferably less than 0.01 ppm measured by ICP-MS, and most preferably 1 ppb measured by ICP-MS. In addition, the silicon precursor compound having Formula I is also preferably substantially free of silicon-containing impurities such as alkylsiloxanes, for example hexamethyldisiloxane, which may have an effect on growth.

[0060] In certain embodiments, a silicon film deposited using the methods described herein is formed using an oxygen source, a reagent or precursor containing oxygen in the presence of oxygen. The oxygen source can be introduced into the reactor in the form of at least one oxygen source and / or can be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases can include, for example, water (H2O) (e.g., deionized water, purified water and / or distilled water), oxygen (O2), a mixture of oxygen and hydrogen, oxygen plasma, ozone (O3), N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2) and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen source can be introduced for a time ranging from about 0.1 seconds to about 100 seconds. In a specific embodiment, the oxygen source comprises water having a temperature of 10°C or higher. In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, and the oxygen source may have a pulse duration less than 0.01 seconds, while the water pulse duration may have a pulse duration less than 0.01 seconds. In yet another embodiment, the purge duration between pulses may be as low as 0 seconds or continuous pulses without a purge in between. The oxygen source or reagent provides an amount of molecules in a ratio of less than 1:1 to the silicon precursor such that at least some carbon is retained in the dielectric film so deposited.

[0061] In some embodiments, the silicon oxide film also includes nitrogen. In these embodiments, the film is deposited using the method described herein and is formed in the presence of a nitrogen-containing source. The nitrogen-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process. Suitable nitrogen-containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma and mixtures thereof. In some embodiments, the nitrogen-containing source includes ammonia plasma or hydrogen / nitrogen plasma source gas, which is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (sccm) or about 1 to about 1000sccm. The nitrogen-containing source can be introduced into the time ranging from about 0.1 to about 100 seconds. In the embodiment where the film is deposited by ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, and the nitrogen-containing source may have a pulse duration less than 0.01 seconds, and the water pulse duration may have a pulse duration less than 0.01 seconds. In yet another embodiment, the purge duration between pulses may be as low as 0 seconds or pulsed continuously without a purge in between.

[0062] Deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2) 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 substances and any byproducts that may remain in the reactor.

[0063] The steps of supplying the precursors, oxygen source, nitrogen-containing source, and / or other precursors, source gases, and / or reagents may be performed to change the stoichiometric composition of the resulting dielectric film by varying the time for supplying them.

[0064] Energy is applied to at least one of a silicon precursor, an oxygen-containing source, or a combination thereof to initiate a reaction and form a dielectric film or coating on the substrate. Such energy may be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF radio frequency source may be used to change the plasma characteristics at the substrate surface. In embodiments where the deposition involves plasma, the plasma generation process may include a direct plasma generation process (wherein the plasma is directly generated in the reactor), or alternatively, a remote plasma generation process (wherein the plasma is generated outside the reactor and supplied to the reactor).

[0065] At least one silicon precursor can be delivered to a reaction chamber in a variety of ways, such as a cyclic CVD or ALD reactor. In one embodiment, a liquid delivery system can be utilized. In an optional embodiment, a combined liquid delivery and flash processing unit can be used, such as, for example, a turbo vaporizer manufactured by MSP of Shoreview, MN, so that low volatility materials can be quantitatively delivered, which results in repeatable delivery and deposition without thermal decomposition of the precursor. In the liquid delivery mode, the precursors described herein can be delivered in pure liquid form, or alternatively, can be used in a solvent formulation or composition comprising it. Therefore, in certain embodiments, the precursor formulation may include a solvent component having appropriate properties (such as may be desirable and advantageous in a given end-use application) to form a film on a substrate.

[0066] For those embodiments in which at least one silicon precursor of formula I is used in a composition comprising a solvent and at least one silicon precursor of formula I described herein, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition by weight percentage is in the range of 0.5 wt % to 99.5 wt % or 0 wt % to 75 wt %. In this or other embodiments, the boiling point (bp) of the solvent is similar to the bp of at least one silicon precursor of formula I, or the difference between the bp of the solvent and the bp of at least one silicon precursor of formula I is 40°C or less, 30°C or less, or 20°C or less, or 10°C or less. Optionally, the difference between the boiling points is within the range of any one or more of the following endpoints: 0, 10, 20, 30 or 40°C. Examples of suitable ranges of bp differences include, but are not limited to, 0 to 40°C, 20 to 30°C, or 10 to 30°C. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkanes (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0067] As previously described, the purity level of at least one silicon precursor of Formula I is high enough to be acceptable for reliable semiconductor manufacturing. In certain embodiments, at least one silicon precursor of Formula I described herein contains less than 2 wt %, or less than 1 wt %, or less than 0.5 wt % of one or more of the following impurities: free amines, free halides or halogen ions, and higher molecular weight species. The higher purity levels of the silicon precursors described herein can be obtained by one or more of the following methods: purification, adsorption, and / or distillation.

[0068] In one embodiment of the methods described herein, a cyclic deposition process such as ALD-like, ALD or PEALD may be used, wherein deposition is performed using at least one silicon precursor and an oxygen source of Formula I. An ALD-like process is defined as a cyclic CVD process, but still provides highly conformal silicon oxide films.

[0069] In certain embodiments, the gas lines connecting the precursor tank to the reaction chamber are heated to one or more temperatures depending on the process requirements, and the container of at least one silicon precursor of Formula I is maintained at one or more temperatures for drum wave. In other embodiments, a solution containing at least one silicon precursor of Formula I is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0070] A flow of argon and / or other gases may be used as a carrier gas to help deliver the vapor of at least one silicon precursor of Formula I to the reaction chamber during the precursor pulse. In certain embodiments, the reaction chamber process pressure is about 1 Torr.

[0071] In a typical ALD or ALD-like process (eg, CCVD process), a substrate (eg, a silicon oxide substrate) is heated on a heating stage in a reaction chamber that is initially exposed to a silicon precursor to allow chemical adsorption of the complex onto the substrate surface.

[0072] A purge gas such as argon purges the unabsorbed excess complex from the process chamber. After sufficient purging, an oxygen source can be introduced into the reaction chamber to react with the absorbed surface, followed by another gas purge to remove the reaction byproducts from the chamber. This process cycle can be repeated to achieve the desired film thickness. In some cases, vacuuming can replace the gas purge of the inert gas, or both can be used to remove unreacted silicon precursor.

[0073] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially, can be performed simultaneously (e.g., during at least a portion of another step), and any combination thereof. The respective steps of supplying precursor and oxygen source gases can be performed by varying the duration of the supply to vary the stoichiometric composition of the resulting dielectric film.

[0074] A specific embodiment of the method for depositing a silicon oxide film on a substrate described herein comprises the following steps:

[0075] a. providing a substrate in a reactor,

[0076] b. introducing into the reactor at least one silicon precursor having formula I as described herein,

[0077] c. purging the reactor with a purge gas,

[0078] d. introducing an oxygen source into the reactor, and

[0079] e. purging the reactor with a purge gas,

[0080] Steps b to e are repeated until a silicon oxide film of a desired thickness is deposited.

[0081] Another embodiment of the method described herein introduces a hydroxyl or OH source, such as H2O vapor, after the oxidation step. The purpose in this embodiment is to refill the anchoring functional groups or reactive sites for the silicon precursor that are anchored on the surface to form a monolayer. The deposition step includes:

[0082] a. providing a substrate in a reactor;

[0083] b. introducing a silicon precursor of formula I into the reactor;

[0084] c. purging the reactor with a purge gas;

[0085] d. introducing an oxygen source into the reactor;

[0086] e. purging the reactor with a purge gas;

[0087] f. introducing water vapor or other hydroxyl source into the reactor; and

[0088] g. purging the reactor with a purge gas,

[0089] Steps b to g are repeated until the desired thickness is deposited.

[0090] In an alternative embodiment of the methods described herein, the depositing step comprises:

[0091] a. providing a substrate in a reactor;

[0092] b. introducing a silicon precursor of formula I into the reactor;

[0093] c. purging the reactor with a purge gas;

[0094] d. introducing an oxygen source into the reactor;

[0095] e. purging the reactor with a purge gas;

[0096] f. introducing water vapor or an OH source into the reactor; and

[0097] g. purging the reactor with a purge gas,

[0098] Steps b to i are repeated until the desired thickness is deposited.

[0099] Yet another embodiment uses hydrogen peroxide or oxygen plasma to remove passivating functional groups or groups such as methyl groups. The deposition steps are as follows:

[0100] a. providing a substrate in a reactor;

[0101] b. introducing a silicon precursor of formula I into the reactor;

[0102] c. purging the reactor with a purge gas;

[0103] d. introducing ozone, hydrogen peroxide or oxygen plasma into the reactor; and

[0104] e. purging the reactor with a purge gas,

[0105] Steps b to e are repeated until the desired film thickness is deposited.

[0106] Process temperatures for the methods described herein are one or more temperatures in the range of 600°C to 1000°C; or 600°C to 750°C; or 600°C to 750°C; or 600°C to 800°C.

[0107] The deposition pressure range is 50 mTorr to 760 Torr or one or more pressures ranging from 500 mTorr to 100 Torr. The purge gas may be selected from an inert gas such as nitrogen, helium or argon. The oxygen source is selected from oxygen, peroxide, ozone or molecular oxygen from a plasma process.

[0108] Therefore, the present invention provides at least the following:

[0109] 1. A method for depositing a silicon oxide film onto a substrate, comprising the steps of:

[0110] a. providing a substrate in a reactor;

[0111] b. introducing into the reactor at least one silicon precursor, wherein the at least one silicon precursor has a structure represented by formula I:

[0112] R 1 R 2 m Si(NR 3 R 4 ) n (I)

[0113] Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl;

[0114] R 4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, and C3 to C 10 Alkylsilyl;

[0115] m is 0 to 2; and

[0116] n is 1 to 3, wherein m+n=3;

[0117] and wherein the silicon precursor is substantially free of one or more impurities selected from the group consisting of halides, metals, and combinations thereof;

[0118] c. purging the reactor with a purge gas;

[0119] d. introducing an oxygen source into the reactor; and

[0120] e. purging the reactor with a purge gas,

[0121] wherein steps b to e are repeated until a desired thickness of silicon oxide is deposited, and wherein the method is performed at one or more temperatures in the range of 600 to 800° C. and one or more pressures in the range of 50 millitorr (mT) to 760 Torr.

[0122] 2. The method according to claim 1, wherein R 3 and R 4 connected to form an annular ring structure.

[0123] 3. The method of claim 1, wherein the at least one silicon precursor is selected from the group consisting of diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, tert-butylaminotriethylsilane, isopropylaminotriethylsilane, diisopropylaminotriethylsilane, pyrrolidonyltriethylsilane, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidonyltrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidonyltrimethylsilane, dimethylsilane, diisopropylaminodimethylsilane, pyrrolidone dimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, tert-butylaminodiethylsilane, isopropylaminodiethylsilane, diisopropylaminodiethylsilane, pyrrolidone diethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, Dipyrrolidinyldimethylsilane, bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(diisopropylamino)diethylsilane, bis(isopropylamino)diethylsilane, bis(tert-butylamino)diethylsilane, dipyrrolidinyldiethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinylmethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, ,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, methylaminotrimethylsilane, n-propylaminotrimethylsilane, isobutylaminotrimethylsilane, n-butylaminotrimethylsilane, cyclohexamidotrimethylsilane, 2-methylpyrrolidinyltrimethylsilane, 2,5-dimethylpyrrolidinyltrimethylsilane, piperidinotrimethylsilane, 1-methylpiperazinyltrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane and mixtures thereof.

[0124] 4. The method of claim 3, wherein the halide in the silicon precursor, if present, comprises chloride ions.

[0125] 5. The silicon precursor of claim 4, wherein the chloride ions, if present, are present at a concentration of 50 ppm or less as measured by IC.

[0126] 6. The silicon precursor of claim 4, wherein the chloride ions, if present, are present at a concentration of 10 ppm or less as measured by IC.

[0127] 7. The silicon precursor of claim 4, wherein the chloride ions, if present, are present at a concentration of 5 ppm or less as measured by IC.

[0128] 8. The method of claim 1, wherein the purge gas is selected from nitrogen, helium and argon.

[0129] 9. The method of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, oxygen / hydrogen, oxygen / water, water vapor, water vapor plasma, hydrogen peroxide, an ozone source, and combinations thereof.

[0130] 10. The method according to claim 1, further comprising the following steps f and g after step e:

[0131] f. introducing water vapor or a hydroxyl source into the reactor; and

[0132] g. Purge the reactor with a purge gas.

[0133] 11. A method for depositing a silicon oxide film, comprising the steps of:

[0134] a. providing a substrate in a reactor;

[0135] b. introducing into the reactor at least one silicon precursor, wherein the at least one silicon precursor has a structure represented by formula I:

[0136] R 1 R 2 m Si(NR 3 R 4 ) n (I)

[0137] Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl;

[0138] R4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, and C3 to C 10 Alkylsilyl;

[0139] m is 0 to 2; and

[0140] n is 1 to 3, wherein m+n=3;

[0141] wherein the silicon precursor is substantially free of one or more impurities selected from the group consisting of halides, metals, and combinations thereof;

[0142] c. purging the reactor with a purge gas;

[0143] d. introducing an oxygen source into the reactor;

[0144] e. purging the reactor with a purge gas;

[0145] f. introducing water vapor or an OH source into the reactor; and

[0146] g. purging the reactor with a purge gas,

[0147] wherein steps b to g are repeated until a desired thickness is deposited, and wherein the process temperature ranges from 600 to 800° C. and the pressure in the reactor ranges from 50 mT to 760 Torr.

[0148] 12. The method according to claim 11, wherein R 3 and R 4 connected to form an annular ring structure.

[0149] 13. The method of claim 11, wherein the at least one silicon precursor is selected from the group consisting of diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, tert-butylaminotriethylsilane, isopropylaminotriethylsilane, diisopropylaminotriethylsilane, pyrrolidonyltriethylsilane, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidonyltrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidonyltrimethylsilane. Aminodimethylsilane, diisopropylaminodimethylsilane, pyrrolidinyldimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, tert-butylaminodiethylsilane, isopropylaminodiethylsilane, diisopropylaminodiethylsilane, pyrrolidonyldiethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, Dipyrrolidinyldimethylsilane, bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(diisopropylamino)diethylsilane, bis(isopropylamino)diethylsilane, bis(tert-butylamino)diethylsilane, dipyrrolidinyldiethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinylmethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, ,6-dimethylpiperidinodimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, methylaminotrimethylsilane, n-propylaminotrimethylsilane, isobutylaminotrimethylsilane, n-butylaminotrimethylsilane, cyclohexamidotrimethylsilane, 2-methylpyrrolidinyltrimethylsilane, 2,5-dimethylpyrrolidinyltrimethylsilane, piperidinotrimethylsilane, 1-methylpiperazinyltrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane and mixtures thereof.

[0150] 14. The method of claim 13, wherein the halide in the silicon precursor, if present, comprises chloride ions.

[0151] 15. The silicon precursor of claim 14, wherein the chloride ions, if present, are present at a concentration of 50 ppm or less as measured by IC.

[0152] 16. The silicon precursor of claim 14, wherein the chloride ions, if present, are present at a concentration of 10 ppm or less as measured by IC.

[0153] 17. The silicon precursor of claim 14, wherein the chloride ions, if present, are present at a concentration of 5 ppm or less as measured by IC.

[0154] 18. The method of claim 11, wherein the purge gas is selected from nitrogen, helium, and argon.

[0155] 19. The method of claim 11, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide, and an ozone source.

[0156] 20. A silicon oxide film produced by claim 1.

[0157] 21. The silicon oxide film produced by claim 11.

[0158] 22. The silicon oxide film of claim 20, wherein the film has a 1.0 e -9 A / cm 2 or lower leakage current, or 1.0e at 4MV / cm -9 A / cm 2 or lower leakage current, or 1.0e at 6MV / cm -8 A / cm 2 or lower leakage current.

[0159] 23. The silicon oxide film of claim 21, wherein the film has a 1.0 e -9 A / cm 2 or lower leakage current, or 1.0e at 4MV / cm -9 A / cm 2 or lower leakage current, or 1.0e at 6MV / cm -8 A / cm 2 or lower leakage current. Example

[0160] Comparative Example 1: Atomic Layer Deposition of Silicon Oxide Films Using Dimethylaminotrimethylsilane with Greater Than 50 ppm Chloride Impurities

[0161] Atomic layer deposition of silicon oxide films was performed using the following precursor: dimethylaminotrimethylsilane (DMATMS). Deposition was performed on a laboratory-scale ALD processing equipment. The silicon precursor was delivered to the chamber by vapor extraction. All gases (e.g., purge and reaction gases or precursors and oxygen sources) were preheated to 100°C before entering the deposition area. The flow rates of gases and precursors were controlled by ALD diaphragm valves with high-speed actuation. The substrate used in the deposition was a 12-inch long silicon strip. A thermocouple was connected to the sample holder to confirm the substrate temperature. Deposition was performed using ozone as the oxygen source gas. Deposition parameters are provided in Table I.

[0162] Table I: Method for atomic layer deposition of silicon oxide films using ozone using DMATMS

[0163]

[0164] Repeat steps b to e until the desired thickness is achieved. The thickness and refractive index of the film are measured using a FilmTek 2000SE ellipsometer by fitting the reflection data of the film to a preset physical model (e.g., the Lorentz Oscillator model). Wet etch rates are performed using a 1:99 volume dilution of 49 wt.% hydrofluoric acid (HF) in deionized water. A thermal oxide wafer is used as a reference for each batch to confirm the solution concentration. A typical thermal oxide wafer wet etch rate for about 0.5 wt.% HF in aqueous solution is The film thickness before and after etching is used to calculate the wet etch rate. The carbon and nitrogen concentrations in the film are analyzed using dynamic secondary ion mass spectrometry (SIMS) technology. The % non-uniformity is calculated from the 6-point measurement using the following formula: % non-uniformity = ((maximum value - minimum value) / (2*average value)). The film density is characterized by X-ray reflectometry (XRR).

[0165] Figure 1 Leakage current curves for silicon oxide deposited with DMAP with greater than 50 ppm chloride impurities at 650°C and 700°C are plotted. The film leakage current is greater than 1.0 e at 2 MW / cm -9 A / cm 2 , greater than 1.0e at 4MV / cm -9 A / cm 2 , greater than 1.0e at 6MV / cm -8 A / cm 2 The film density of silicon oxide deposited from DMATMS ranges from 2.08 to 2.23 g / cm 3 .

[0166] Working Example 1: Atomic Layer Deposition of Silicon Oxide Films Using Dimethylaminotrimethylsilane with 2 ppm Chloride Impurities

[0167] Silicon oxide films were deposited using dimethylaminotrimethylsilane with 2 ppm chloride impurities at 650°C and 700°C, respectively. Figure 2 The leakage current curves are plotted, showing higher breakdown voltage and lower leakage current, especially for the silicon oxide films deposited at 700°C. The leakage current of the 700°C film is below 1.0e at 2MW / cm -9 A / cm 2 , below 1.0e at 4MV / cm - 9 A / cm 2 , below 1.0e at 6MV / cm -8 A / cm 2 .

[0168] Although the present invention has been illustrated and described above with reference to certain specific embodiments and examples, the present invention is not intended to be limited to the details shown. Rather, various modifications may be made to the details within the scope and range of equivalents of the claims without departing from the spirit of the present invention. It is expressly intended that, for example, all ranges broadly stated in this document include within their scope all narrower ranges that fall within the broader ranges.

Claims

1. A method for depositing a silicon oxide film onto a substrate, comprising the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one silicon precursor, wherein the at least one silicon precursor has a structure represented by formula I: R 1 R 2 m Si(NR 3 R 4 ) n (I), Where R 1 , R 2 and R 3 Each independently selected from a linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl; R 4 selected from hydrogen, linear or branched C1 to C 10 Alkyl and C6 to C 10 Aryl, and C3 to C 10 Alkylsilyl; m is 0 to 2; and n is 1 to 3, wherein m+n=3; c. purging the reactor with a purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with a purge gas, wherein steps b to e are repeated until a desired thickness of silicon oxide is deposited, and wherein the method is carried out at one or more temperatures in the range of 700 to 750° C. and one or more pressures in the range of 50 millitorr (mT) to 760 Torr; and wherein the chloride ions in the silicon precursor are present at a concentration of 5 ppm or less as measured by ion chromatography or at a concentration of 0 ppm as measured by ion chromatography.

2. The method according to claim 1, further comprising the following steps f and g after step e: f. introducing water vapor or an OH source into the reactor; and g. purging the reactor with a purge gas, Steps b to g are repeated until the desired thickness is deposited.

3. The method according to claim 1, wherein R 3 and R 4 connected to form an annular ring structure.

4. The method of claim 1, wherein the at least one silicon precursor is selected from the group consisting of diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, tert-butylaminotriethylsilane, isopropylaminotriethylsilane, diisopropylaminotriethylsilane, pyrrolidonyltrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diisopropylaminotrimethylsilane, pyrrolidonyltrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, tert-butylaminotriethylsilane, Silane, isopropylaminodimethylsilane, diisopropylaminodimethylsilane, pyrrolidone dimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, tert-butylaminodiethylsilane, isopropylaminodiethylsilane, diisopropylaminodiethylsilane, pyrrolidone diethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(ethylmethylamino)dimethylsilane, bis(diisopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, dipyrrolidone dimethylsilane, bis(dimethylamino)dimethylsilane bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(diisopropylamino)diethylsilane, bis(isopropylamino)diethylsilane, bis(tert-butylamino)diethylsilane, dipyrrolidinyldiethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinylmethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinomethylsilane trimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, methylaminotrimethylsilane, n-propylaminotrimethylsilane, isobutylaminotrimethylsilane, n-butylaminotrimethylsilane, cyclohexamidotrimethylsilane, 2-methylpyrrolidinyltrimethylsilane, 2,5-dimethylpyrrolidinyltrimethylsilane, piperidinotrimethylsilane, 1-methylpiperazinyltrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane and mixtures thereof. The method according to claim 1 , wherein the purge gas is selected from nitrogen, helium and argon.

6. The method of claim 1, wherein the oxygen source is selected from oxygen, molecular oxygen from a plasma process, peroxides; or selected from oxygen plasma, a mixture of oxygen and hydrogen, water, ozone, and combinations thereof.

7. The method of claim 1, wherein the method is carried out at one or more temperatures in the range of 700 to 720°C.

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