Organic amino-functionalized cyclic oligosiloxanes for depositing silicon-containing films

Abstract

Disclosed herein are organoamino-functionalized cyclic oligosiloxanes having at least two silicon and two oxygen atoms and an organoamino group, and methods for making the organoamino-functionalized cyclic oligosiloxanes. Also disclosed are methods of depositing a silicon and oxygen containing film using the organoamino-functionalized cyclic oligosiloxanes.

Description

[0001] This application is a divisional application of Chinese patent application filed on April 11, 2019, with application number 201910290443.1 and entitled "Organoamino-functionalized cyclic oligosiloxanes for depositing silicon-containing films".

[0002] Citation of relevant applications

[0003] This application claims the benefit of U.S. Provisional Application No. 62 / 655,982, filed April 11, 2018. Background Technology

[0004] The present invention relates to organosilicon compounds that can be used to deposit silicon and oxygen-containing films (e.g., silicon oxide, silicon oxycarbonitride, silicon oxycarbide, carbon-doped silicon oxide, and other silicon and oxygen-containing films), methods for depositing silicon oxide-containing films using these compounds, and films obtained from the compounds and methods.

[0005] This document describes novel organoamino-functionalized cyclic oligomeric oligomeric siloxane precursor compounds and compositions and methods comprising these organoamino-functionalized cyclic oligomeric siloxane precursor compounds for depositing silicon-containing films (e.g., but not limited to silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide) by thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes or combinations thereof. More specifically, this document describes compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing films or materials at one or more deposition temperatures of about 600°C or lower (including, for example, about 25°C to about 300°C).

[0006] Atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) are processes used to deposit conformal films, such as silicon oxide, at low temperatures (<500°C). In both ALD and PEALD processes, precursors and reactive gases (such as oxygen or ozone) are pulsed in a number of cycles to form a monolayer of silicon oxide in each cycle. However, silicon oxide deposited at low temperatures using these processes may contain levels of impurities that can be detrimental in some semiconductor applications, such as, but not limited to, carbon (C) or hydrogen (H). To address this issue, one possible solution is to increase the deposition temperature to 500°C or higher. However, at these higher temperatures, the conventional precursors used in the semiconductor industry tend to be self-reactive, thermally decomposed, and deposited in chemical vapor deposition (CVD) mode rather than ALD mode. Compared to ALD deposition, CVD mode deposition has reduced conformability, especially for the high aspect ratio structures required in many semiconductor applications. Furthermore, CVD mode deposition offers less control over film or material thickness compared to ALD mode deposition.

[0007] It is known in the art that it can be used at relatively low temperatures (<300°C) and at relatively high growth per cycle (GPC>). / Cycle) deposits organoaminosilane and chlorosilane precursors containing silicon films using atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) processes.

[0008] Examples of known precursors and methods are disclosed in the following publications, patents and patent applications.

[0009] US Patent No. 7,084,076B2 describes the deposition of silicon oxide films in an alkaline-catalyzed ALD process using halogen- or NCO-substituted disiloxane precursors.

[0010] US Publication No. 2015087139AA describes the deposition of silicon-containing films using amino-functionalized carbosilanes via thermal ALD or PEALD processes.

[0011] US Patent No. 9,337,018B2 describes the deposition of silicon-containing films using organic amino silane via thermal ALD or PEALD processes.

[0012] U.S. Patent Nos. 8,940,648B2, 9,005,719B2 and 8,912,353B2 describe the deposition of silicon-containing films using organoamino silanes via thermal ALD or PEALD processes.

[0013] US Publication No. US2015275355AA describes the deposition of silicon-containing films using mono- and bis(organoamino)alkylsilanes via thermal ALD or PEALD processes.

[0014] US Publication No. 2015376211A describes the deposition of silicon-containing films using trimethylsilylamines substituted with mono(organoamino)-, halido-, and pseudohalo groups via thermal ALD or PEALD processes.

[0015] Publication No. WO15105337 and U.S. Patent No. 9,245,740B2 describe the deposition of silicon-containing films using alkylated trimethylsilylamine via thermal ALD or PEALD processes.

[0016] Publication No. WO15105350 describes the deposition of silicon-containing films using a 4-membered ring cyclodisilazane having at least one Si-H bond via a thermal ALD or PEALD process.

[0017] US Patent No. 7,084,076B2 describes the deposition of silicon oxide films in an alkaline-catalyzed ALD process using halogen- or NCO-substituted disiloxane precursors.

[0018] US Publication No. US2018223047A discloses amino-functionalized linear and cyclic oligomeric siloxanes (having at least two silicon atoms and two oxygen atoms as well as an organic amino group), and methods for depositing silicon- and oxygen-containing films.

[0019] The disclosures of the patents and patent applications identified above are incorporated herein by reference.

[0020] Despite the aforementioned developments, there is a need in the art for precursors and methods for depositing silicon oxide films at high growth per cycle (GPC) to maximize the yield of semiconductor manufacturing facilities. While some precursors are capable of > / Cyclic GPC deposition, but these precursors have drawbacks such as low-quality films (elemental contamination, low density, low electrical properties, high wet etch rate), high process temperature, need for catalysts, high cost, production of low conformability films, and other disadvantages. Summary of the Invention

[0021] This invention addresses the problems associated with conventional precursors and processes by providing silicon- and oxygen-containing precursors, particularly organic amino-functionalized cyclic oligosiloxanes (having at least two silicon and two oxygen atoms, and an organic amino group for anchoring the cyclic oligosiloxane unit to a substrate surface), as part of a process for depositing silicon- and oxygen-containing films. Compared to those described in the background section above, the polysilicon precursors disclosed in this invention have novel structures, thus offering advantages in one or more aspects regarding the cost or convenience of precursor synthesis, precursor physical properties (including thermal stability, reactivity, or volatility), the process of depositing silicon-containing films, or the properties of the deposited silicon-containing films.

[0022] This document discloses a composition comprising at least one organic amino-functionalized oligosiloxane compound selected from formulas A and B:

[0023]

[0024] Where R 1 Selected from linear C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C 10 alkynyl and C3-C 10 Aryl; R 2 Selected from hydrogen, C1-C 10 Straight-chain alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C10 alkynyl and C4-C 10 Aryl, wherein R 1 and R 2 Connected to form a heterocyclic structure or a heterocyclic aryl structure, or not connected to form a cyclic structure; and R 3 -R 9 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl and C4-C 10 Aryl.

[0025] According to a more preferred embodiment, R 1 Selected from C3-C6 cycloalkyl and C3-C6 aryl; R 2 Selected from hydrogen and C1-C4 alkyl; and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups. Alternatively, R 1 and R 2 Connect to form C3-C 10 Heterocyclic structure or C3-C 10 Heterocyclic aryl structure, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0026] This document also describes a method for depositing stoichiometric or non-stoichiometric silicon and oxygen-containing materials or films (e.g., but not limited to silicon oxide, carbon-doped silicon oxide, silicon oxynitride films, or carbon-doped silicon oxynitride films) at relatively low temperatures (e.g., at 600°C or lower) in plasma-enhanced ALD (PEALD), plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), plasma-enhanced flowable chemical vapor deposition (PEFCVD), plasma-enhanced ALD-like processes, or ALD processes using oxygen-containing reactant sources, nitrogen-containing reactant sources, or combinations thereof.

[0027] In one aspect, this document discloses a method for depositing a silicon- and oxygen-containing film onto a substrate, the method comprising the steps of: (a) providing a substrate in a reactor; and (b) introducing at least one silicon precursor compound selected from formulas A and B into the reactor.

[0028]

[0029] Where (i)R 1 Selected from C3-C 10 cycloalkyl and C3-C10 Aryl; R 2 Selected from hydrogen and C1-C4 alkyl; and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups; (ii)R 1 and R 2 Connect to form C3-C 10 Heterocyclic structure or C3-C 10 Heterocyclic aryl structure, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0030] This article also discloses a method for preparing the above-mentioned compounds, and a membrane formed from the compounds.

[0031] The embodiments of the present invention can be used individually or in combination with each other. Attached Figure Description

[0032] Figure 1 This is a graph depicting the plasma-enhanced atomic layer deposition growth rate as a function of the precursor pulse time of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane and bis(diethylamino)silane (each at 100 and 300 °C).

[0033] Figure 2 This is a graph depicting the film plasma-enhanced atomic layer deposition growth rate and wet etching rate as a function of the O2 plasma power of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane when deposition is performed at 300°C.

[0034] Figure 3 This is a graph depicting the film plasma-enhanced atomic layer deposition growth rate and wet etching rate as a function of the O2 plasma power of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane when deposition is performed at 100°C.

[0035] Figure 4 This is a graph depicting the film plasma-enhanced atomic layer deposition growth rate and wet etching rate as a function of O2 plasma time for 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane when deposition is performed at 100°C. Detailed Implementation

[0036] Unless otherwise stated herein or obviously contradicted by the context, the terms “a / an” and “the” and similar designations in the context of describing the invention (particularly in the context of the following claims) shall be interpreted as encompassing both the singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” shall be interpreted as open-ended terms (i.e., “including but not limited to”). Unless otherwise stated herein, the description of numerical ranges herein is intended only as a shorthand method of individually referring to each individual value falling within that range, and each individual value is incorporated into this specification as if it were individually described herein. Unless otherwise stated herein or obviously contradicted by the context, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the invention and does not constitute a limitation on the scope of the invention. No language in the specification should be construed as indicating that any unclaimed element is necessary for the implementation of the invention.

[0037] This document describes compositions and methods relating to forming stoichiometric or non-stoichiometric films or materials comprising silicon and oxygen (e.g., but not limited to silicon oxide, carbon-doped silicon oxide films, silicon oxynitride films, or carbon-doped silicon oxynitride films, or combinations thereof) at one or more temperatures of about 600°C or lower, or about 25°C to about 600°C, and in some embodiments, 25°C to about 300°C. The films described herein are deposited in deposition processes such as atomic layer deposition (ALD) or in ALD-like processes such as, but not limited to, plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), or plasma-enhanced flowable chemical vapor deposition (PEFCVD). The low-temperature deposition method described herein (e.g., one or more deposition temperatures from approximately ambient temperature to 600°C) provides films or materials exhibiting at least one or more of the following advantages: a density of about 2.1 g / cc or greater, low chemical impurities, high conformability in thermal atomic layer deposition, plasma-enhanced atomic layer deposition (ALD) processes, or plasma-enhanced ALD-like processes, the ability to adjust the carbon content in the resulting film; and / or a film with a density of 5 Å / s when measured in 0.5 wt% dilute HF. Or even lower etching rates. For carbon-doped silicon oxide films, a carbon content greater than 1% is desirable, among other properties (e.g., but not limited to a density of about 1.8 g / cc or higher or about 2.0 g / cc or higher), to adjust the etching rate to below 0.5 wt% in dilute HF. The value of / sec.

[0038] The methods disclosed herein can be implemented using equipment known in the art. For example, the methods can employ reactors conventional in the semiconductor manufacturing field.

[0039] Without wishing to be bound by any theory or explanation, it is believed that the effectiveness of the precursor compositions disclosed herein can vary with the number of silicon atoms and, in particular, the silicon atomic bonds. The precursors disclosed herein typically have 3 to 5 silicon atoms and 5 to 8 silicon-oxygen bonds.

[0040] The precursors disclosed herein have structures that differ from those known in the art, and therefore can perform better than conventional silicon-containing precursors and provide relatively high GPC, resulting in higher quality films with favorable wet etching rates or less elemental contamination.

[0041] This document discloses compositions for depositing films selected from silicon oxide, carbon-doped silicon oxide, or silicon carbon oxynitride films using a vapor deposition process, the compositions comprising a compound having formula A or formula B:

[0042]

[0043] Where R 1 Selected from linear C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C 10 alkynyl and C4-C 10 Aryl; R 2 Selected from hydrogen, C1-C 10 Straight-chain alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C 10 alkynyl and C3-C 10 Aryl, wherein R 1 and R 2 Connected to form a heterocyclic or heterocyclic aryl structure, or not connected to form a cyclic structure; and R 3 -R 9 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl and C3-C 10 Aryl.

[0044] In a preferred embodiment, R 1 Selected from linear C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C 10 alkynyl and C3-C 10 Aryl, R 2 Selected from C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 Heterocyclic aryl. R 3 -R 9 Each is independently selected from hydrogen and methyl. In another preferred embodiment, R 1 and R 2 Linked to form a heterocyclic or heterocyclic aryl structure, and R 3 -R 9 Each is independently selected from hydrogen or C1-C4 alkyl groups.

[0045] According to a more preferred embodiment, R 1 Selected from C5-C 10 cycloalkyl and C3-C 10 Aryl; R 2 Selected from hydrogen and C1-C4 alkyl; and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups. Alternatively, R 1 and R 2 The linkages form a heterocyclic structure with 3-10 carbon atoms or a heterocyclic aryl structure with 3-10 carbon atoms, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0046] In the above formula and throughout the specification, the term "oligosiloxane" refers to a compound containing at least two repeating -Si-O-siloxane units, preferably at least three repeating -Si-O-siloxane units, and may be cyclic or linear, preferably cyclic.

[0047] In the above formula and throughout the specification, the term "alkyl" refers to a straight-chain or branched functional group having 1 to 10 carbon atoms. Exemplary straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In some embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, alkoxy, dialkylamino, or combinations thereof attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto. The alkyl group may be saturated or optionally unsaturated.

[0048] In the above formula and throughout the specification, the term "cycloalkyl" refers to a cyclic functional group having 3 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0049] In the above formula and throughout the specification, the term "alkenyl" means a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

[0050] In the above formula and throughout the specification, the terms "dialkylamino," "alkylamino," or "organic amino" denote the group R. 1 R 2 N-, where R 1 and R 2 Independently selected from straight-chain or branched C1-C6 alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic groups. In some cases, R 1 and R 2 Connect to form a ring-shaped structure; in other cases, R 1 and R 2 They are not connected to form a ring-shaped structure. Where R... 1 and R 2 Exemplary organic amino groups linked to form a ring include, but are not limited to, pyrrolidinyl groups (wherein R...) 1 =propyl and R 2 =Me), 1,2-piperidinyl (where R 1 =propyl and R 2 =Et), 2,6-dimethylpiperidinyl (where R 1 =Isopropyl, R 2 =sec-butyl) and 2,5-dimethylpyrrolidinyl (wherein R 1 =R 2 =Isopropyl).

[0051] In the above formula and throughout the specification, the term "aryl" means 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, o-xylyl, 1,2,3-triazolyl, pyrrole, pyridyl, and furanyl.

[0052] Throughout this specification, the term "alkyl hydrocarbon" refers to a straight-chain or branched C1-C hydrocarbon. 20 Hydrocarbons, cyclic C6-C 20 Hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0053] Throughout the specification, the term "alkoxy" refers to C1-C 10 -OR 1 Group, wherein R 1 As defined above. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0054] Throughout the specification, the term "carboxylic acid ester" refers to C2-C... 12 -OC(=O)R 1 Group, wherein R 1 As defined above. Exemplary carboxylic acid ester groups include, but are not limited to, acetate (-OC(=O)Me), ethyl carboxylate (-OC(=O)Et), isopropyl carboxylate (-OC(=O)iPr), and benzoic acid ester (-OC(=O)Ph).

[0055] Throughout the specification, the term "aromatic hydrocarbons" refers to C6-C6 hydrocarbons. 20 Aromatic hydrocarbons. Exemplary aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0056] In the above formula and throughout the specification, the term "heterocyclic structure" refers to a non-aromatic saturated, unsaturated, or aromatic monocyclic or polycyclic ring system containing about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur. Preferred heterocycles contain about 5 to about 6 ring atoms. The prefixes nitro, oxy, or sulfide preceding the heterocycle indicate that at least nitrogen, oxygen, or sulfur atoms are present as ring atoms. Heterocyclic structures may optionally be substituted. Exemplary heterocyclic structures include piperidinyl, pyridinyl, 2-methylpiperidinyl, 2,6-dimethylpiperidinyl, morpholino, pyrrolyl, and 2,5-dimethylpyrrolyl.

[0057] In the above formula and throughout the specification, the term "heterocyclic aryl structure" refers to an aromatic ring system of about 3 to about 10 atoms, preferably about 5 to about 10 atoms, wherein one or more atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur. Preferred heterocyclic aryl structures contain about 5 to about 6 ring atoms, including at least one carbon, nitrogen, oxygen, or sulfur atom. The heterocyclic aryl structure may optionally be substituted. Exemplary heterocyclic aryl structures include pyrrole, imidazolyl, and pyrazolyl groups.

[0058] Exemplary organic amino-functionalized cyclic oligosiloxanes of formula AB are listed in Table 1:

[0059] Table 1. Exemplary organic amino-functionalized cyclic oligosiloxanes of formula AB:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] Compounds of formula A or B can be synthesized, for example, by catalytic dehydrogenation coupling of cyclotrisiloxane or cyclotetrasiloxane with an organic amine (e.g., reaction (1) for cyclotrisiloxane; cyclotetrasiloxane can also be used as in reaction (3)) or by reaction of chlorinated cyclotrisiloxane with an organic amine or a metal salt of an organic amine (e.g., reaction (2); chlorinated cyclotetrasiloxane can also be used as in reaction (4)). The R group in the reaction is as defined above;

[0067]

[0068]

[0069] Preferably, the molar ratio of cyclotrisiloxane or cyclotetrasiloxane to organic amine in the reaction mixture is about 4:1, 3:1, 2:1, 1:1.0, 1:1.5, 1:2, 1:3, 1:4, or 1:10.

[0070] The catalysts used in the methods of the present invention in reactions (1) and (3) are catalysts that promote the formation of silicon-nitrogen bonds. Exemplary catalysts that can be used with the methods described herein include, but are not limited to, the following: alkaline earth metal catalysts; halogen-free group, transition metal, lanthanide, and actinide catalysts; and halogen-containing group, transition metal, lanthanide, and actinide catalysts.

[0071] 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 ester], 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- i [Pr2-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 amines, imines, alkyl groups, hydrides, and silane-alkyl complexes (M = Ca, Mg, Sr, Ba).

[0072] Exemplary halogen-free, main group, transition metal, lanthanide, and actinide catalysts include, but are not limited to, the following: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 2,2'-bipyridine, phenanthroline, B(C6F5)3, BR3 (R = straight-chain, branched, or cyclic C1 to C2). 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 Alkyl group), AlR3 (R = straight chain, branched chain or cyclic C1 to C2) 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 alkoxy), (C5H5)2TiR2 (R = alkyl, H, alkoxy, organic amino, silanealkyl), (C5H5)2Ti(OAr)2[Ar = (2,6-( iPr)2C6H3)],(C5H5)2Ti(SiHRR')PMe3 (where R and R' are independently selected from H, Me, and Ph), TiMe2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphino)ethane), bis(benzene)chromium(O), Cr(CO)6, Mn2(CO) 12 Fe(CO)5, Fe3(CO) 12 (C5H5)Fe(CO)2Me, Co2(CO)8, Ni(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- i Pr, 1-SiMe3, 1,3-(SiMe3)2; R'=Me, Ph), [{Ni(η-CH2:CHSiMe2)2O}2{μ-(η-CH2:CHSiMe2)2O}], Cu(I) acetate, CuH, [tris(4,4-dimethyl-2-oxazolinyl)phenylboronic acid ester]ZnH, (C5H5)2ZrR2 (R=alkyl, H, alkoxy, organic amino, silanealkyl), Ru3(CO) 12 , [(Et3P)Ru(2,6-di-trimethylmethyl(mesityl)thiophenol ester)][B[3,5-(CF3)2C6H3]4],[(C5Me5)Ru(R3P) x (NCMe) 3-x ] + (where R is selected from linear, branched, or cyclic C1 to C1) 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(diphenylphosphine)methane), Rh2(μ-SiRH)2(CO)2(dppm)2(R = Ph, Et, C6H 13 ), Pd / C, tris(dibenzylideneacetone)palladium(0), tetra(triphenylphosphine)palladium(0), acetic acid Pd(II), (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-ylidene)], Yb(η 2 -Ph2CNPh)(hmpa)3 (hmpa = hexamethylphosphoramide), W(CO)6, Re2(CO) 10 Os3(CO) 12Ir4(CO) 12 , (acetylacetone)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), ruthenium on alumina, palladium on carbon, nickel on carbon, osmium on carbon, platinum(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst), bis(tri-tert-butylphosphine)platinum(O), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4], and other halogen-free M n+Complexes (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). The catalysts listed above, as well as pure noble metals (such as ruthenium, platinum, palladium, rhodium, osmium), can also be immobilized on supports. Supports are solids with high surface areas. Typical support materials include, but are not limited to: alumina, MgO, zeolite, carbon, monolithic cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO, and TiO2. Preferred supports are carbon (e.g., platinum-carbon, palladium-carbon, rhodium-carbon, ruthenium-carbon), alumina, silica, and MgO. The metal loading of the catalyst ranges from about 0.01 wt% to about 50 wt%. A preferred range is from about 0.5 wt% to about 20 wt%. A more preferred range is from about 0.5 wt% to about 10 wt%. The catalyst requiring activation can be activated by many known methods. Heating the catalyst under vacuum is a preferred method. The catalyst can be activated before being added to the reaction vessel or before reactants are added to the reaction vessel. The catalyst may contain a promoter. A promoter is a substance that is not itself a catalyst, but increases the efficiency (activity and / or selectivity) of the active catalyst when mixed in small amounts. Promoters are typically metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu, and Au and / or their oxides. They can be added separately to the reaction vessel, or they can be part of the catalyst itself. For example, Ru / Mn / C (ruthenium carbon promoted by manganese) or Pt / CeO2 / Ir / SiO2 (platinum-silica promoted by cerium dioxide and iridium). Some promoters can function as catalysts on their own, but they can improve the activity of the main catalyst when used in combination with it. A catalyst can act as a promoter for other catalysts. In this case, the catalyst can be called a bimetallic (or multimetallic) catalyst. For example, Ru / Rh / C can be called a ruthenium-rhodium-carbon bimetallic catalyst, or rhodium-promoted ruthenium-carbon. An active catalyst is a substance that acts as a catalyst in a specific chemical reaction.

[0073] Exemplary halogen-containing catalysts, including but not limited to the following, are main group, transition metal, lanthanide, and actinide catalysts: 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, C uBr2, Cu(PPh3)3Cl, ZnCl2, [(C6H6)RuX2]2 (X = Cl, Br, I), (Ph3P)3RhCl (Wilkinson catalyst), [RhCl (cyclooctadiene)]2, di-μ-chloro-tetracarbonyl dirhodium(I), bis(triphenylphosphine)rhodium(I)carbonyl chloride, 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).

[0074] The molar ratio of catalyst to cyclotrisiloxane or cyclotetrasiloxane in the reaction mixture ranges from 0.1:1, 0.05:1, 0.01:1, 0.005:1, 0.001:1, 0.0005:1, 0.0001:1, 0.00005:1, or 0.00001:1. In one specific embodiment, 0.05 to 0.07 equivalents of catalyst are used per amount of cyclotrisiloxane or cyclotetrasiloxane. In another specific embodiment, 0.00008 equivalents of catalyst are used per amount of cyclotrisiloxane or cyclotetrasiloxane.

[0075] In some embodiments, the reaction mixture comprising a cyclotrisiloxane or cyclotetrasiloxane, an organic amine, and a catalyst further comprises an anhydrous solvent. Exemplary solvents may include, but are not limited to, linear, branched, cyclic, or polyethers (e.g., tetrahydrofuran (THF), diethyl ether, diethylene glycol dimethyl ether, and / or tetraethylene glycol dimethyl ether); linear, branched, or cyclic alkanes, alkenes, aromatics, and halogenated hydrocarbons (e.g., pentane, hexane, toluene, and dichloromethane). If added, the selection of one or more solvents may be influenced by their compatibility with the reagents contained in the reaction mixture, the solubility of the catalyst, and / or the separation process of the selected intermediates and / or final products. In other embodiments, the reaction mixture does not contain a solvent.

[0076] In the methods described herein, the reaction between a cyclotrisiloxane or a cyclotetrasiloxane and an organic amine occurs at one or more temperatures ranging from about 0°C to about 200°C, preferably from 0°C to about 100°C, and more preferably from 0°C to 30°C. Exemplary temperatures for the reaction include ranges having one or more of the following endpoints: 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100°C. A suitable temperature range for the reaction may be determined by the physical properties of the reagents and optionally the solvents. Examples of specific reactor temperature ranges include, but are not limited to, 0°C to 80°C or 0°C to 30°C.

[0077] In some embodiments of the method described herein, the reaction pressure may be from about 1 to about 115 psia or from about 15 to about 45 psia. In some embodiments in which the cyclotrisiloxane or cyclotetrasiloxane is a liquid under ambient conditions, the reaction is carried out at atmospheric pressure. In some embodiments in which the cyclotrisiloxane or cyclotetrasiloxane is a gas under ambient conditions, the reaction is carried out at a pressure higher than 15 psia.

[0078] In some embodiments, one or more reagents may be introduced into the reaction mixture as a liquid or vapor. In embodiments where one or more reagents are added as vapor, a non-reactive gas such as nitrogen or an inert gas may be used as a carrier gas to deliver the vapor to the reaction mixture. In embodiments where one or more reagents are added as liquid, pure reagents may be added, or the reagents may be diluted with a solvent. The reagents are fed into the reaction mixture until the desired conversion to a crude mixture or crude liquid containing an organoamino-functionalized cyclic oligosiloxane product has been achieved. In some embodiments, the reaction may be carried out continuously by replenishing reactants and removing reaction products and crude liquid from the reactor.

[0079] Crude mixtures containing compounds of formula AB, catalysts, and potentially residual organic amines, solvents, or undesirable products may require separation processes. Examples of suitable separation processes include, but are not limited to, distillation, evaporation, membrane separation, filtration, gas-phase transfer, extraction, fractionation using reversed-phase columns, and combinations thereof.

[0080] Reactions 1-4 are exemplary chemical preparation methods, but are not intended to limit the preparation of compounds of formula A or B in any way.

[0081] The silicon precursor compound of formula A or B according to the invention and compositions comprising the silicon precursor compound of formula A or B according to the invention are preferably substantially free of halide ions. As used herein, the term "substantially free" when referring to halide ions (or halides), such as chlorides (i.e., chlorinated substances such as HCl or silicon compounds having at least one Si-Cl bond) and fluorides, bromides, and iodides, means less than 5 ppm (by weight) as measured by ICP-MS, preferably less than 3 ppm as measured by ICP-MS, more preferably less than 1 ppm as measured by ICP-MS, and most preferably 0 ppm as measured by ICP-MS. Chlorides are known to act as decomposition catalysts for silicon precursor compounds of formula A or B. Significant levels of chloride in the final product can lead to degradation of the silicon precursor compound. The gradual degradation of the silicon precursor compound can directly affect the film deposition process, making it difficult for semiconductor manufacturers to achieve film specifications. Furthermore, the higher degradation rate of the silicon precursor compound negatively impacts shelf life or stability, making it difficult to guarantee a shelf life of 1-2 years. Therefore, the accelerated decomposition of silicon precursor compounds raises safety and performance concerns related to the formation of these flammable and / or spontaneously combustible byproducts. Silicon precursor compounds of formula A or B are preferably substantially free of metal ions, such as Li. + Na + K + Mg 2+ Ca 2+ Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ Cr 3+ As used herein, the term "substantially free" when referring to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm, as measured by ICP-MS. In some embodiments, the silicon precursor compound of formula A or B is free of metal ions, such as Li + Na + K + Mg 2+ Ca 2+Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ Cr 3+ As used herein, the term "free of" metallic impurities, when referring to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, or noble metals such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in synthesis, means less than 1 ppm, preferably 0.1 ppm (by weight), as measured by ICP-MS or other analytical methods for measuring the metal.

[0082] In another embodiment, a method is provided for depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of:

[0083] a) Provide a substrate in the reactor;

[0084] b) Introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor is selected from formula A and B, wherein the R group is as defined above;

[0085]

[0086] c) Purge the reactor with purging gas;

[0087] d) Introduce an oxygen source into the reactor; and

[0088] e) Purge the reactor with purge gas.

[0089] Steps b through e are repeated until a film of the desired thickness is deposited; and the method is carried out at one or more temperatures ranging from about 25°C to 600°C.

[0090] The method disclosed herein forms a silicon oxide film having at least one of the following properties: a density of at least about 2.1 g / cc; a wet etching rate of less than about 1 g / cc as measured in a 1:100 dilute HF acid solution (0.5 wt% dHF) of HF:water. Until the electrical leakage at 6MV / cm is less than about 1e-8A / cm 2 The hydrogen impurities measured by secondary ion mass spectrometry (SIMS) are less than approximately 5e20 at / cc.

[0091] In some embodiments of the methods and compositions described herein, for example, a silicon-containing dielectric layer is deposited on at least a portion of a substrate using a chemical vapor deposition (CVD) process within a reaction chamber. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide (“GaAs”), silicon, and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxial silicon, silicon dioxide (“SiO2”), silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductor, integrated circuit, flat panel display, and flexible display applications. The substrate may have additional layers such as silicon, SiO2, organosilicon glass (OSG), fluorinated silicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, organic-inorganic composites, photoresists, organic polymers, porous organic and inorganic materials and composites, and metal oxides such as aluminum oxide and germanium oxide. Other layers may also be germanium silicates, aluminosilicates, copper and aluminum, as well as diffusion barrier materials, such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W or WN.

[0092] The deposition methods disclosed herein may include 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 precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof. In some embodiments, a purge gas such as Ar is supplied to the reactor at a flow rate of about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted material and any byproducts that may remain in the reactor.

[0093] A purge gas, such as argon, is used to remove unabsorbed excess composite material from the processing chamber. After thorough purging, an oxygen source can be introduced into the reaction chamber to react with the absorbed surface, followed by another gas purging to remove reaction byproducts from the chamber. This process can be repeated cyclically to achieve the desired film thickness. In some cases, pumping can be used instead of inert gas purging, or both can be used to remove unreacted silicon precursors.

[0094] Throughout this specification, the term "ALD or ALD sample" refers to processes including, but not limited to, those that: a) sequentially introduce each reactant, comprising silicon precursors and reactive gases, into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) expose each reactant, comprising silicon precursors and reactive gases, to a substrate by moving or rotating the substrate to different sections of the reactor, with each section separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0095] The method of the present invention is carried out by using an ALD process that includes an ozone or oxygen source containing plasma, wherein the plasma may also contain an inert gas, such as one or more of the following: oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide plasma (such as N2O, NO, NO2) plasma with or without inert gas, carbon oxide plasma (such as CO2, CO) plasma with or without inert gas, and combinations thereof.

[0096] The oxygen-containing plasma source can be generated in situ or optionally remotely. In one particular embodiment, the oxygen-containing source contains oxygen and flows or is introduced along with other reagents during method steps b to d, such as, but not limited to, at least one silicon precursor and optionally an inert gas.

[0097] In some embodiments, the compositions described herein, and those used in the disclosed methods, further comprise a solvent. Exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In some embodiments, the boiling point of the silicon precursor differs from that of the solvent by 40°C or less. In some embodiments, the composition can be delivered to a reaction chamber for a silicon-containing membrane via direct liquid injection.

[0098] For those embodiments in which at least one silicon precursor of formula A to B is used in a composition comprising a solvent, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition, by weight percentage, ranges from 0.5% to 99.5% by weight or from 10% to 75% by weight. In this or other embodiments, the boiling point (bp) of the solvent is similar to the bp of the silicon precursor of formula A to B, or the bp of the solvent differs from the bp of the silicon precursor of formula A to B by 40°C or less, 30°C or less, 20°C or less, or 10°C. Alternatively, the boiling point difference is within a range having one or more of the following endpoints: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of bp difference 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 (such as 1,4-dioxane, dibutyl ether), tertiary amines (such as pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (such as benzyl nitrile), alkyl hydrocarbons (such as octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (such as toluene, mesitylene), tertiary amino ethers (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0099] In some embodiments, the silicon oxide or carbon-doped silicon oxide film deposited using the methods described herein is formed in the presence of an oxygen-containing source including ozone, water (H2O) (e.g., deionized water, purified water, and / or distilled water), oxygen (O2), oxygen plasma, NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. The oxygen-containing source is provided by, for example, an in-situ or remote plasma generator to provide an oxygen-containing plasma source, such as oxygen plasma, a plasma containing oxygen and argon, a plasma containing oxygen and helium, ozone plasma, water plasma, nitrous oxide plasma, or carbon dioxide plasma. In some embodiments, the oxygen-containing plasma source comprises an oxygen source gas introduced into the reactor at a flow rate of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing plasma source may be introduced for about 0.1 to about 100 seconds. In one specific embodiment, the oxygen-containing plasma source comprises water at a temperature of 10°C or higher. In embodiments where the membrane is deposited via a PEALD or plasma-enhanced cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 to about 10 seconds, about 0.5 to about 20 seconds, about 1 to about 100 seconds) depending on the volume of the ALD reactor, and the oxygen-containing plasma source may have a pulse duration less than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).

[0100] In one or more of the above embodiments, the oxygen-containing plasma source is selected from oxygen plasma with or without an inert gas, water vapor plasma with or without an inert gas, nitrogen oxide (N2O, NO, NO2) plasma with or without an inert gas, carbon oxide (CO2, CO) plasma with or without an inert gas, and combinations thereof. In some embodiments, the oxygen-containing plasma source further comprises an inert gas. In these embodiments, the inert gas is selected from argon, helium, nitrogen, hydrogen, or combinations thereof. In alternative embodiments, the oxygen-containing plasma source does not comprise an inert gas.

[0101] The corresponding steps of supplying precursors, oxygen sources and / or other precursors, source gases and / or reagents can be performed by changing the timing of their supply to alter the stoichiometric composition of the resulting dielectric film.

[0102] Energy is applied to at least one of the silicon precursors, oxygen-containing sources, or combinations thereof of formulas A to B to initiate a reaction and form a dielectric film or coating on a substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helical wave plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some embodiments, a secondary RF source can be used to modify the plasma characteristics at the substrate surface. In embodiments where plasma deposition is involved, the plasma generation process can include a direct plasma generation process (where plasma is generated directly in the reactor) or a remote plasma generation process (where plasma is generated outside the reactor and supplied to the reactor).

[0103] At least one silicon precursor can be delivered to the reaction chamber in various ways, such as in a plasma-enhanced cyclic CVD or PEALD reactor or a batch furnace reactor. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combined liquid delivery and flash evaporation unit, such as a turbine evaporator manufactured by MSP Corporation, Shoreview, MN, can be used to enable the quantitative delivery of low-volatility materials, resulting in repeatable delivery and deposition without thermal decomposition of the precursor. In liquid delivery configurations, the precursors described herein can be delivered in pure liquid form or used in solvent formulations or compositions containing them. Thus, in some embodiments, the precursor formulation may contain a solvent component with suitable properties (such as those that may be desired and advantageous in a given end-use application) to form a film on a substrate.

[0104] As previously stated, the purity level of at least one silicon precursor is sufficiently high to be acceptable for reliable semiconductor manufacturing. In some embodiments, the at least one silicon precursor described herein contains one or more of the following impurities: less than 2% by weight, less than 1% by weight, or less than 0.5% by weight: free amines, free halides or halide ions, and substances of higher molecular weight. The high purity level of the silicon precursor described herein can be obtained by one or more of the following methods: purification, adsorption, and / or distillation.

[0105] In one embodiment of the method described herein, a plasma-enhanced cyclic deposition process, such as PEALD-like or PEALD, can be used, wherein deposition is performed using at least one silicon precursor and an oxygen plasma source. The PEALD-like process is defined as a plasma-enhanced cyclic CVD process, but still provides highly conformal silicon- and oxygen-containing films.

[0106] In one embodiment of the present invention, a method for depositing a silicon- and oxygen-containing film on at least one surface of a substrate is described herein, wherein the method includes the following steps:

[0107] a. Provide a substrate in the reactor;

[0108] b. Introduce at least one silicon precursor having formulas A to B as defined above into the reactor;

[0109] c. Purge the reactor with purging gas;

[0110] d. Introduce an oxygen-containing source, including plasma, into the reactor; and

[0111] e. Purge the reactor with purge gas.

[0112] In this method, steps b through e are repeated until a film of the desired thickness is deposited on the substrate.

[0113] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in a variety of orders, can be performed sequentially, can be performed simultaneously (e.g., during at least a portion of another step), and any combination thereof. For example, the corresponding steps of supplying the precursor and oxygen source gas can be performed by varying the duration of their supply to change the stoichiometric composition of the resulting dielectric film. Moreover, the purge time after the precursor or oxidant step can be minimized to <0.1 s, thereby increasing yield.

[0114] In one specific embodiment, the method described herein deposits a high-quality silicon- and oxygen-containing film on a substrate at a temperature below 300°C. The method includes the following steps:

[0115] a. Provide a substrate in the reactor;

[0116] b. Introduce at least one silicon precursor having formulas A to B as described herein into the reactor;

[0117] c. Purge the reactor with purge gas to remove at least a portion of the unabsorbed precursors;

[0118] d. Introduce an oxygen-containing plasma source into the reactor; and

[0119] e. Purge the reactor with purge gas to remove at least a portion of the unreacted oxygen source.

[0120] Steps b through e are repeated until a silicon-containing film of the desired thickness is deposited.

[0121] In another specific embodiment, the method described herein deposits a high-quality silicon- and oxygen-containing film on a substrate at a temperature above 550°C. The method includes the following steps:

[0122] a. Provide a substrate in the reactor;

[0123] b. Introduce at least one organic amino-functionalized cyclic oligosiloxane precursor having the formulas A to B described herein into the reactor;

[0124] c. Purge the reactor with purge gas to remove at least a portion of the unabsorbed precursors;

[0125] d. Introduce an oxygen-containing plasma source into the reactor; and

[0126] e. Purge the reactor with purge gas to remove at least a portion of the unreacted oxygen source.

[0127] Steps b through e are repeated until a silicon-containing film of the desired thickness is deposited.

[0128] It is believed that organoamino-functionalized cyclic oligomeric siloxane precursors of formulas A to B (especially those containing R) can decompose at temperatures above 600°C and potentially lead to undesirable chemical vapor deposition. 3 -R 9 (Not hydrogen) is preferred for this method because they either do not contain any Si-H groups or the number of Si-H groups is limited. However, it is possible, under certain conditions, such as using short precursor pulses or low reactor pressure, that the method can also use organic amino-functionalized cyclic oligomeric oligosiloxane precursors of formulas A to B (where R... 3 -R 9 The process (either of which is hydrogen) is carried out at temperatures above 600°C without significant undesirable chemical vapor deposition or precursor decomposition on the surface.

[0129] Another method disclosed herein uses a silicon precursor compound having a chemical structure represented by formulas A to B as defined above, plus an oxygen source to form a carbon-doped silicon oxide film.

[0130] Another exemplary method is described below:

[0131] a. Provide a substrate in the reactor;

[0132] b. Contacting vapor generated from at least one silicon precursor compound having a structure represented by formulas A to B as defined above with or without a co-flowing oxygen source to chemically absorb the precursor onto a heated substrate.

[0133] c. Blow away any unabsorbed precursors;

[0134] d. Introduce an oxygen source onto a heated substrate to react with the absorbed precursor; and,

[0135] e. Purge away any unreacted oxygen sources.

[0136] Repeat steps b through e until the desired thickness is achieved.

[0137] In another particular embodiment, the method described herein deposits a high-quality silicon oxynitride film on a substrate. The method includes the following steps:

[0138] a. Provide a substrate in the reactor;

[0139] b. Introduce at least one silicon precursor having formulas A to B as described herein into the reactor;

[0140] c. Purge the reactor with purge gas to remove at least a portion of the unabsorbed precursors;

[0141] d. Introduce a nitrogen-containing plasma source into the reactor; and

[0142] e. Purge the reactor with purge gas to remove at least a portion of the unreacted nitrogen source.

[0143] Steps b through e are repeated until a nitrogen-containing silicon oxide film of the desired thickness is deposited.

[0144] Another exemplary method is described below:

[0145] a. Provide a substrate in the reactor;

[0146] b. Contacting a vapor generated from at least one silicon precursor compound having a structure represented by formulas A to B as defined above with or without a co-current nitrogen source to chemically absorb the precursor on a heated substrate;

[0147] c. Blow away any unabsorbed precursors;

[0148] d. Introducing a nitrogen source onto a heated substrate to react with the absorbed precursor; and,

[0149] e. Purge away any unreacted nitrogen sources.

[0150] Repeat steps b through e until the desired thickness is achieved.

[0151] Various commercial ALD reactors, such as single-wafer, half-batch, batch furnace, or roll-to-roll reactors, can be used to deposit solid silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide.

[0152] The process temperatures described herein use one or more of the following temperatures as endpoints: 0°C, 25°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, 350°C, 375°C, 400°C, 425°C, 450°C, 500°C, 525°C, 550°C, 600°C, 650°C, 700°C, 750°C, 760°C, and 800°C. Exemplary temperature ranges include, but are not limited to, the following: about 0°C to about 300°C; or about 25°C to about 300°C; or about 50°C to about 290°C; or about 25°C to about 250°C; or about 25°C to about 200°C.

[0153] On the other hand, a method is provided for depositing a silicon- and oxygen-containing film by flowable chemical vapor deposition (FCVD), the method comprising:

[0154] A substrate containing surface features is placed in a reactor, wherein the substrate is maintained at one or more temperatures in the range of about -20°C to about 400°C, and the pressure of the reactor is maintained at 100 Torr or lower;

[0155] Introduce at least one compound selected from formulas A to B as defined herein;

[0156] An oxygen source is provided to the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features;

[0157] Annealing the film at one or more temperatures from about 100°C to 1000°C to coat at least a portion of the surface features; and

[0158] A substrate is treated with an oxygen source at one or more temperatures from about 20°C to about 1000°C to form a silicon-containing film on at least a portion of the surface features.

[0159] On the other hand, a method is provided for depositing a silicon- and oxygen-containing film by flowable chemical vapor deposition (FCVD), the method comprising:

[0160] A substrate containing surface features is placed in a reactor, wherein the substrate is maintained at one or more temperatures from about -20°C to about 400°C, and the pressure of the reactor is maintained at 100 Torr or less;

[0161] Introduce at least an organic amino-functionalized cyclic oligosiloxane selected from formulas A to B as defined herein;

[0162] A nitrogen source is provided to the reactor to react with at least one compound to form a film that covers at least a portion of a surface feature;

[0163] Annealing the film at one or more temperatures from about 100°C to 1000°C to coat at least a portion of the surface features; and

[0164] A substrate is treated with an oxygen source at one or more temperatures from about 20°C to about 1000°C to form a silicon-containing film on at least a portion of the surface features.

[0165] In some embodiments, the oxygen source is selected from water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and mixtures thereof. In other embodiments, the nitrogen source is selected from, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof. In still other embodiments, the nitrogen source includes ammonia plasma, plasma containing nitrogen and argon, plasma containing nitrogen and helium, or plasma containing hydrogen and nitrogen source gas. In this or other embodiments, the method steps are repeated until the surface feature is filled with a silicon-containing film. In embodiments where water vapor is used as the oxygen source in a flowable chemical vapor deposition method, the substrate temperature is from about -20°C to about 40°C or from about -10°C to about 25°C.

[0166] In another embodiment of the method described herein, a film deposited by ALD, ALD-sample, PEALD, PEALD-sample, or FCVD, or such deposited film, is subjected to a processing step (post-deposition). The processing step may be performed during at least a portion of the deposition step, after the deposition step, or in combinations thereof. Exemplary processing steps include, but are not limited to, treatment by high-temperature thermal annealing; plasma treatment; ultraviolet (UV) light treatment; laser treatment; electron beam treatment; and combinations thereof, to affect one or more properties of the film.

[0167] In another embodiment, a vessel or container for depositing a silicon-containing film is provided, comprising one or more silicon precursor compounds described herein. In a particular embodiment, the container comprises at least one pressurized container (preferably a stainless steel container having the design disclosed in U.S. Patent Nos. US7334595, US6077356, US5069244, and US5465766, the disclosures of which are incorporated herein by reference). The container may comprise glass (borosilicate or quartz glass) or 316, 316L, 304, or 304L type stainless steel alloys (UNS designations S31600, S31603, S30400, S30403), equipped with suitable valves and fittings to allow delivery of one or more precursors to a reactor for a CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurized container made of stainless steel, and the purity of the precursor is 98% by weight or higher or 99.5% by weight or higher, which is suitable for most semiconductor applications. The headspace of the vessel or container is filled with an inert gas selected from helium, argon, nitrogen, and combinations thereof.

[0168] In some embodiments, the gas line connecting the precursor tank to the reaction chamber is heated to one or more temperatures according to process requirements, and the container for at least one silicon precursor is maintained at one or more temperatures for bubbling. In other embodiments, a solution containing at least one silicon precursor is injected into an evaporator maintained at one or more temperatures for direct liquid injection.

[0169] A stream of argon and / or other gases can be used as a carrier gas to help deliver the vapor of at least one silicon precursor to the reaction chamber during the precursor pulse process. In some embodiments, the reaction chamber process pressure is about 50 mTorr to 10 Torr. In other embodiments, the reaction chamber process pressure can be up to 760 Torr (e.g., about 50 mTorr to about 100 Torr).

[0170] In typical PEALD or PEALD-like processes (such as PECCVD process), the substrate, such as a silicon oxide substrate, is heated on a heater stage in a reaction chamber, which is initially exposed to silicon precursors to allow the composite to be chemisorbed onto the substrate surface.

[0171] Compared to films deposited under the same conditions using previously disclosed silicon precursors, films deposited using silicon precursors having formulas A to B as described herein have improved properties, such as, but not limited to, wet etch rates lower than the wet etch rate of the film before the processing step, or densities higher than the density before the processing step. In a particular embodiment, the film thus deposited is processed intermittently during the deposition process. These intermittent or deposition-in-process processing may be performed, for example, after each ALD cycle, after a certain number of ALD cycles (e.g., but not limited to, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles).

[0172] The precursors of formulas A to B exhibit / Cycle or higher growth rate.

[0173] In embodiments where the film is treated with a high-temperature annealing step, the annealing temperature is at least 100°C or higher than the deposition temperature. In this or other embodiments, the annealing temperature is in the range of about 400°C to about 1000°C. In this or other embodiments, the annealing treatment can be carried out in a vacuum (<760 Torr), an inert environment, or an oxygen-containing environment (such as H2O, N2O, NO2, or O2).

[0174] In embodiments where the membrane undergoes UV treatment, the membrane is exposed to broadband UV light, or optionally to a UV source having a wavelength ranging from about 150 nanometers (nm) to about 400 nm. In a particular embodiment, after the desired membrane thickness is achieved, the deposited membrane is exposed to UV light in a chamber different from the deposition chamber.

[0175] In embodiments where the membrane is treated with plasma, a passivation layer (such as SiO2 or carbon-doped SiO2) is deposited to prevent chlorine and nitrogen contaminants from penetrating into the membrane during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0176] In one embodiment of plasma treatment of the membrane, the plasma source is selected from hydrogen plasma, plasma containing hydrogen and helium, or plasma containing hydrogen and argon. Hydrogen plasma reduces the dielectric constant of the membrane and enhances its resistance to damage during subsequent plasma ashing processes while maintaining the overall carbon content almost unchanged.

[0177] Not intended to be limited by any particular theory, it is believed that silicon precursor compounds having chemical structures represented by formulas A to B as defined above can be anchored by reacting organic amino groups with hydroxyl groups on the substrate surface to provide multiple Si-O-Si segments per molecule of precursor, thus increasing the growth rate of silicon oxide or carbon-doped silicon oxide compared to conventional silicon precursors such as bis(tert-butylamino)silane or bis(diethylamino)silane, which have only one silicon atom.

[0178] In some embodiments, silicon precursors having formulas A to B as defined above can also be used as dopants for metal-containing films, such as, but not limited to, metal oxide films or metal oxynitride films. In these embodiments, metal-containing films are deposited using ALD or CVD processes (such as those described herein) with the use of metal alkoxides, metal amides, or volatile organometallic precursors. Examples of suitable metal alkoxide precursors that can be used with the methods disclosed herein include, but are not limited to: group 3 to 6 metal alkoxides, group 3 to 6 metal complexes having both alkoxy and alkyl-substituted cyclopentadienyl ligands, group 3 to 6 metal complexes having both alkoxy and alkyl-substituted pyrroleyl ligands, group 3 to 6 metal complexes having both alkoxy and diketonate ligands, and group 3-6 metal complexes having both alkoxy and ketone ester ligands.

[0179] Examples of suitable metal amide precursors that can be used with the methods disclosed herein include, but are not limited to, tetra(dimethylamino)zirconium (TDMAZ), tetra(diethylamino)zirconium (TDEAZ), tetra(ethylmethylamino)zirconium (TEMAZ), tetra(dimethylamino)hafnium (TDMAH), tetra(diethylamino)hafnium (TDEAH), and tetra(ethylmethylamino)hafnium (TEMAH), tetra(dimethylamino)titanium (TDMAT), tetra(diethylamino)titanium (TDEAT), tetra(ethylmethylamino)titanium (TEMAT), tert-butyliminotris(diethylamino)tantalum (TBTDET), and tert-butyliminotris(dimethylamino)tantalum (TBTD). MT), tert-butyliminotris(ethylmethylamino)tantalum (TBTEMT), ethyliminotris(diethylamino)tantalum (EITDET), ethyliminotris(dimethylamino)tantalum (EITDMT), ethyliminotris(ethylmethylamino)tantalum (EITEMT), tert-pentyliminotris(dimethylamino)tantalum (TAIMAT), tert-pentyliminotris(diethylamino)tantalum, penta(dimethylamino)tantalum, tert-pentyliminotris(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinations thereof. Examples of suitable organometallic precursors that can be used with the methods disclosed herein include, but are not limited to, group 3 metal cyclopentadienyl compounds or alkylcyclopentadienyl compounds. The exemplary group 3 to 6 metals mentioned herein include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

[0180] In some embodiments, the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the film may have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is contemplated that films with other dielectric constants (e.g., higher or lower) may be formed depending on the desired end use of the film. Examples of silicon-containing films formed using the silicon precursors and methods described herein with precursors of formulas A to B have the formula Si x O y C z N v H w The silicon content is in the range of about 10% to about 40%; O is in the range of about 0% to about 65%; C is in the range of about 0% to about 75% or about 0% to about 50%; N is in the range of about 0% to about 75% or about 0% to 50%; and H is in the range of about 0% to about 50% (atomic weight%), where x+y+z+v+w = 100 atomic weight%, as determined, for example, by XPS or other methods. Another example of a silicon-containing film formed using the silicon precursors and methods of formulas A to B described herein is silicon carbonoxynitride, wherein the carbon content, measured by XPS, is from 1 atomic% to 80 atomic%. Yet another example of a silicon-containing film formed using the silicon precursors and methods of formulas A to B described herein is an amorphous silicon film, wherein the sum of the nitrogen and carbon contents, measured by XPS, is <10 atomic%, preferably <5 atomic%, and most preferably <1 atomic%.

[0181] As previously described, the methods described herein can be used to deposit silicon-containing films on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, oxysilicon carbide, oxynitride, silicon oxycarbonitride, oxycarbonitride, antireflective coatings, photoresists, germanium, germanium-containing materials, boron-containing materials, Ga / As, flexible substrates, organic polymers, porous organic and 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 chemical mechanical planarization (CMP) and anisotropic etching processes.

[0182] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage, coatings on support materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin-film transistors (TFTs), light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), IGZOs, and liquid crystal displays (LCDs). Potential uses for the resulting solid silicon oxide or carbon-doped silicon oxide include, but are not limited to, shallow trench isolation, interlayer dielectric layers, passivation layers, etch stop layers, portions of dual spacers, and sacrificial layers for patterning.

[0183] The methods described herein provide high-quality silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide films. The term "high-quality" refers to a film exhibiting one or more of the following characteristics: a density of about 2.1 g / cc or higher, 2.2 g / cc or higher, or 2.25 g / cc or higher; as measured in a dilute HF acid solution (0.5 wt% dHF) of HF and water at a 1:100 ratio. / s or lower / s or lower / s or lower / s or lower / s or lower / s or lower / s or lower / s or lower wet etching rates; up to 6MV / cm at approximately 1e-8A / cm 2 Or even lower leakage current; and hydrogen impurities such as approximately 5e20 at / cc or lower as measured by SIMS; and combinations thereof. Regarding the etching rate, thermally grown silicon oxide films exhibit [percentage missing] in 0.5 wt% HF. Etching rate of / s.

[0184] In some embodiments, one or more silicon precursors having formulas A to B described herein can be used to form silicon and oxygen-containing films that are solid and non-porous or substantially non-porous.

[0185] Therefore, the present invention provides at least the following:

[0186] 1. A composition comprising at least one organic amino-functionalized cyclic oligosiloxane compound selected from formulas A and B:

[0187]

[0188] Where (i)R 1 Selected from C3-C 10 cycloalkyl and C3-C 10 Aryl, R 2 Selected from hydrogen and C1-C4 alkyl groups, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups; or (ii)R 1 and R 2 Connect to form C3-C 10 Heterocyclic structure or C3-C 10 Heterocyclic aryl structures, wherein any one of them may be substituted with one, two or more methyl groups, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0189] 2. The composition according to claim 1, further comprising at least one selected from solvent and purge gas.

[0190] 3. The composition according to claim 1 or 2, wherein the composition is substantially free of one or more impurities selected from halides, metal ions, metals and combinations thereof.

[0191] 4. The composition according to any one of items 1-3, wherein R 1 Selected from C3-C 10 cycloalkyl and C3-C 10 Aryl, R 2 Selected from hydrogen and C1-C4 alkyl groups, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0192] 5. The composition according to any one of items 1-3, wherein R 1 and R 2 Connect to form C3-C 10 Heterocyclic structure or C3-C 10 Heterocyclic aryl structures, wherein any one of them may be substituted with one, two or more methyl groups, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0193] 6. The composition according to any one of claims 1-5, wherein the organoamino-functionalized cyclic oligomeric siloxane compound is selected from: 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethyl... Amino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-piperidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino 2-Phenylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Phenylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Phenylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclopentylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Pyrrolidinyl-2,4,6-Trimethylcyclotrisiloxane, 2-Pyrrolidinyl-2,4,6-Trimethylcyclotrisiloxane, 2-Piperidinyl-2,4,6-Trimethylcyclotrisiloxane, 2-(2-Methylpiperidinyl)-2,4,6-Trimethylcyclotrisiloxane, 2-(2,6 (-Dimethylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2,6-Dimethylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0194] 7. A method for preparing organoamino-functionalized cyclic oligosiloxane compounds selected from formulas A and B:

[0195]

[0196] The method includes the following steps:

[0197] As shown in reaction (1) or (3), the cyclotrisiloxane of formula (i) or the cyclotetrasiloxane of formula (iii) reacts with an organic amine in the presence of a catalyst:

[0198]

[0199]

[0200] Or, as shown in reaction (2) or (4), react with organic amines or metal salts of organic amines in the presence of a catalyst:

[0201]

[0202] Where R 1 Selected from linear C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C3-C 10 alkenyl, C3-C 10 alkynyl and C3-C 10 Aryl, R 2 Selected from C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0203] 8. The method according to item 7, wherein R 3 -R 9 Each is independently selected from hydrogen and methyl.

[0204] 9. The method according to item 7, wherein in formulas A and B, R 1 Selected from C3-C10 cycloalkyl and C3-C 10 Aryl, R 2 Selected from hydrogen and C1-C4 alkyl groups, and R 3 -R 9 Each is independently selected from hydrogen and C1-C4 alkyl groups.

[0205] 10. The method according to item 7, wherein in formulas A and B, R 1 and R 2 Connect to form C3-C 10 Heterocyclic structure or C3-C 10 Heterocyclic aryl structures, any one of which may be substituted by one, two or more methyl groups.

[0206] 11. A method for depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of:

[0207] a) Provide a substrate in the reactor;

[0208] b) Introducing at least one organic amino-functionalized cyclic oligosiloxane compound as defined in any one of items 1-6 into the reactor;

[0209] c) Purge the reactor with purge gas;

[0210] d) Introducing at least one of an oxygen source and a nitrogen source into the reactor; and

[0211] e) Purge the reactor with purge gas.

[0212] Steps b through e are repeated until a film of the desired thickness is deposited; and the method is carried out at one or more temperatures ranging from about 25°C to 600°C.

[0213] 12. A silicon- and oxygen-containing film comprising at least one of the following characteristics: a density of at least about 2.1 g / cc; a wet etch rate of 5 or less relative to thermal oxides measured in 0.5 wt% dHF solution; and an electrical leakage of less than about 1e-8 A / cm up to 6 MV / cm. 2 The hydrogen impurities measured by secondary ion mass spectrometry (SIMS) are less than approximately 5e20 at / cc.

[0214] 13. A stainless steel container for containing a composition according to any one of claims 1-6.

[0215] 14. The stainless steel container according to claim 13, further comprising an inert headspace gas selected from helium, argon, nitrogen, and combinations thereof.

[0216] 15. The method according to claim 11, wherein the at least one organic amino-functionalized cyclic oligomeric siloxane compound is introduced into the reactor together with at least one selected from a solvent and an inert gas.

[0217] The following embodiments are provided to illustrate certain aspects of the invention and should not be construed as limiting the scope of the appended claims.

[0218] Working Example

[0219] Example 1: Synthesis of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane.

[0220] Under nitrogen protection, 2,4,6,8-tetramethylcyclotetrasiloxane (400 g, 1.66 mol) was added to Ru3(CO). 12 A stirred solution of pyrrolidine (4.00 g, 0.00626 mol), pyrrolidine (39.43 g, 0.554 mol), and THF (100 g, 1.39 mol) was added. After stirring for 2 hours, the second portion of pyrrolidine (39.43 g, 0.554 mol) was added to the stirred reaction mixture. After stirring for 4 hours, the third portion of pyrrolidine (39.43 g, 0.554 mol) was added to the stirred reaction mixture. Bubbles were released, and the reaction solution was stirred overnight at room temperature. The solvent was removed under reduced pressure, and the crude product was purified by fractional distillation to provide the desired product, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS analysis showed the following mass peaks: m / z = 309 (M+), 295, 281, 267, 253, 240, 226, 208, 194, 180, 166, 148, 134, 120, 106, 84, 71.

[0221] Example 2: Synthesis of 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0222] Under nitrogen protection, 2-chloro-2,4,6,8-tetramethylcyclotetrasiloxane (0.15 g, 0.00055 mol) was added dropwise to a stirred solution of N-cyclohexylmethylamine (0.09 g, 0.0008 mol) and triethylamine (0.07 g, 0.0007 mol) in hexane (1 mL). The resulting white slurry was stirred overnight at room temperature. The solid was removed by filtration, and the filtrate was determined by GC-MS to contain the desired product, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks: m / z = 351 (M+), 336 (M-15), 323, 308, 292, 280, 266, 252, 239, 225, 207, 193, 179, 165, 154, 147, 133, 123, 112, 98, 83, 73.

[0223] Examples 3-8: Synthesis of other organic amino-functionalized cyclic oligosiloxanes.

[0224] Further organoamino-functionalized cyclic oligosiloxanes were synthesized in a manner similar to that described in Examples 1 and 2, and characterized by GC-MS. Table 2 provides the molecular weight (MW), structure, and corresponding major MS fragment peaks for each compound to confirm their identity.

[0225] Table 2. Organic amino-functionalized cyclic oligosiloxanes.

[0226]

[0227]

[0228] Example 9: Thermal stability of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane.

[0229] 2-Pyrrolidinyl-2,4,6,8-Tetramethylcyclotetrasiloxane was heated at 80 °C for 7 days. GC analysis showed that the content of 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane decreased from 99.24% to an average of 98.95%, confirming that 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane possesses excellent thermal stability and is suitable as a precursor for vapor deposition processes.

[0230] Example 10: PEALD silica using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor with 27.1 MHz plasma.

[0231] Plasma-enhanced ALD (PEALD) was performed in a commercial side-flow reactor (a 300 mm PEALD device manufactured by ASM) equipped with a 27.1 MHz direct plasma capability and a fixed 3.5 mm spacing between electrodes. The precursor was heated to 70 °C in a stainless steel bubbler and delivered to the chamber with Ar carrier gas. All reported depositions were performed on native oxide-containing Si substrates. Film thickness and refractive index were measured using a FilmTek 2000SE ellipsometer. Wet etch rate (WER) measurements were performed using a 1:99 (0.5 wt%) dilute hydrofluoric acid (HF) solution. Thermal oxide wafers were used as standards for each set of experiments to confirm the activity of the etch solution. Before starting to collect the WER of the bulk film, the sample was etched for 15 seconds to remove any surface layer. The typical wet etch rate of a thermal oxide wafer with a 1:99 (0.5 wt%) dHF aqueous solution was obtained using this procedure.

[0232] Deposition was performed under the conditions described in Table 3 below, using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane as the silicon precursor and O2 plasma as the oxygen source. The precursor was fed into the chamber with an Ar carrier gas flow rate of 200 sccm. Steps b to e were repeated multiple times to obtain silicon oxide of the desired thickness for measurement.

[0233] Table 3. PEALD silica deposition process using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane in a commercial side-stream PEALD reactor

[0234]

[0235] For 100°C deposition, film deposition parameters and growth per cycle (GPC) are shown in Table 4, and for 300°C deposition, they are shown in Table 5. Depositions 1-6 and 13-18 show GPC relative to precursor pulse time at deposition temperatures of 100°C and 300°C. Figure 1 The saturation curves of GPC for 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane relative to the precursor pulse number are shown. It can be seen that GPC increases with the precursor pulse number and then saturates, indicating the ALD behavior of the precursor. Deposition at 100 °C shows a higher GPC than at 300 °C. BDEAS (bis(diethylamino)silane) deposition under similar conditions... Figure 1 The values ​​shown are for comparison; 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane shows a much higher GPC than BDEAS. Depositions 7-12 and 19-23 show GPC and film relative WER as a function of varying deposition pressure, oxygen plasma time, or oxygen plasma power. Figure 2 The film GPC and WER are shown as a function of O2 plasma power at a deposition temperature of 300°C. Figure 3 The GPC and WER of the film are shown relative to the O2 plasma power at deposition temperature of 100 °C. GPC decreases slightly with increasing oxygen plasma power, while WER decreases with increasing oxygen plasma power. Films deposited at higher temperatures exhibit lower WER. Figure 4 The graph shows the membrane GPC and WER relative to O2 plasma time at 100°C deposition. GPC decreases slightly with increasing oxygen plasma time, while WER decreases with increasing oxygen plasma time. A lower membrane WER indicates higher membrane quality.

[0236] Table 4. PEALD silica film deposition parameters and deposition GPC using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane at 100 °C.

[0237]

[0238]

[0239] Table 5. PEALD silica film deposition parameters and deposition GPC using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane at 300 °C.

[0240]

[0241] Samples 9 and 10, deposited at 100°C, and samples 21 and 22, deposited at 300°C, were subjected to vacuum thermal annealing at 600°C. The WER of the films was measured before and after annealing and summarized in Table 6. The SIMS data before and after annealing are summarized in Table 7. It can be seen that the WER and hydrogen content decreased significantly after thermal annealing. For the samples deposited at 100°C, the deposited films showed high N content, which decreased significantly after thermal annealing.

[0242] Table 6. WER of different samples before and after vacuum heat annealing at 600℃.

[0243]

[0244]

[0245] Table 7. Film impurity levels before and after vacuum heat annealing at 600℃.

[0246]

[0247] Example 11: Thermal atomic layer deposition (predicted) of silicon oxide film using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane.

[0248] Atomic layer deposition of silicon oxide films was performed using 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane as the silicon precursor. Deposition was carried out on a laboratory-scale ALD processing apparatus. The silicon precursor was transported into the chamber via vapor suction. All gases (e.g., purge and reactant gases or precursor and oxygen source) were preheated to 100°C before entering the deposition zone. The substrate used for deposition was a 12-inch long silicon strip. Thermocouples were attached to the sample holder to confirm the substrate temperature. Ozone was used as the oxygen source gas for deposition. The deposition process and parameters are provided in Table 8. Steps 1 through 6 were repeated until the desired thickness was achieved.

[0249] Table 8. Thermal atomic layer deposition process of silicon oxide film using ozone as oxygen source on a laboratory-scale ALD treatment device.

[0250] Step 1 6 seconds Empty reactor <100mT Step 2 variable Quantitative feeding of silicon precursor Reactor pressure is typically <2 Torr. Step 3 6 seconds Purge the reactor with nitrogen. <![CDATA[1.5 slpm N2 flow]]> Step 4 6 seconds Empty reactor <100mT Step 5 variable Quantitative feeding of oxygen source ozone Step 6 6 seconds Purge the reactor with nitrogen. <![CDATA[1.5 slpm N2 flow]]>

[0251] At 300°C, the deposited film is a pure silicon oxide film with carbon doping that is undetectable by XPS. At 100°C, a carbon-doped silicon oxide film is formed, and this film has a lower WER compared to the film at 300°C. The growth per cycle (GPC) at both 300°C and 100°C is greater than [value missing]. / cycle.

[0252] Comparative Example 12a: 2,4,6,8-Tetramethylcyclotetrasiloxane (TMCTS) silicon oxide PEALD was used in a laminar flow reactor with 27.1 MHz plasma.

[0253] TMCTS was deposited using a silicon precursor and O2 plasma reactant. The TMCTS was delivered to the chamber via vapor suction, without a carrier gas. Steps b through e in Table 3 were repeated multiple times to obtain silicon oxide of the desired thickness for measurement. Film deposition parameters, deposition GPC, and wafer uniformity are shown in Table 9. The deposited wafers exhibited poor uniformity, and the GPC did not saturate with increasing precursor pulses, indicating poor CVD deposition of TMCTS. Therefore, the nonfunctionalized cyclic oligosiloxane TMCTS is unsuitable as an ALD precursor.

[0254] Table 9. PEALD silicon oxide film deposition parameters, deposition GPC, and wafer uniformity of TMCTS.

[0255]

[0256] Comparative Example 12b: Silica PEALD of bis(diethylamino)silane (BDEAS) was used in a laminar flow reactor with 27.1 MHz plasma.

[0257] Deposition was performed using BDEAS as the silicon precursor and O2 plasma under the conditions described in Table 3 above. The precursor was fed into the chamber with an Ar carrier gas flow rate of 200 sccm. Steps b to e were repeated multiple times to obtain silicon oxide of the desired thickness for measurement. Film deposition parameters and deposition GPC are shown in Table 10. Figure 1 The GPC is shown relative to different precursor flow times. BDEAS shows a much lower GPC than 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane.

[0258] Table 10. PEALD silica film deposition parameters and deposition GPC for BDEAS.

[0259]

[0260] While the invention has been described with reference to certain preferred embodiments, those skilled in the art will understand that various changes can be made and elements can be substituted in an equivalent manner without departing from the scope of the invention. Furthermore, many modifications can be made to adapt particular situations or materials to the teachings of the invention without departing from its essential scope. Therefore, it is intended that the invention be limited to particular embodiments, but rather that it encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for depositing a silicon- and oxygen-containing film by flowable chemical vapor deposition (FCVD), the method comprising: A substrate containing surface features is placed in a reactor, wherein the substrate is maintained at one or more temperatures in the range of -20°C to 400°C, and the pressure of the reactor is maintained at 100 Torr or lower; Introduces at least one compound, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane. Trisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-piperidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,4,6,6,8,8- Heptamethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclopentylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-piperidinyl-2,4,6-trimethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotetrasiloxane Trisiloxane, 2-phenylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,68-Tetramethylcyclotetrasiloxane, 2-phenylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane; An oxygen source is provided to the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; The film is annealed at one or more temperatures from 100°C to 1000°C to cover at least a portion of the surface features; and A substrate is treated with an oxygen source at one or more temperatures from 20°C to 1000°C to form a silicon-containing film on at least a portion of the surface features.

2. A method for depositing a silicon- and oxygen-containing film by flowable chemical vapor deposition (FCVD), the method comprising: A substrate containing surface features is placed in a reactor, wherein the substrate is maintained at one or more temperatures ranging from -20°C to 400°C, and the pressure of the reactor is maintained at 100 Torr or lower; Introduces at least one compound, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane. Trisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-piperidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,4,6,6,8,8- Heptamethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclopentylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-piperidinyl-2,4,6-trimethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotetrasiloxane Trisiloxane, 2-phenylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,68-Tetramethylcyclotetrasiloxane, 2-phenylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane; A nitrogen source is provided to the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; The film is annealed at one or more temperatures from 100°C to 1000°C to cover at least a portion of the surface features; and A substrate is treated with an oxygen source at one or more temperatures from 20°C to 1000°C to form a silicon-containing film on at least a portion of the surface features.

3. The method according to claim 1 or 2, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidinyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)- 2,4,4,6,6-Pentamethylcyclotrisiloxane, 2-Cyclohexylmethylamino-2,4,4,6,6-Pentamethylcyclotrisiloxane, 2-Phenyloamino-2,4,4,6,6-Pentamethylcyclotrisiloxane, 2-Phenylomethylamino-2,4,4,6,6-Pentamethylcyclotrisiloxane, 2-Cyclohexylamino-2,4,4,6,6-Pentamethylcyclotrisiloxane, 2-Cyclopentylamino-2,4,4,6,6-Pentamethylcyclotrisiloxane.

4. The method according to claim 1 or 2, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-piperidinyl-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-(2, 6-Dimethylpiperidinyl)-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclopentylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane.

5. The method according to claim 1 or 2, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidinyl-2,4,6-trimethylcyclotrisiloxane, 2-piperidinyl-2,4,6-trimethylcyclotrisiloxane, 2-(2-methylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-(2,6-dimethylpiperidinyl)-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane.

6. The method according to claim 1 or 2, wherein the at least one compound is selected from: 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2-methylpiperidinyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2-(2,6-dimethylpiperidinyl) 2-Cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

7. The method according to claim 1 or 2, wherein the oxygen source is selected from water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and mixtures thereof.

8. The method according to claim 2, wherein the nitrogen source is selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamine plasma, and mixtures thereof.

9. The method according to claim 8, wherein the organic amine is selected from tert-butylamine, dimethylamine, diethylamine, isopropylamine, and mixtures thereof.

10. The method of claim 8, wherein the alkoxyamine plasma is an ethanolamine plasma.

11. The method of claim 2, wherein the nitrogen source comprises an ammonia plasma, a plasma containing nitrogen and argon, a plasma containing nitrogen and helium, or a plasma containing hydrogen and a nitrogen source gas.

12. The method according to claim 1 or 2, wherein water vapor is used as an oxygen source and the substrate temperature is -20°C to 40°C or -10°C to 25°C.

13. The method according to claim 1 or 2, wherein the membrane undergoes a processing step selected from treatment by high-temperature thermal annealing; plasma treatment; ultraviolet (UV) light treatment; laser treatment; electron beam treatment; and combinations thereof.

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