Method for depositing a film

Abstract

An atomic layer deposition method for depositing a film within surface features of a substrate is disclosed. The method may include placing a substrate having surface features in a reactor. An organic passivator can be introduced into the reactor, and the organic passivator can react with a portion of the exposed hydroxyl radicals in the surface features. Subsequently, unreacted organic passivator can be purged, and then a precursor can be introduced. The precursor can react with the remaining exposed hydroxyl radicals that did not interact with the organic passivator. Subsequently, unreacted precursor can be purged, and an oxygen source or a nitrogen source can be introduced into the reactor to form a film within the surface features.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application for patent claims priority to U.S. Provisional Patent Application No. 62 / 954,053, filed December 27, 2019.

[0002] Generally, the present disclosure relates to methods for depositing films, and more particularly to atomic layer deposition methods for depositing films into surface features of a substrate. [Background technology]

[0003] Atomic layer deposition is a chemical process utilized to deposit thin films on substrates. In many instances, substrates undergoing atomic layer deposition processes have one or more of the following high aspect ratio surface features formed thereon: pores, trenches, shallow trench isolation, vias, re-entrant features, or the like. Generally, these high aspect ratio features have openings, top regions, and bottom regions, and films formed thereon should have low porosity.

[0004] In conventional atomic layer deposition, as film growth occurs during gap filling, the opening of the surface feature narrows. Ultimately, the narrowing of the opening prevents reactants from migrating to the lower portion of the surface feature, including both the top and bottom regions. This restriction prevents further film growth within the surface feature, thereby resulting in a film formed within the surface feature with greater than desired porosity.

[0005] U.S. Patent Application Publication No. 2019 / 0203354 discloses a method and system for adjusting the conformality of metal oxide films in atomic layer deposition using chemical inhibition. Inhibitor precursors for metal oxide deposition may include chelating agents such as diketones.

[0006] U.S. Patent Nos. 10,199,212 and 10,043,656 teach a method and apparatus for selectively depositing silicon- or metal-containing dielectric materials onto silicon or metal surfaces, selective to silicon oxide or silicon nitride materials, using acetyl chloride as a blocking agent.

[0007] Accordingly, the present disclosure is directed to overcoming one or more of the above-mentioned problems and / or other problems associated with known atomic layer deposition methods. Summary of the Invention

[0008] According to one aspect of the present invention, an atomic layer deposition method for depositing a film within surface features of a substrate is disclosed. The method may include placing a substrate having surface features in a reactor, the surface features containing exposed hydroxyl radicals. The reactor may be heated to one or more temperatures ranging from ambient temperature to about 700°C and optionally maintained at a pressure of 100 torr or less. An organic passivating agent may then be introduced into the reactor, where the organic passivating agent may react with some of the exposed hydroxyl groups of the surface features.

[0009] The reactor can then be purged of unreacted organic passivating agent using an inert gas, followed by introducing a precursor gas having at least one organic amino group to react with unreacted hydroxyl groups on the surface features. This can then be followed by introducing an inert gas into the reactor to purge the unreacted precursor, and then an oxygen or nitrogen source can be introduced to form a film within the surface features. Finally, the reactor can be purged of unreacted oxygen or nitrogen sources and any by-products using an inert gas. The steps from introducing the organic passivating agent into the surface features to purging the unreacted oxygen or nitrogen sources and by-products from the reactor using an inert gas can be repeated until the surface features are completely filled.

[0010] Generally, the organic passivator can be selected from acetals, ketals, orthoesters, and orthocarbonates. More specifically, the organic passivator can be selected from the group consisting of .... More specifically, the organic passivator can be selected from the group consisting of acetals, ketals, orthoesters. More specifically, the organic passivator IR 1 R 2 C(OR 3 ) an acetal or ketal having the formula: II.R 1 C(OR 3 ) an orthoester having the formula: III.C(OR 3 ) orthocarbonate having the formula 4 (In the formula, R 1 But hydrogen, C1~C 10 Straight or branched alkyl, C3-C containing oxygen or nitrogen 10 Straight or branched chain alkyl, C3-C 10 Straight or branched chain cyclic alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl and C3-C 10 aromatic hydrocarbons, R 2 and R 3 However, C1~C 10 Straight or branched alkyl, C3-C containing oxygen or nitrogen 10 Straight or branched chain alkyl, C3-C 10 Straight or branched chain cyclic alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl and C3-C 10 aromatic hydrocarbons).

[0011] In an exemplary embodiment, the organic passivator is at least one compound selected from the group consisting of tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-propyl orthocarbonate, trimethyl orthoacetate, triethyl orthoacetate, 1,1,1-triethoxypentane, 1,1,1-triethoxyheptane, triethyl orthobenzoate, 2,2-diethoxypropane, 1,1-diethoxy-1-phenylethane, 4,4-diethoxyheptane, 4,4-diethoxynonane, trimethyl orthoformate, trimethyl orthoformate, and tri-n-propyl orthoformate.

[0012] The precursor can be selected from the group consisting of organoaminosilanes, organoaminodisilanes, organoaminotrisilylamines, organoaminosiloxanes, organoaminocyclosiloxanes, organoaminotitaniums, organoaminohafniums, organoaminozirconiums, organoaminotantalums, organoaminotungsten, organoaminomolybdenums, organoaminoaluminums, alkylaluminums, and metal alkoxides. Furthermore, the oxygen source can be selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and an organoamine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof. The nitrogen source can be selected from the group consisting of ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, N2 plasma, ammonia plasma, hydrogen / nitrogen plasma, and combinations thereof.

[0013] The surface features of the present disclosure may have a depth:width aspect ratio of at least 2:1 or greater, or even at least 4:1. In some examples, the surface features have widths of 100 nm or less and may be vias, trenches, or a combination of vias and trenches.

[0014] In some embodiments, the thickness of the film produced at each point after performing the steps from introducing the organic passivating agent into the surface features to purging unreacted oxygen or nitrogen source and by-products from the reactor with an inert gas is greater toward the bottom of the surface features than toward the top of the surface features. DETAILED DESCRIPTION OF THE INVENTION

[0015] Detailed Description of the Invention Described herein are compositions and processes for filling surface features, such as vias or trenches, with silicon- or metal oxide-containing films using atomic layer deposition (ALD) processes or processes similar to ALD, such as, but not limited to, cyclic chemical vapor deposition. According to an exemplary embodiment, a non-silicon-containing passivating agent reacts with exposed hydroxyl groups on the substrate surface features to create "occupied" reactive sites on the surface features. The occupation of the reactive sites then prevents the reaction of the organoaminosilane with the occupied reactive sites, thus preventing film growth in certain areas of the surface features. The dosing of the passivating agent is controlled to limit diffusion of the passivating agent to lower areas of the surface features. Thus, the upper substrate surface and the top of the surface features are more passivated than the bottom of the trench structure, which in turn results in smaller film growth near the upper substrate surface and the top of the surface features, and larger film growth near the bottom of the substrate features. This method of limiting film growth near the upper substrate surface and the top of surface features maintains openings for precursor and oxygen sources to access the underlying spaces within the surface features and completely fill such spaces with the desired film.

[0016] When a passivating agent is not used during film growth, such as in conventional ALD conformal film growth methods, the opening of the surface feature narrows as film growth occurs during gap filling. Eventually, this narrowing prevents penetration to the bottom of the surface feature, which in turn prevents further film growth inside the trench and causes porosity within the surface feature. A similar defect phenomenon is observed when the passivating agent diffuses to the bottom of the trench, resulting in conformal film growth during trench filling.

[0017] One method described by an exemplary embodiment includes: a) placing one or more substrates having hydroxyl groups on their surface and high aspect ratio surface features into a reactor; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing at least one organic passivating agent into the reactor to react with the hydroxyl groups on the top surface regions of the features; d) purging unreacted organic passivating agent using an inert gas; e) introducing vapor of a deposition precursor having at least one organic amino group to react with the unreacted hydroxyl groups; f) purging unreacted precursors using an inert gas; g) introducing an oxygen source precursor; and h) purging with an inert gas Steps c) to h) are repeated until the feature is completely filled.

[0018] Another method described by an exemplary embodiment includes: a) introducing a silicon substrate having a suitable topography into a deposition chamber; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing at least one organic passivating agent into the reactor to react with the hydroxyl groups on the top surface regions of the features; d) purging unreacted organic passivating agent using an inert gas; e) introducing vapor of a deposition precursor having at least one organic amino or halogeno group to react with the non-passivated surface; f) purging unreacted precursors using an inert gas; g) introducing a nitrogen source precursor; and h) purging with an inert gas Includes.

[0019] The organic passivating agent described in this invention has the following formula: IV.R 1 R 2 C(OR 3 ) an acetal or ketal having the formula: VR 1 C(OR 3 ) an orthoester having the formula: VI.C(OR 3 ) orthocarbonate having the formula 4 (In the formula, R 1 But hydrogen, C1~C 10 Straight or branched alkyl, C3-C containing oxygen or nitrogen 10 Straight or branched chain alkyl, C3-C 10 Straight or branched chain cyclic alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl and C3-C 10 aromatic hydrocarbons, R 2 and R 3 However, C1~C 10 Straight or branched alkyl, C3-C containing oxygen or nitrogen 10 Straight or branched chain alkyl, C3-C 10 Straight or branched chain cyclic alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl and C3-C 10aromatic hydrocarbons).

[0020] In one or more embodiments described above, the oxygen source is selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and an organic amine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.

[0021] In one or more of the embodiments described above, the nitrogen source includes, but is not limited to, ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, N2 plasma, ammonia plasma, hydrogen / nitrogen plasma, and combinations thereof.

[0022] Without being bound by theory, it is believed that in step c), the chamber pressure, pulse time or vapor flow of the organic passivating agent, or the R 1~3 It is believed that an organic passivating agent is introduced with tightly controlled group size to react primarily with the hydroxy groups on the top surface region of the feature, and in step e), a deposition precursor having at least one organic amino group reacts with the unreacted hydroxyls on the bottom of the feature to anchor the silicon- or metal-containing fragments. Step g) oxidizes and removes the organic passivating underlayer to regenerate the hydroxyls on the top surface region of the feature while forming a silicon- or metal oxide-containing film on the bottom of the feature, thereby achieving complete deposition of the silicon- or metal oxide-containing film.

[0023] Some exemplary organic passivating agents that can be utilized in the processes described herein are listed in Table 1 below. Table 1: Exemplary Passivators [Table 1]

[0024] Deposition precursors for silicon oxide, silicon nitride, metal nitrides, or metal oxides having at least one organic amino or halogeno group can be selected from the group consisting of organic aminosilanes, organic aminodisilanes, organic aminotrisilylamines, organic aminosiloxanes, organic aminocyclosiloxanes, organic aminotitanium, organic aminohafnium, organic aminozirconium, organic aminotantalum, organic aminotungsten, organic aminomolybdenum, organic aminoaluminum, alkyl aluminum, metal alkoxides, and any other silicon- or metal-containing precursors that can be utilized to deposit silicon oxide, carbon-doped silicon oxide, and metal oxides.

[0025] Examples of organic aminosilanes include, but are not limited to, di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, bis(dimethylamino)silane, bis(ethylmethylamino)silane, bis(tert-butylamino)silane, di-isopropylaminomethylsilane, di-sec-butylaminomethylsilane, dimethylaminodimethylsilane, dimethylaminotrimethylsilane, bis(dimethylamino)methylsilane, tetrakis(dimethylamino)silane, tris(dimethylamino) Silanes include iso-propylaminotrimethylsilane, tert-butylaminotrimethylsilane, iso-butylaminotrimethylsilane, cyclohexylaminotrimethylsilane, pyrrolidinotrimethylsilane, 2-methylpyrrolidinotrimethylsilane, 2,5-dimethylpyrrolidinotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 1-methylpiperazinotrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, and imidazolyltrimethylsilane.

[0026] Examples of organoaminodisilanes include, but are not limited to, di-iso-propylaminodisilane and di-sec-butylaminodisilane.

[0027] Examples of organic aminotrisilylamines include, but are not limited to, di-iso-propylaminotrisilylamine, diethylaminotrisilylamine, iso-propylaminotrisilylamine, and cyclohexylmethylaminotrisilylamine.

[0028] Examples of organoaminosiloxanes include, but are not limited to, 1-dimethylamino-pentamethyldisiloxane, 1-diethylamino-pentamethyldisiloxane, 1-ethylmethylamino-pentamethyldisiloxane, 1,3-bis(dimethylamino)tetramethyldisiloxane, 1-dimethylamino-heptamethyltrisiloxane, and 1,5-bis(dimethylamino)hexamethyltrisiloxane.

[0029] Examples of organic aminocyclosiloxanes include, but are not limited to, 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, siloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2- Includes dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidino-2,4,6,8-tetramethylcyclotetrasiloxane and 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0030] Examples of organoaminotitanium include, but are not limited to, tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium, and tetrakis(ethylmethylamino)titanium.

[0031] Examples of organic aminohafnium compounds include, but are not limited to, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), ), cyclopentadienyl tris(dimethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NMeEt)3), ethylcyclopentadienyl tris(dimethylamino)hafnium (EtCpHf(NMeEt)3), cyclopentadienyl tris(dimethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NEt2)3), ethylcyclopentadienyl tris(dimethylamino)hafnium bis(ethylamino)hafnium (EtCpHf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(di methylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium ((Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NEt2)3), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NEt2)2), (N-methyl-2,[N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino] and bis(ethylmethylamino)hafnium.

[0032] Examples of organic amino zirconium compounds include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyltris(dimethylamino)zirconium (EtCpZr(NMe2) 3), cyclopentadienyl tris(dimethylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyl tris(dimethylamino)zirconium (MeCpZr(NMeEt)3), ethylcyclopentadienyl tris(dimethylamino)zirconium (EtCpZr(NMeEt)3), cyclopentadienyl tris(dimethylamino)zirconium (CpHf(NEt2)3), methylcyclopentadienyl tris(dimethylamino)zirconium (MeCpZr(NEt2)3), ethylcyclopentadienyl tris(di methylamino)zirconium (EtCpZr(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMeEt)2), bis(methylcyclopentadienyl)bis(di methylamino)zirconium ((MeCp)2Zr(NMeEt)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NMeEt)2), bis(cyclopentadienyl)bis(dimethylamino)zirconium ((Cp2Zr(NEt2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NEt2)3), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp)2Zr(NEt2)2), (N-methyl-2,These include (N-ethyl-2,4-cyclopentadiene-1-ethaneamino)bis(dimethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino)bis(dimethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino)bis(diethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino)bis(diethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino)bis(ethylmethylamino)zirconium, and (N-ethyl-2,4-cyclopentadiene-1-ethaneamino)bis(ethylmethylamino)zirconium.

[0033] Examples of organoaminotantalum include, but are not limited to, (tert-butylimino)tris(dimethylamino)tantalum, (tert-butylimino)tris(diethylamino)tantalum, and (tert-butylimino)tris(ethylmethylamino)tantalum.

[0034] Examples of organoaminotungsten include, but are not limited to, bis(tert-butylimino)bis(dimethylamino)tungsten, bis(tert-butylimino)bis(diethylamino)tungsten, and bis(tert-butylimino)bis(ethylmethylamino)tungsten.

[0035] Examples of organoaminomolybdenum include, but are not limited to, bis(tert-butylimino)bis(dimethylamino)molybdenum, bis(tert-butylimino)bis(diethylamino)molybdenum, and bis(tert-butylimino)bis(ethylmethylamino)molybdenum.

[0036] Examples of organoaminoaluminums include, but are not limited to, tris(dimethylamino)aluminum, tris(diethylamino)aluminum, and tris(ethylmethylamino)aluminum.

[0037] Examples of alkylaluminum include, but are not limited to, trimethylaluminum and triethylaluminum.

[0038] Examples of metal oxides include, but are not limited to, titanium isopropoxide, titanium methoxide, titanium ethoxide, and aluminum isopropoxide.

[0039] Examples of halogenosilanes include trichlorosilane, dichlorosilane, monochlorosilane, hexachlorodisilane, N-methyl-1,1,1,3,3,3-hexachlorodisilazane, silicon tetrachloride, 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1, 3-Disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-trisilapentane, 1,1,3,3,5,5-hexachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5-pentachloro-1,3,5 -Trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3,5-trisilapentane, 1-iodo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1,3-triiodo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-diiodo-1,3-dimethyl-1,3-disilacyclobutane, 1,1,1,4,4, 4-Hexachloro-1,4-disilabutane, 1,1,1,4,4,4-hexachloro-2-methyl-1,4-disilabutane, 2,2,5,5,5-pentachloro-2,5-disilapentane, 2,2,5,5,5-pentachloro-3-methyl-2,5-disilapentane, 2,2,5,5-tetrachloro-2,5-disilahexane, 2,2,5,5-tetrachloro-3-methyl-2,5-disilahexane, 1,1,1,5,5,5-hexachloro-1,5-disilapentane, 2,2,6,6-tetrachloro-3-methyl-2,6-disilaheptane, 1,1,4,4-Tetrachloro-1,4-disilapentane, 1,1,4,4-tetrachloro-2-methyl-1,4-disilapentane, 1,1,4,4,4-pentachloro-1,4-disilabutane, 1,1,4,4,4-pentachloro-2-methyl-1,4-disilabutane, 1,4,4,4-tetrachloro-1,4-disilabutane, 1,4,4,4-tetrachloro-2-methyl-1,4-disilabutane, 1,4,4-trichloro-1,4-disilapentane, 1,4,4-trichloro-2-methyl-1,4-disilapentane, 1,1,5,5,5-pentachloro-1,5-disilapentane, 1,1,5,5,5-pentachloro-2-methyl-1,5-disilapentane, 1,1,5,5-tetrachloro- This includes 1,5-disilahexane, 1,1,5,5-tetrachloro-2-methyl-1,5-disilahexane, 1,5,5,5-tetrachloro-1,5-disilapentane, 1,5,5,5-tetrachloro-2-methyl-1,5-disilapentane, 1,5,5-trichloro-1,5-disilahexane, 1,5,5-trichloro-2-methyl-2,6-disilahexane, 1,1,1,3,3,3-hexachloro-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, and 1,1,1,3,3,3-hexachloro-2-ethyl-1,3-disilapropane.

[0040] The substrate comprises surface features. As used herein, the term "surface feature" or "feature" refers to a substrate or partially fabricated substrate comprising one or more of the following: pores, trenches, shallow trench isolation (STI), vias, reentrant features, or the like. In one particular embodiment, the surface feature has a width of 100 μm or less, a width of 1 μm or less, a width of 0.5 μm or less, or a width of 50 nm or less. In this or other embodiments, the aspect ratio (depth:width) of the surface feature, if present, is 2:1 or greater, 3:1 or greater, 4:1 or greater, 10:1 or greater, 20:1 or greater, or 40:1 or greater. A high aspect ratio refers to 2:1 or greater for widths of 100 nm or less, preferably 3:1 or greater for widths of 100 nm or less, and most preferably 4:1 or greater for widths of 100 nm or less. Trench materials include Si, SiO2, SiN x , carbon-doped silicon oxide, or a combination thereof.

[0041] In the formula above and throughout this specification, the term "straight-chain alkyl" refers to a straight-chain functional group having 1 to 10, 3 to 10, or 1 to 6 carbon atoms. In the formula above and throughout this specification, the term "branched-chain alkyl" refers to a straight-chain functional group having 3 to 10, or 1 to 6 carbon atoms. Exemplary straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplary branched-chain alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, an alkyl group may have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or a combination thereof. In other embodiments, an alkyl group does not have one or more functional groups attached thereto. An alkyl group may be saturated or, alternatively, unsaturated.

[0042] As noted above, the methods described herein can be used to deposit silicon oxide or metal oxide on at least a portion of a substrate and within surface features, including vias and / or trenches. Examples of suitable substrates include, but are not limited to, silicon, SiO2, titanium nitride, tungsten nitride, tantalum nitride, vanadium nitride, metals, such as germanium, copper, titanium, tungsten, cobalt, ruthenium, platinum, palladium, aluminum, and combinations thereof.

[0043] The films are compatible with a variety of subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0044] 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), IGZO, and liquid crystal displays (LCDs). [Example]

[0045] Example 1: Inhibition of silicon oxide film growth on trench structures Film deposition was performed in a 300 mm plasma-enhanced atomic layer deposition (PEALD) tool using the FLR design. The reactor consisted of an outer and inner chamber with dedicated pressure control. Ar was flowed through the outer chamber to maintain pressure, while all reactive chemicals for deposition were flowed through the inner chamber. The process and its conditions are shown in Table 2. Table 2: Processes and conditions that inhibit silicon oxide growth [Table 2]

[0046] Steps c through h of the process outlined above can be repeated until the desired thickness is reached.

[0047] Filmtek TM A 3000 reflection and transmission spectrometer was used to measure the thickness and refractive index of the deposited films, while a scanning electron microscope (SEM) and a transmission electron microscope (TEM) were used to investigate the quality of the films.

[0048] Using di-sec-butylaminosilane (DSBAS) as the deposition precursor, O2 plasma as the oxygen source, and triethyl orthoacetate (TEOA) as the organic passivator, blanket silicon oxide films were deposited using the process described in Table 2. TEOA immersion times were varied from 0 s (no TEOA passivator) to 60 s. The susceptor temperature was set to 300 °C.

[0049] When no TEOA soak was used (0 s), the growth per cycle (GPC) was 1.18 Å / cycle, while longer TEOA soak times inhibited the growth of silicon oxide films to 0.16 Å / cycle.

[0050] Growth of silicon oxide films using a 0.5 s TEOA soak time was performed on trench structures with a 10:1 aspect ratio and 150 nm openings. The TEOA exposure time was selected in a semi-wet mode, so that the passivator exposure at the top of the trench was greater than that at the bottom of the trench. The semi-wet mode can vary depending on the type of ALD reactor and should be obtained by experiments similar to those in this example for a given ALD reactor.

[0051] The TEM measurements of the thickness of the deposited silicon oxide film at different positions in the trench are shown in Table 3. Table 3: Thickness of SiO2 films deposited for trench structures with 10:1 aspect ratio [Table 3]

[0052] The film thickness at the top is thinner than that at the bottom, indicating that TEOA prevents film deposition at the top portion of the trench structure, allowing complete gap filling when shorter TEOA exposure times are used.

[0053] Example 2: Blocking the growth of SiNx deposited using N2 plasma for trench structures Film deposition was performed in a 300 mm PEALD tool using the FLR design. The reactor consisted of an outer and inner chamber with dedicated pressure control. Ar was flowed through the outer chamber to maintain pressure, while all reaction chemicals for deposition were flowed through the inner chamber. The process and its conditions are shown below in Table 4. Table 4: Process and conditions for blocking SiNx growth [Table 4]

[0054] In this process, steps 3 to 9 can be repeated until the desired thickness is achieved.

[0055] In this example, di-sec-butylaminosilane (DSBAS) was used as the silicon precursor. Triethyl orthoacetate (TEOA) was used as the organic blocker, with a flow time of 0-10 seconds. Filmtek TM The thickness and refractive index of the deposited films were measured using a 3000 reflection and transmission instrument.

[0056] Table 5 below shows the effect of TEOA on reducing the GPC of SiNx films. Table 5 shows that after 10 seconds of TEOA exposure in each cycle, the film growth decreased to 0.06 Å / cycle. This is ~45% lower GPC than films grown without TEOA passivation, demonstrating the dose sensitivity of the passivation process. Table 5: GPC of SiNx film growth after TEOA exposure [Table 5]

[0057] A TEOA soak time of 0.5 s was used to fabricate silicon nitride (SiN) trench structures with a 10:1 aspect ratio and 150 nm openings. x The growth of the TEOA film was investigated. The TEOA exposure time was selected in a semi-wet mode. Therefore, the exposure of the passivator at the top of the trench was greater than that at the bottom of the trench.

[0058] TEM measurements of the thickness of the deposited silicon nitride film at different positions in the trench are shown in Table 6. Table 6: SiN deposited for trench structures with 10:1 aspect ratio x Film thickness [Table 6]

[0059] The film thickness at the top was thinner than that at the bottom, indicating that TEOA prevented film deposition at the top portion of the trench structure, allowing complete gap filling when shorter TEOA exposure times were used.

[0060] Example 3: Growth of silicon oxide films on trench structures without passivation agents Film deposition was performed in a 300 mm plasma-enhanced atomic layer deposition (PEALD) tool using the FLR design. The reactor consisted of an outer and inner chamber with dedicated pressure control. Ar was flowed through the outer chamber to maintain pressure, while all reactive chemicals for deposition were flowed through the inner chamber. The process and its conditions are shown in Table 7. Table 7: Process and conditions for growth of silicon oxide films without passivation agents. [Table 7] Steps c to f can be repeated multiple times to fill the gap.

[0061] In this example, silicon oxide was deposited using di-sec-butylaminosilane (DSBAS) as the deposition precursor and O2 plasma as the oxygen source, utilizing the process and conditions described above in Table 7.

[0062] The TEM measurements of the deposited silicon oxide films at different locations are shown in Table 8 below. Table 8: Thickness of SiO2 films deposited for trench structures with aspect ratios of 10:1 [Table 8]

[0063] As shown above in Table 8, films deposited without a passivator have conformal film deposition.

[0064] Example 4: Growth of a film into a trench structure using long-term passivator exposure The process and conditions in this example were the same as those outlined in Table 2 above, except for the organic passivator soak time. A blanket film of silicon oxide was deposited using di-sec-butylaminosilane (DSBAS) as the deposition precursor, O2 plasma as the oxygen source, and triethyl orthoacetate as the organic passivator. The TEOA soak time was selected to be 5 seconds.

[0065] TEM measurements of the thickness of the deposited films at different positions in the trench are shown in Table 9. Table 9: Thickness of silicon oxide films deposited for trench structures of 10:1 [Table 9]

[0066] The film thickness at the top is similar to that at the bottom, indicating conformal deposition, suggesting that longer exposure times of the passivator may not be suitable for complete filling as it reacts with the surfaces within the trench and reacts uniformly at both the top and bottom.

[0067] The above description is meant to be merely exemplary, and thus modifications can be made to the embodiments described herein without departing from the scope of the disclosure. Accordingly, these modifications are intended to be within the scope of the disclosure and within the scope of the appended claims. The following embodiments can be given as examples of the present invention. (Appendix 1) 1. An atomic layer deposition method for depositing a film within a surface feature of a substrate, comprising: a) placing a substrate having surface features in a reactor, the surface features having exposed hydroxyl radicals; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing at least one organic passivating agent selected from the group consisting of acetals, ketals, orthoesters, and orthocarbonates into the reactor to react with a portion of the exposed hydroxyl groups of the surface features; d) purging the reactor of unreacted organic passivating agent using an inert gas; e) introducing a precursor gas having at least one organic amino group to react with any unreacted hydroxyl groups on said surface features; f) purging unreacted precursor from the reactor using an inert gas; g) introducing a source of oxygen or a source of nitrogen into the reactor; and h) purging unreacted oxygen or nitrogen source and any by-products with an inert gas; wherein steps c) through h) are repeated until the surface features are completely filled. (Appendix 2) The organic passivator has the following formula: IR 1 R 2 C(OR 3 ) 2 an acetal or ketal having the formula II.R 1 C(OR 3 ) 3 an orthoester having the formula: III.C(OR 3 ) 4 Orthocarbonate having the formula (In the formula, R 1 But hydrogen, C 1 ~C 10 Straight or branched alkyl, oxygen or nitrogen containing C 3 ~C 10 Straight or branched chain alkyl, C 3 ~C 10 Linear or branched cyclic alkyl, C 2 ~C 10 Alkenyl, C 2 ~C 10 Alkynyl and C 3 ~C 10 aromatic hydrocarbons, R 2 and R 3 But C 1 ~C 10 Straight or branched alkyl, oxygen or nitrogen containing C 3 ~C 10 Straight or branched chain alkyl, C 3 ~C 10 Linear or branched cyclic alkyl, C 2 ~C 10 Alkenyl, C 2 ~C 10 Alkynyl and C 3 ~C 10 2. The method of claim 1, wherein the hydrocarbon is selected from the group consisting of: (Appendix 3) 3. The method of claim 2, wherein the organic passivator comprises at least one compound selected from the group consisting of tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-propyl orthocarbonate, trimethyl orthoacetate, triethyl orthoacetate, 1,1,1-triethoxypentane, 1,1,1-triethoxyheptane, triethyl orthobenzoate, 2,2-diethoxypropane, 1,1-diethoxy-1-phenylethane, 4,4-diethoxyheptane, 4,4-diethoxynonane, trimethyl orthoformate, trimethyl orthoformate, and tri-n-propyl orthoformate. (Appendix 4) 4. The method of claim 3, wherein the organic passivator comprises triethyl orthoacetate. (Appendix 5) 2. The method of claim 1, wherein the precursor is selected from the group consisting of organoaminosilanes, organoaminodisilanes, organoaminotrisilylamines, organoaminosiloxanes, organoaminocyclosiloxanes, and organoaminotitanium, organoaminohafnium, organoaminozirconium, organoaminotantalum, organoaminotungsten, organoaminomolybdenum, organoaminoaluminum, alkylaluminum, and metal alkoxides. (Appendix 6) 2. The method of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and an organic amine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof. (Appendix 7) The nitrogen source is ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, N 2 2. The method of claim 1, wherein the plasma is selected from the group consisting of plasma, ammonia plasma, hydrogen / nitrogen plasma, and combinations thereof. (Appendix 8) 2. The method of claim 1, wherein the surface features have a depth:width aspect ratio of at least 2:1 or greater. (Appendix 9) 9. The method of claim 8, wherein the aspect ratio is at least 4:1. (Appendix 10) 9. The method of claim 8, wherein the surface features have a width of 100 nm or less. (Appendix 11) 2. The method of claim 1, wherein the surface feature is a via. (Appendix 12) 2. The method of claim 1, wherein the surface feature is a trench. (Appendix 13) 2. The method of claim 1, wherein the surface features are vias and trenches. (Appendix 14) 2. The method of claim 1, wherein the film produced at each point after steps c) through h) is thicker toward the bottom of the surface feature than toward the top of the surface feature.

Claims

1. 1. An atomic layer deposition method for depositing a film within a surface feature of a substrate, comprising: a) placing a substrate having surface features in a reactor, said surface features having exposed hydroxyl radicals; b) heating the reactor to one or more temperatures ranging from ambient temperature to about 700°C, and optionally maintaining the reactor at a pressure of 100 torr or less; c) introducing into the reactor at least one organic passivating agent comprising at least one compound selected from the group consisting of tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-propyl orthocarbonate, trimethyl orthoacetate, triethyl orthoacetate, 1,1,1-triethoxypentane, 1,1,1-triethoxyheptane, triethyl orthobenzoate, 2,2-diethoxypropane, 1,1-diethoxy-1-phenylethane, 4,4-diethoxyheptane, 4,4-diethoxynonane, trimethyl orthoformate, triethyl orthoformate, and tri-n-propyl orthoformate; d) purging the reactor of unreacted organic passivating agent using an inert gas; e) di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, bis(dimethylamino)silane, bis(ethylmethylamino)silane, bis(tert-butylamino)silane, di-isopropylaminomethylsilane, di-sec-butylaminomethylsilane, dimethylaminodimethylsilane, dimethylaminotrimethylsilane, bis(dimethylamino)methylsilane, tetrakis(dimethylamino)silane, tris(dimethylamino)silane, isopropylaminotrimethylsilane, tert-butylamino Isotrimethylsilane, isobutylaminotrimethylsilane, cyclohexylaminotrimethylsilane, pyrrolidinotrimethylsilane, 2-methylpyrrolidinotrimethylsilane, 2,5-dimethylpyrrolidinotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 1-methylpiperazinotrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, diisopropylaminodisilane, di-sec-butylaminodisilane, diisopropylaminodisilane Aminotrisilylamine, diethylaminotrisilylamine, isopropylaminotrisilylamine, cyclohexylmethylaminotrisilylamine, 1-dimethylamino-pentamethyldisiloxane, 1-diethylamino-pentamethyldisiloxane, 1-ethylmethylamino-pentamethyldisiloxane, 1,3-bis(dimethylamino)tetramethyldisiloxane, 1-dimethylamino-heptamethyltrisiloxane, 1,5-bis(dimethylamino)hexamethyltrisiloxane, 2-dimethylamino-2,4,4,6,6-pentamethylcyclohexyl siloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane,2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2 -iso-propylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium, tetrakis(ethylmethylamino)titanium, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2)3), methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyl tris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyl tris(dimethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NMeEt)3), ethylcyclopentadienyl tris(dimethylamino)hafnium (EtCpHf(NMeEt)3), cyclopentadienyl tris(dimethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyl tris(dimethylamino)hafnium (MeCpHf(NEt2)3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NEt 2 ) 3 ),Bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)hafnium [N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(ethylmethylamino)hafnium, [N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(ethylmethylamino)hafnium, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyltris(dimethylamino)zirconium (CpZr(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)zirconium (MeCpZr(NMe 2 ) 3 ),Ethylcyclopentadienyl tris(dimethylamino)zirconium (EtCpZr(NMe2)3), cyclopentadienyl tris(dimethylamino)zirconium (CpZr(NMeEt)3), methylcyclopentadienyl tris(dimethylamino)zirconium (MeCpZr(NMeEt)3), ethylcyclopentadienyl tris(dimethylamino)zirconium (EtCpZr(NMeEt)3), cyclopentadienyl tris(dimethylamino)zirconium (CpHf(NEt2)3), methylcyclopentadienyl tris(dimethylamino)zirconium (MeCpZr(NEt2)3), ethylcyclopentadienyl tris(dimethylamino)zirconium (EtCpZr(NEt2)3 ), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp 2 Zr(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp) 2 Zr(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp) 2 Zr(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp 2 Zr(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp) 2 Zr(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(dimethyl, bis(dimethylamino)zirconium ((EtCp) 2 Zr(NMeEt) 2 ), bis(cyclopentadienyl)bis(dimethylamino)zirconium ((Cp 2 Zr(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp) 2 Zr(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((EtCp) 2 Zr(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(dimethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(diethylamino)zirconium, (N-methyl-2,4-cyclopentadiene-1-ethaneamino]bis(ethylmethylamino)zirconium, (N-ethyl-2,4-cyclopentadiene-1-ethaneamino]bis(ethylmethylamino)zirconium, (tert-butylimino)tris(dimethylamino)tantalum, (tert-butylimino)tris(diethylamino)tantalum, (te introducing a precursor gas having at least one organic amino group selected from the group consisting of bis(tert-butylimino)tris(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten, bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, bis(tert-butylimino)bis(dimethylamino)molybdenum, bis(tert-butylimino)bis(diethylamino)molybdenum, bis(tert-butylimino)bis(ethylmethylamino)molybdenum, tris(dimethylamino)aluminum, tris(diethylamino)aluminum, and tris(ethylmethylamino)aluminum to react with any unreacted hydroxyl groups on the surface features; f) purging the reactor of unreacted precursors using an inert gas; g) introducing an oxygen source or a nitrogen source into the reactor; and h) purging unreacted oxygen or nitrogen source and any by-products with an inert gas; wherein steps c) through h) are repeated until the surface features are completely filled.

2. The method of claim 1 , wherein the organic passivator comprises triethyl orthoacetate.

3. 10. The method of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and an organic amine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.

4. The nitrogen source is ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, N 2 10. The method of claim 1, wherein the plasma is selected from the group consisting of ammonia plasma, hydrogen / nitrogen plasma, and combinations thereof.

5. The method of claim 1 , wherein the surface features have a depth:width aspect ratio of at least 2:1 or greater.

6. The method of claim 5 wherein the aspect ratio is at least 4:

1.

7. The method of claim 5 , wherein the surface features have a width of 100 nm or less.

8. The method of claim 1 , wherein the surface feature is a via.

9. The method of claim 1 , wherein the surface feature is a trench.

10. The method of claim 1 , wherein the surface features are vias and trenches.

11. 10. The method of claim 1, wherein the film produced at each point after steps c) through h) is thicker toward the bottom of the surface feature than toward the top of the surface feature.

Images