Composition for non-conformal deposition of silicon-containing films and method of using the same

Abstract

An atomic layer deposition method for depositing a non-conformal silicon and oxygen containing film into surface features including vias and / or trenches on one or more substrates.

Description

[0001] Cross-referencing of related patent applications

[0002] This application claims the benefit of U.S. Application No. 62 / 898047, filed September 10, 2019. The disclosure of Application No. 62 / 898047 is incorporated herein by reference. Technical Field

[0003] This document describes compositions and methods for manufacturing electronic devices. More specifically, it describes compounds for nonconformally depositing silicon oxide films on semiconductor features, or for completely filling semiconductor features, including vias and / or trenches, with silicon- or metal oxide films without defects, and compositions and methods comprising such compounds. Background Technology

[0004] There is a need in the art for compositions for depositing silicon- or metal oxide films or combinations thereof to fill openings on high aspect ratio features on a semiconductor substrate, as well as methods and deposition techniques using said compositions and employing chemical inhibition.

[0005] US Patent Publication US20190203354 discloses a method and system for using chemical inhibition to conformally modulate metal oxide films in atomic layer deposition (ALD) processes. The inhibitory precursor used for metal oxide deposition may include chelating agents, such as diketones.

[0006] U.S. Patent Nos. US10199212 and US10043656 disclose methods and apparatus for selectively depositing silicon-containing or metal-containing dielectric materials on silicon or metal surfaces that are selective to silicon oxide or silicon nitride materials. Acetyl chloride is used as a sealing agent. Summary of the Invention

[0007] The compositions and methods described herein overcome the problems of the prior art by providing compositions and methods for depositing non-conformal silicon oxide or depositing silicon-containing / metal oxide films to fill features including vias and / or trenches on features including vias and / or trenches. Film deposition is performed using a typical atomic layer deposition (ALD) method, which includes:

[0008] a. Place one or more substrates having hydroxyl groups on their surface and having features including through holes and / or trenches into the reactor, and heat the reactor to one or more temperatures in the range of ambient temperature to about 700°C, and optionally maintain the reactor at a pressure of 100 Torr or less.

[0009] b. Introduce into the reactor a reactor having the formula R 1 R 2 R 3 The first precursor of SiX(I), where R 1 R2 R 3 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C2-C 10 alkenyl, C2-C 10 alkynyl and C4-C 10 Aryl; X is a nitrogen-containing heteroatom cyclic group that preferentially reacts with those hydroxyl groups on the characteristic top surface region;

[0010] c. Purge the unreacted first precursor with an inert gas;

[0011] d. Introducing an oxygen source; and

[0012] e. Use an inert gas to purge unreacted oxygen sources and byproducts;

[0013] Steps b through e are repeated until the feature is covered by non-conformal silicon oxide.

[0014] In one or more of the above embodiments, the oxygen source is selected from oxygen, oxygen plasma, water vapor plasma, a mixture of water and organic amines, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof. Attached Figure Description

[0015] Figure 1 TEM images of a non-conformal silicon oxide film grown in a trench at 600°C using pyrrolithic trimethylsilane (16-second precursor pulse time) as described in Example 2 are shown, illustrating the non-conformal silicon oxide in the trench, i.e., thicker at the top and thinner in the middle and bottom of the trench from the left TEM image to the right TEM image. Detailed Implementation

[0016] This article describes compositions and methods relating to filling vias or trenches with films containing silicon or metal oxides in atomic layer deposition (ALD) or ALD-like processes, such as, but not limited to, cyclic chemical vapor deposition (CCVD). In this invention, a first precursor having at least one nitrogen-containing heteroatom cyclic group selected from pyrrole, substituted pyrrole, 2-pyrrolinyl, substituted pyrrolinyl, imidazolyl, substituted imidazolyl, 2-imidazolinyl, substituted 2-imidazolinyl, pyrazolyl, substituted pyrazolyl, 1,2,3-triazolyl, 2-pyrazolyl, substituted pyrazolyl, 1,4-dihydropyridyl, substituted 1,4-dihydropyridyl, 1,2-dihydropyridyl, substituted 1,2-dihydropyridyl, 1,2,3,4-tetrahydropyridyl, and substituted 1,2,3,4-tetrahydropyridyl is used to react with exposed surface hydroxyl groups on the substrate, and preferentially reacts with hydroxyl groups on the top surface regions of features of the substrate, such as vias and trench surface features, and thus provides non-conformal deposition of silicon oxide on said features. The term "substituted" refers to the substitution of one or more hydrogen atoms in a cyclic group with one or more alkyl groups such as methyl, ethyl, isopropyl, and n-propyl. The dosage of the first precursor will be controlled to limit diffusion to the bottom of the feature. Therefore, more of the first precursor will be deposited on the substrate surface and the top portion of the feature than on the bottom portion, allowing for higher film growth near the surface of the feature and lower film growth near the bottom. This method of limiting film growth at the lower regions of trenches or other features allows openings to be reserved for the second precursor and oxygen source to completely fill the gaps with the film of interest. Without being bound by any theory, it is believed that due to the delocalization of electrons in the C=CN-Si bonds, the Si-N bonds in the first precursor having at least one C=C bond connected to a nitrogen atom are much stronger than those in the precursor without any C=C bonds connected to a nitrogen atom, making those precursors much less reactive to hydroxyl groups and therefore preferably reacting more with hydroxyl groups positioned towards the top of the feature.

[0017] When no passivating agent is used during film growth in the trenches, as in typical ALD conformal film growth, the openings at or near the substrate surface narrow as film growth proceeds during gap filling. Ultimately, this will prevent further film growth within the trenches and lead to increased porosity.

[0018] In one embodiment, the method for non-conformal silicon oxide deposition on a substrate having features, as described in this invention, includes:

[0019] a. Place one or more substrates having hydroxyl groups on their surface and having features including through holes and / or trenches into the reactor, and heat the reactor to one or more temperatures in the range of ambient temperature to about 700°C, and optionally maintain the reactor at a pressure of 100 Torr or less.

[0020] Introduce into the reactor a reactor with formula R 1 R 2 R 3 The first precursor of SiX(I), where R 1 R 2 R 3 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C2-C 10 alkenyl, C2-C 10 alkynyl and C4-C 10 Aryl; X is a nitrogen-containing heteroatom cyclic group that preferentially reacts with those hydroxyl groups on the characteristic top surface region;

[0021] c. Purge the unreacted first precursor with an inert gas;

[0022] d. Introducing an oxygen source; and

[0023] e. Use an inert gas to purge unreacted oxygen sources and byproducts;

[0024] Steps b through e are repeated until the feature is covered by non-conformal silicon oxide.

[0025] In another embodiment, the method described in this invention for filling interstices in silicon oxide or metal oxide on a substrate having features includes:

[0026] a. Place one or more substrates having hydroxyl groups on their surface and having features including through holes and / or trenches into the reactor, and heat the reactor to one or more temperatures in the range of ambient temperature to about 700°C, and optionally maintain the reactor at a pressure of 100 Torr or less.

[0027] b. Introduce into the reactor a reactor having the formula R 1 R 2 R 3 The first precursor of SiX(I), where R 1 R 2 R 3 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C2-C 10 alkenyl, C2-C 10 alkynyl and C4-C 10 Aryl; X is a nitrogen-containing heteroatom cyclic group that preferentially reacts with those hydroxyl groups on the characteristic top surface region;

[0028] c. Purge the unreacted first precursor with an inert gas;

[0029] d. Introduce the vapor of a second precursor having at least one organic amino group to react with those unreacted hydroxyl groups;

[0030] e. Purge unreacted precursors with an inert gas;

[0031] f. Introducing an oxygen source; and

[0032] g. Use an inert gas to purge unreacted oxygen sources and byproducts;

[0033] Steps b to g are repeated until the feature is filled from bottom to top. In some embodiments, R 1 R 2 R 3 At least one of them is selected from linear C6 to C16. 10 Alkyl, branched C6 to C 10 Alkyl, C6 to C 10 cycloalkyl, C4 to C 10 Heterocyclic groups, C2 to C 10 alkenyl, C2 to C 10 alkynyl and C4 to C 10 Aryl groups provide a larger footprint when reacting with hydroxyl groups on the feature surface, thus making it difficult for those precursors to enter small vias or trenches. At the same time, selecting a second precursor with a smaller molecular size to react with hydroxyl groups inside the vias or trenches promotes better bottom-up filling.

[0034] In Formula I and throughout this 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, n-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 groups such as methoxy, ethoxy, isopropoxy, and n-propoxy, dialkylamino groups such as dimethylamino, or combinations thereof. 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.

[0035] Throughout the foregoing and the entire specification, the term "inert gas" refers to an inert gas selected from helium, argon, neon, nitrogen, and combinations thereof. In some embodiments, the inert gas used in the purging steps (i.e., c, e, or g) is the same. In other embodiments, the inert gas used in the purging steps (i.e., c, e, or g) may be different.

[0036] Throughout the foregoing and the entire specification, the term "hydroxyl group" refers to a hydroxyl group present on an existing surface or generated by the substrate during the process. 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.

[0037] In Formula I above and throughout this 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.

[0038] In Formula I above and throughout the specification, the term "nitrogen-containing heteroatom cyclic group" refers to a C3 to C4 group having at least one C=C bond directly connected to a nitrogen atom. 10 Heterocyclic groups. Exemplary nitrogen-containing heteroatom cyclic groups include, but are not limited to, pyrrole, substituted pyrrole, 2-pyrrolinyl, substituted pyrrolinyl, imidazolyl, substituted imidazolyl, 2-imidazolyl, substituted 2-imidazolyl, pyrazolyl, substituted pyrazolyl, 1,2,3-triazolyl, 2-pyrazolyl, substituted pyrazolyl, 1,4-dihydropyridyl, substituted 1,4-dihydropyridyl, 1,2-dihydropyridyl, substituted 1,2-dihydropyridyl, 1,2,3,4-tetrahydropyridyl, and substituted 1,2,3,4-tetrahydropyridyl. Examples of such groups include 3-methylpyrrolithyl, 2-methylpyrrolithyl, 3,4-dimethylpyrrolithyl, 3-ethylpyrrolithyl, 2,5-dimethylpyrrolithyl, 2,4-dimethylpyrrolithyl, 2,3-dimethylpyrrolithyl, 2,3-dihydro-3-methylpyrrolithyl, 2,3-dihydro-5-methyl-1h-pyrrolithyl, 3,4-dihydro-4-methylpyrrolithyl, 2,3-dihydro-2,2-dimethylpyrrolithyl, 2,3-dihydro-3,5-dimethylpyrrolithyl, 2-methylimidazolyl, 4-methylimidazolyl, 2-ethylimidazolyl, 2,4-dimethylimidazolyl, and 4,5-dimethylimidazolyl. The group includes 2-methylimidazolinyl, 4-methyl-2-imidazolinyl, 4,4-dimethyl-2-imidazolinyl, 4-methylpyrazolyl, 5-methylpyrazolyl, 3-methylpyrazolyl, 5-methyl-1,2,3-triazolyl, 4,5-dimethyl-1,2,3-triazolyl, 4-methyl-4,5-dihydropyrazolyl, 5-methyl-2-pyrazolyl, 3-methyl-2-pyrazolyl, 1,4-dihydro-4-methylpyridinyl, 1,4-dihydro-2-methylpyridinyl, 1,2,3,4-tetrahydro-5-methylpyridinyl, and 1,2,3,4-tetrahydro-5,6-dimethylpyridinyl.

[0039] Table 1 lists non-limiting examples of nitrogen-containing heteroatom cyclic groups that can be bonded to silicon atoms to form silicon precursors as first precursors.

[0040]

[0041]

[0042] Table 1. Non-limiting examples of nitrogen-containing heteroatom cyclic groups

[0043] In Formula I above and throughout the specification, the term "alkenyl" means a group having one or more carbon-carbon double bonds and having 2 to 10, 2 to 8, or 2 to 6 carbon atoms.

[0044] In Formula I above and throughout the specification, the term "alkynyl" means a group having one or more carbon-carbon triple bonds and having 2 to 10, 2 to 8, or 2 to 6 carbon atoms.

[0045] In Formula I above and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 3-10 carbon atoms or 6-10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0046] The first precursor has at least one linker to a chemical formula R. 1 R 2 R 3 The C=C bond of the nitrogen atom in the organoaminosilane of SiX(I), where R 1 R 2 R 3 Each is independently selected from hydrogen, straight-chain C1-C 10 Alkyl, branched C3-C 10 Alkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic group, C2-C 10 alkenyl, C2-C 10 alkynyl and C4-C 10 Aryl group; X is selected from pyrrole, substituted pyrrole, 2-pyrrolinyl, substituted pyrrolinyl, imidazolyl, substituted imidazolyl, 2-imidazolyl, substituted 2-imidazolyl, pyrazolyl, substituted pyrazolyl, 2-pyrazolyl, substituted pyrazolyl, 1,2,3-triazolyl, 1,4-dihydropyridyl, substituted 1,4-dihydropyridyl, 1,2-dihydropyridyl, and substituted 1,2-dihydropyridyl. In some embodiments, R 1 R 2 and R 3All are methyl groups; therefore, silicon precursors are suitable for non-conformal heating or plasma-enhanced ALD silicon oxide at temperatures of 500°C or higher, preferably 550°C or higher, because Si-Me is more stable than Si-H or Si-Et. Examples of the first precursor include, but are not limited to, pyrrolyltrimethylsilane, pyrrolyldimethyloctylsilane, 2,5-dimethylpyrrolyltrimethylsilane, 2-pyrrololinyltrimethylsilane, imidazolyltrimethylsilane, 2-imidazolinyltrimethylsilane, pyrrolyltrimethylsilane, 1,2,3-triazolyltrimethylsilane, and 2-pyrrolyltrimethylsilane.

[0047] The second precursor for silicon oxide or metal oxide having at least one organic amino group may be selected from organic amino silanes, organic amino ethoxysilanes, organic amino trimethylsilylamines, organic amino siloxanes, organic amino cyclosiloxanes, and organic amino titanium, organic amino hafnium, organic amino zirconium, organic amino tantalum, organic amino tungsten, organic amino molybdenum, organic amino aluminum, alkyl aluminum, metal alkoxides, and any other silicon or metal precursor that may be used to deposit silicon oxide, carbon-doped silicon oxide, or metal oxide.

[0048] Examples of organoaminosilanes include, but are not limited to, diisopropylaminosilane, disec-butylaminosilane, bis(diethylamino)silane, bis(dimethylamino)silane, bis(ethylmethylamino)silane, bis(tert-butylamino)silane, diisopropylaminomethylsilane, disec-butylaminomethylsilane, dimethylaminodimethylsilane, dimethylaminotrimethylsilane, bis(dimethylamino)methylsilane, tetra(dimethylamino)silane, tri(dimethylamino)silane, etc. Isopropylaminotrimethylsilane, tert-butylaminotrimethylsilane, isobutylaminotrimethylsilane, cyclohexaneaminotrimethylsilane, pyrrolyltrimethylsilane, 2-methylpyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, piperidinyltrimethylsilane, 2,6-dimethylpiperidinyltrimethylsilane, 1-methylpiperazinyltrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, and imidazolyltrimethylsilane.

[0049] Examples of organic aminosilanes include, but are not limited to, diisopropylaminosilane and disec-butylaminosilane.

[0050] Examples of organic aminotrimethylsilylamines include, but are not limited to, diisopropylaminotrimethylsilylamine, diethylaminotrimethylsilylamine, isopropylaminotrimethylsilylamine, and cyclohexylmethylaminotrimethylsilylamine.

[0051] 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.

[0052] Examples of organoaminocyclosiloxanes 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, 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, and 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane. Oxyalkane, 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, and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0053] Examples of organic amino titanium include, but are not limited to, tetra(dimethylamino)titanium, tetra(diethylamino)titanium, and tetra(ethylmethylamino)titanium.

[0054] Examples of organic amino hafnium include, but are not limited to, tetra(dimethylamino)hafnium (TDMAH), tetra(diethylamino)hafnium (TDEAH), tetra(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe2)3), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMeEt)3), and methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMeEt)3). 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 (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 Hafnium((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium(Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(dimethylamino)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-2,4-cyclopentadien-1-ethylamino)bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadien-1-ethylamino)bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadien-1-ethylamino)bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadien-1-ethylamino)bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadien-1-ethylamino)bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadien-1-ethylamino)bis(ethylmethylamino)hafnium.

[0055] Examples of organic aminozirconium include, but are not limited to, tetra(dimethylamino)zirconium (TDMAZ), tetra(diethylamino)zirconium (TDEAZ), tetra(ethylmethylamino)zirconium (TEMAZ), cyclopentadienyl tri(dimethylamino)zirconium (CpZr(NMe2)3), methylcyclopentadienyl tri(dimethylamino)zirconium (MeCpZr(NMe2)3), ethylcyclopentadienyl tri(dimethylamino)zirconium (EtCpZr(NMe2)3), cyclopentadienyl tri(dimethylamino)zirconium (CpZr(NMeEt)3), and methylcyclopentadienyl tri(dimethylamino)zirconium (MeCpZr(NMeEt)3). 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 (Cp2Zr(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium ((MeCp)2Zr(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium Bis(cyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMeEt)2), Bis(methylcyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMeEt)2), Bis(methylcyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NMeEt)2), Bis(ethylcyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NEt2)2), Bis(methylcyclopentadienyl)bis(dimethylamino)zirconium (Cp2Zr(NEt2)3), Bis(ethyl ... (Dimethylamino)zirconium ((EtCp))2Zr(NEt2)2), (N-methyl-2,4-cyclopentadien-1-ethylamino]bis(dimethylamino)zirconium, (N-ethyl-2,4-cyclopentadien-1-ethylamino]bis(dimethylamino)zirconium, (N-methyl-2,4-cyclopentadien-1-ethylamino]bis(diethylamino)zirconium, (N-ethyl-2,4-cyclopentadien-1-ethylamino]bis(diethylamino)zirconium, (N-methyl-2,4-cyclopentadien-1-ethylamino]bis(ethylmethylamino)zirconium, (N-ethyl-2,4-cyclopentadien-1-ethylamino]bis(ethylmethylamino)zirconium, (N-ethyl-2,4-cyclopentadien-1-ethylamino]bis(ethylmethylamino)zirconium.

[0056] Examples of organic amino tantalum include, but are not limited to, (tert-butylimino)tris(dimethylamino)tantalum, (tert-butylimino)tris(diethylamino)tantalum and (tert-butylimino)tris(ethylmethylamino)tantalum.

[0057] Examples of organic amino tantalum 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.

[0058] Examples of organic aminomolybdenum 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.

[0059] Examples of organic aminoaluminum include, but are not limited to, tris(dimethylamino)aluminum, tris(diethylamino)aluminum, and tris(ethylmethylamino)aluminum.

[0060] Examples of alkyl aluminum include, but are not limited to, trimethylaluminum, triethylaluminum, tri-tert-butylaluminum (TTBA), bis(2-methyl-2-propyl)-(2-methyl-1-propyl)aluminum, (2-methyl-2-propyl)bis(2-methyl-1-propyl)aluminum, tri(2-methyl-1-propyl)aluminum, and tri(neopentyl)aluminum.

[0061] Examples of metal oxides include, but are not limited to, titanium isopropoxide, titanium methanol, titanium ethanol, and aluminum isopropoxide.

[0062] In some implementations, directional dry etching can be performed before the introduction of the second precursor to remove some of the as-deposited silicon oxide from the bottom of the feature, in order to promote better bottom-up filling, especially for metal oxides.

[0063] In some embodiments, the substrate includes surface features. As used herein, the term "surface feature" or "feature" means a substrate or a portion thereof comprising one or more of the following: apertures, trenches, shallow trench isolation (STI), vias, recessed features, etc. In one particular embodiment, the surface feature has a width of 100 μm or less, 1 μm or less, 0.5 μm or less, or 50 nm or less. In this or other embodiments, the aspect ratio (depth to width ratio) of the surface feature (if present) is 2:1 or greater, or 3:1 or greater, or 4:1 or greater, or 10:1 or greater, or 20:1 or greater, or 40:1 or greater. A high aspect ratio means 2:1 or greater, wherein the width is 100 nm or less, preferably 3:1 or greater, wherein the width is 100 nm or less, and most preferably 4:1 or greater, wherein the width is 100 nm or less. The trench material may be selected from Si, SiO2, SiN. x Carbon-doped silicon oxide or a combination thereof.

[0064] In the above formula and throughout the specification, the term "linear alkyl" refers to a linear functional group having 1-10, 3-10, or 1-6 carbon atoms. In the above formula and throughout the specification, the term "branched alkyl" refers to a linear functional group having 3 to 10 or 1 to 6 carbon atoms. Exemplary linear 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 connected thereto, such as, but not limited to, alkoxy, dialkylamino, or combinations thereof. In other embodiments, the alkyl group does not have one or more functional groups connected thereto. The alkyl group may be saturated or unsaturated.

[0065] As previously described, the methods described herein can be used to deposit silicon oxide or metal oxides into surface features including vias and / or trenches on at least a portion of a substrate. 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.

[0066] The film is compatible with a variety of subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0067] 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).

[0068] Working Example

[0069] General film deposition

[0070] Atomic layer deposition of silicon oxide films was performed using the following precursor: pyrrolotrimethylsilane. 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 reaction gases or precursor and oxygen source) were preheated to 100°C before entering the deposition zone. Gas and precursor flow rates were controlled using an ALD diaphragm valve with high-speed actuation. The substrate used for deposition was a 12-inch silicon strip. For conformal testing, a patterned wafer sample was placed on a sample holder for deposition. Thermocouples were connected to the sample holder to confirm the substrate temperature. Ozone was used as the oxygen source gas for deposition. Deposition parameters are provided in Table I, where the terms pulse or feed are interchangeable and represent the steps of introducing the silicon precursor or oxygen source into the reactor.

[0071] Table 1. Process for atomic layer deposition of silicon oxide films with an oxygen source using pyrrolotrimethylsilane

[0072]

[0073] Repeat steps b through e until the desired thickness is achieved. The film thickness and refractive index (RI) are measured using a FilmTek 2000SE ellipticity meter by fitting the reflection data from the film to a pre-set physical model (e.g., a Lorentz oscillator model). The growth rate (GPC) per cycle is defined in angstroms. The calculated silicon oxide thickness was divided by the number of cycles. Precursor growth rates were shown to saturate with increasing precursor feed time and ozone time at various substrate temperatures, indicating the ALD performance of the precursor. Wet etching rates were performed using a 1% solution of 49% hydrofluoric acid (HF) in deionized water (approximately 0.5 wt% HF). Thermal oxide wafers were used as a reference for each batch to confirm the solution concentration. For 0.5 wt% HF in deionized water, the typical wet etching rate (WER) for thermal oxide wafers was... Wet etching rate is calculated using film thicknesses before and after etching. Relative WER is calculated as the WER of silicon oxide from pyrrolithyltrimethylsilane / dimethylaminotrimethylsilane divided by the WER of thermal oxides measured under the same conditions.

[0074] Example 1. Thermal atomic layer deposition of silicon oxide using pyrrolidinyltrimethylsilane / dimethylaminotrimethylsilane and ozone. Thermal atomic layer deposition using pyrrolidinyltrimethylsilane and dimethylaminotrimethylsilane was performed according to Table 1. Table 2 summarizes the growth rate per cycle (GPC) at substrate temperatures of 600°C, 650°C, and 700°C. / cycle).

[0075] Table 2. GPC of pyrrolidinyltrimethylsilane vs. dimethylaminotrimethylsilane

[0076]

[0077] Table 2 shows that the GPC of pyrrolithyltrimethylsilane is lower than that of dimethylaminotrimethylsilane at 600°C and 650°C, indicating that pyrrolithyltrimethylsilane is less reactive than dimethylaminotrimethylsilane. Table 3 lists the relative wet etch rate (WER) of silicon oxide, showing that silicon oxide deposited by pyrrolithyltrimethylsilane has a lower WER than silicon oxide deposited by dimethylaminotrimethylsilane.

[0078] Table 3. Relative WER of pyrrolotrimethylsilane vs. dimethylaminotrimethylsilane

[0079]

[0080] Example 2. Proof of concept for the growth of a non-conformal silicon oxide film deposited on top of a trench structure using pyrrolithic trimethylsilane and ozone.

[0081] TEM was used to study non-conformal thermally deposited silicon oxide films via pyrrolithic trimethylsilane. The trench dimensions were approximately 50 nm wide and 600 nm deep. Deposition was performed at 600 °C with precursor pulse times of 2, 16, and 48 seconds and an ozone flow of 20 seconds. The films were non-conformal within the trenches, i.e., thicker at the top and thinner in the middle and bottom, indicating that pyrrolithic trimethylsilane is a unique precursor providing non-conformal deposition, likely due to its stronger Si-N bonds compared to dimethylaminotrimethylsilane. Table 4 shows the average film thickness at the top, middle, and bottom of the trenches.

[0082] Figure 1 TEM images show the growth of a nonconformal silicon oxide film on a trench using pyrrolithic trimethylsilane (16-second precursor pulse time) at 600 °C, demonstrating the nonconformal silicon oxide in the trench, i.e., thicker at the top and thinner in the middle and bottom of the trench.

[0083] Table 4. Film thickness measured at different locations in trenches deposited by pyrrolithic trimethylsilane at 600 °C.

[0084]

Claims

1. An atomic layer deposition method for depositing a film containing silicon and oxygen into surface features comprising vias and / or trenches on a substrate, the method comprising: a. placing the substrate having exposed hydroxyl groups on the surface features into a reactor, and heating the reactor to at least one temperature ranging from ambient temperature to 700 °C, and optionally maintaining the reactor at a pressure of 100 Torr or less; b. introducing into the reactor a first precursor of SiX(I) having the formula R 1 R 2 R 3 SiX(I), wherein R 1 , R 2 , R 3 are each independently selected from the group consisting of hydrogen, linear C1-C 10 alkyl, branched C3-C 10 alkyl, C3-C 10 cycloalkyl, C3-C 10 heterocyclyl, C2-C 10 alkenyl, C2-C 10 alkynyl, and C4-C 10 aryl, and X is a nitrogen containing heteroatom cyclic group, wherein the nitrogen containing heteroatom cyclic group is a C3 to C 10 heterocyclic group having at least one C=C bond directly attached to a nitrogen atom, to react with the exposed hydroxyl group; c. purging the reactor with an inert gas of any unreacted first precursor; d. introducing an oxygen source into the reactor; and e. purging with an inert gas any unreacted oxygen source and any byproducts, wherein steps b through e are repeated until the surface features are covered with a predetermined amount of the film containing silicon and oxygen; characterized in that the film containing silicon and oxygen is a non-conformal film.

2. The method of claim 1, wherein X is selected from the group consisting of pyrrolyl, substituted pyrrolyl, 2-pyrrolinyl, substituted 2-pyrrolinyl, imidazolyl, substituted imidazolyl, 2-imidazolinyl, substituted 2-imidazolinyl, pyrazolyl, substituted pyrazolyl, 1,2,3-triazolyl, 2-pyrazolinyl, substituted pyrazolinyl, 1,4-dihydropyridinyl, substituted 1,4-dihydropyridinyl, 1,2-dihydropyridinyl, substituted 1,2-dihydropyridinyl, 1,2,3,4-tetrahydropyridinyl, and substituted 1,2,3,4-tetrahydropyridinyl, wherein when X is substituted, the substituents are selected from the group consisting of linear and branched alkyl groups.

3. The method of claim 2, wherein X is selected from the group consisting of 3-methylpyrrolyl, 2-methylpyrrolyl, 3,4-dimethylpyrrolyl, 3-ethylpyrrolyl, 2,5-dimethylpyrrolyl, 2,4-dimethylpyrrolyl, 2,3-dimethylpyrrolyl, 2,3-dihydro-3-methyl-pyrrolyl, 2,3-dihydro-5-methyl-1h-pyrrolyl, 3,4-dihydro-4-methylpyrrolyl, 2,3-dihydro-2,2-dimethylpyrrolyl, 2,3-dihydro-3,5-dimethylpyrrolyl, 2-methylimidazolyl, 4-methylimidazolyl, 2-ethylimidazolyl, 2,4-dimethylimidazolyl, 4,5-dimethylimidazolyl, 2-methylimidazolinyl, 4-methyl-2-imidazolinyl, 4,4-dimethyl-2-imidazolinyl, 4-methylpyrazolyl, 5-methyl-pyrazolyl, 3-methylpyrazolyl, 5-methyl-1,2,3-triazolyl, 4,5-dimethyl-1,2,3-triazolyl, 4-methyl-4,5-dihydro-pyrazolyl, 5-methyl-2-pyrazolinyl, 3-methyl-2-pyrazolinyl, 1,4-dihydro-4-methylpyridinyl, 1,4-dihydro-2-methylpyridinyl, 1,2,3,4-tetrahydro-5-methylpyridinyl, and 1,2,3,4-tetrahydro-5,6-dimethylpyridinyl.

4. The method of claim 1, wherein the first precursor is at least one selected from the group consisting of pyrrolyltrimethylsilane, pyrrolyldimethyloctylsilane, 2,5- dimethylpyrrolyltrimethylsilane, 2-pyrrolinyltrimethylsilane, imidazolyltrimethylsilane, 2- imidazolinyltrimethylsilane, pyrazolyltrimethylsilane, 1,2,3-triazolyltrimethylsilane, and 2- pyrazolinyltrimethylsilane.

5. 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.

6. The method of claim 1, wherein the surface feature has a depth to width aspect ratio of at least 2:

1.

7. The method of claim 6, wherein the depth to width aspect ratio is at least 4:

1.

8. The method of claim 1, wherein the surface feature has a width of 100 nm or less.

9. An atomic layer deposition method for depositing a film comprising silicon oxide or a metal oxide into a surface feature comprising a via and / or a trench on a substrate, the method comprising: a. placing the substrate having exposed hydroxyl groups on the surface feature into a reactor, and heating the reactor to a temperature ranging from ambient temperature to 700 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. introducing into the reactor a first precursor of SiX(I) having the formula R 1 R 2 R 3 SiX(I), wherein R 1 , R 2 , R 3 are each independently selected from the group consisting of hydrogen, linear C1-C 10 alkyl, branched C3-C 10 alkyl, C3-C 10 cycloalkyl, C3-C 10 heterocyclyl, C2-C 10 alkenyl, C2-C 10 alkynyl, and C4-C 10 aryl, and X is a nitrogen-containing heteroatom cyclic group, wherein the nitrogen- containing heteroatom cyclic group is a C3 to C 10 heterocyclic group having at least one C=C bond directly attached to a nitrogen atom, to react with the exposed hydroxyl group; c. purging any unreacted first precursor from the reactor using an inert gas; d. introducing a vapor of a second precursor having at least one organic amino group to react with any unreacted hydroxyl groups; e. purging any unreacted second precursor from the reactor using an inert gas; f. introducing an oxygen source into the reactor; and g. purging any unreacted oxygen source and byproducts using an inert gas wherein steps b through g are repeated until the surface feature is filled from the bottom up with the silicon oxide or the metal oxide from the surface feature; and wherein the film comprising silicon oxide or a metal oxide is a non-conformal film.

10. The method of claim 9, wherein X is selected from the group consisting of pyrrolyl, substituted pyrrolyl, 2-pyrrolinyl, substituted 2-pyrrolinyl, imidazolyl, substituted imidazolyl, 2-imidazolinyl, substituted 2-imidazolinyl, pyrazolyl, substituted pyrazolyl, 1,2,3-triazolyl, 2-pyrazolinyl, substituted 2-pyrazolinyl, 1,4-dihydropyridinyl, substituted 1,4-dihydropyridinyl, 1,2-dihydropyridinyl, substituted 1,2-dihydropyridinyl, 1,2,3,4-tetrahydropyridinyl, and substituted 1,2,3,4-tetrahydropyridinyl, wherein when X is substituted, the substituents are selected from the group consisting of linear and branched alkyl groups.

11. The method of claim 10, wherein X is selected from the group consisting of 3- methylpyrrolyl, 2-methylpyrrolyl, 3,4-dimethylpyrrolyl, 3-ethylpyrrolyl, 2,5- dimethylpyrrolyl, 2,4-dimethylpyrrolyl, 2,3-dimethylpyrrolyl, 2,3-dihydro-3-methyl- pyrrolyl, 2,3-dihydro-5-methyl-lh-pyrrolyl, 3,4-dihydro-4-methylpyrrolyl, 2,3-dihydro- 2,2-dimethylpyrrolyl, 2,3-dihydro-3,5-dimethylpyrrolyl, 2-methylimidazolyl, 4- methylimidazolyl, 2-ethylimidazolyl, 2,4-dimethylimidazolyl, 4,5-dimethylimidazolyl, 2-methylimidazolinyl, 4-methyl-2-imidazolinyl, 4,4-dimethyl-2-imidazolinyl, 4- methylpyrazolyl, 5-methyl-pyrazolyl, 3-methylpyrazolyl, 5-methyl-l,2,3-triazolyl, 4,5- dimethyl-l,2,3-triazolyl, 4-methyl-4,5-dihydro-pyrazolyl, 5-methyl-2-pyrazolinyl, 3- methyl-2-pyrazolinyl, l,4-dihydro-4-methylpyridinyl, l,4-dihydro-2-methylpyridinyl, 1,2,3,4-tetrahydro-5-methylpyridinyl, and l,2,3,4-tetrahydro-5,6-dimethylpyridinyl.

12. The method of claim 9, wherein the first precursor is at least one selected from the group consisting of pyrrolyltrimethylsilane, pyrrolyldimethyloctylsilane, 2,5- dimethylpyrrolyltrimethylsilane, 2-pyrrolinyltrimethylsilane, imidazolyltrimethylsilane, 2-imidazolinyltrimethylsilane, pyrazolyltrimethylsilane, l,2,3-triazolyltrimethylsilane, and 2-pyrazolinyltrimethylsilane.

13. The method of claim 9, wherein the oxygen source is selected from the group consisting of oxygen, oxygen plasma, water vapor plasma, a mixture of water and organic amine, hydrogen peroxide, nitrous oxide, ozone, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.

14. The method of claim 9, wherein the second precursor is selected from the group consisting of organoaminosilane, organoaminoethysilane, organoaminotrimethylsilylamine, organoaminosiloxane, organoaminocyclosiloxane, and organoamino titanium, organoamino hafnium, organoamino zirconium, organoamino tantalum, organoamino tungsten, organoamino molybdenum, organoamino aluminum, alkyl aluminum, and metal alkoxide.

15. The method of claim 14, wherein the second precursor is an organoaminosilane selected from the group consisting of diisopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, bis(dimethylamino)silane, bis(ethylmethylamino)silane, bis(tert-butylamino)silane, diisopropylaminomethylsilane, di-sec-butylaminomethylsilane, dimethylaminodimethylsilane, dimethylamino-trimethylsilane, bis(dimethylamino)methylsilane, tetra(dimethylamino)silane, tri(dimethylamino)silane, isopropylamino-trimethylsilane, tert-butylamino-trimethylsilane, isobutylamino-trimethylsilane, cyclohexaaminotrimethylsilane, pyrrolidinyl-trimethylsilane, 2-methylpyrrolidinyl-trimethylsilane, 2,5-dimethylpyrrolidinyl-trimethylsilane, piperidinyl-trimethylsilane, 2,6-dimethylpiperidinyl-trimethylsilane, 1-methylpiperazinyl-trimethylsilane, pyrrolyl-trimethylsilane, 2,5-dimethylpyrrolyl-trimethylsilane, and imidazolyl-trimethylsilane.

16. The method of claim 9, wherein the surface features have a depth-to-width aspect ratio of at least 2:

1.

17. The method of claim 16, wherein the depth-to-width aspect ratio is at least 4:

1.

18. The method of claim 9, wherein the surface features have a width of 100 nm or less.

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