JP-7855039-B2 - Deposition of carbon-doped silicon oxide

Inventors

• メイリャン ワン
• シンチエン レイ
• ハリピン チャンドラ
• マシュー アール．マクドナルド

Assignees

• バーサム マテリアルズ ユーエス，リミティド ライアビリティ カンパニー

Dates

Publication Date

20260507

Application Date

20240905

Priority Date

20190205

Claims (5)

1. A method for depositing a carbon-doped silicon oxide film onto a substrate, a) A step of providing the substrate into the reactor; b) Equations A and B : Selected from the group consisting of, where R1 is selected from linear C1 - C10 alkyl groups, branched C3 - C10 alkyl groups, C3 - C10 cyclic alkyl groups, C3 - C10 heterocyclic groups, C3 - C10 alkenyl groups, C3 - C10 alkynyl groups and C4 - C10 aryl groups; R2 is selected from the group consisting of hydrogen, linear C1 - C10 alkyl groups, branched C3 - C10 alkyl groups, C3 - C10 cyclic alkyl groups, C3 - C10 heterocyclic groups, C2 - C10 alkenyl groups, C2 - C10 alkynyl groups and C4 - C10 aryl groups, where R1 and R2 in formula A or B are either linked to form a cyclic ring structure or not linked to form a cyclic ring structure; R Step 3-9 involves introducing at least one first silicon precursor into the reactor, each independently selected from hydrogen, a linear C1 - C10 alkyl group, a branched C3 - C10 alkyl group, a C3 - C10 cyclic alkyl group, a C2 - C10 alkenyl group, a C2 -C10 alkynyl group, and a C4- C10 aryl group; c) Purging the reactor with a purge gas to remove at least a portion of any of the at least one first silicon precursor that has not been absorbed by the substrate; d) A step of introducing an oxygen-containing plasma source into a reactor and reacting it with at least one first silicon precursor to form a first silicon-containing film; e) Purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing plasma source; f) A step of repeating steps b) to e) until a first silicon-containing film of the desired thickness is deposited; g) A step of introducing at least one second silicon precursor having the formula R 3 x Si (NR 1 R 2 ) 4-x , where R 1-3 are defined as above and x = 1, 2 or 3 into the reactor; h) Purging the reactor with a purge gas to remove at least a portion of any of the at least one second silicon precursor that has not been absorbed into the first silicon-containing membrane; i) A step of introducing an oxygen-containing source into the reactor to form a second silicon-containing film; j) A step of purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing sources; k) a step of repeating steps g) to j) until a second silicon-containing film of a desired thickness is deposited, wherein the method is carried out at one or more temperatures in the range of 20°C to 300°C.
2. The method according to claim 1, wherein each of R1-2 is a C1 - C4 alkyl group.
3. The method according to claim 1, wherein R 1-3 are each independently selected from the group consisting of methyl and ethyl.
4. The first silicon precursor compound is 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-diethyl Mino-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 Roxane, 2-iso-propylamino-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-2,4,4,6,6-pentamethylcyclo Risiloxane, 2-pyrrolyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-2,5-dimethylpiperidino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylamino-2, 4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidin-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-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-pyrrolidino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethyl Amino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-2,5-dimethylpiperidino The method according to claim 1, selected from the group consisting of no-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-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.
5. The method according to claim 1, wherein at least one second silicon precursor compound is selected from the group consisting of di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, and bis(tert-butylamino)silane.

Description

Cross-reference of related applications: This application claims priority to U.S. Provisional Application 62/801248, filed on 5 February 2019, the entire contents of which are incorporated herein by reference for all possible purposes. This invention relates to organosilicon compounds that can be used to deposit silicon and oxygen-containing films, including carbon-doped silicon oxide films; to methods for using these compounds to deposit silicon oxide-containing films; and to films obtained from these compounds and methods. Atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) are processes used, for example, to deposit silicon oxide conformal films at low temperatures (<500°C). In both ALD and PEALD processes, the precursor and reactive gas (e.g., oxygen or ozone) are separated and pulsed for a specific number of cycles, repeatedly forming a silicon oxide monolayer in each cycle. Organic aminosilane and chlorosilane precursors are known in the art and can be used to deposit silicon-containing films at relatively low temperatures (<300°C) and relatively high growth rates per cycle (GPC > 1.0 Å/cycle) by atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) processes. In the art, there is a demand for compositions and methods for using such compositions to deposit silicon-containing films with high carbon content (e.g., carbon content of about 10 at% or more as measured by X-ray photoelectron spectroscopy (XPS)) for specific applications in the electronics industry. Some important characteristics of carbon-doped silicon-containing films are wet etching resistance and hydrophobicity. Generally speaking, the introduction of carbon into silicon-containing films helps to reduce the wet etching rate and increase hydrophobicity. Further advantages of adding carbon to silicon-containing films include reducing the dielectric constant and/or providing improvements to other electrical or physical properties of the film. Examples of known precursors and methods are disclosed in the following publications, patents, and patent applications. U.S. Patent Application Publication No. 2015/087139 describes the use of amino-functionalized carbosilane for depositing silicon-containing films by a thermal ALD process or a PEALD process. U.S. Patent No. 9,337,018 describes the use of organic aminodisilanes for depositing silicon-containing films by a thermal ALD process or a PEALD process. U.S. Patents 8,940,648, 9,005,719, and 8,912,353 describe the use of organic aminosilanes for depositing silicon-containing films by thermal ALD or PEALD processes. U.S. Patent Application Publication No. 2015/275355 describes the use of mono and bis(organicamino)alkylsilanes for depositing silicon-containing films by a thermal ALD process or a PEALD process. U.S. Patent Application Publication No. 2015/376211 describes the use of mono(organic amino)-substituted, halide-substituted, and pseudo-halide-substituted trisilylamines for depositing silicon-containing films by thermal ALD or PEALD processes. International Publication No. 15/105350 describes the use of a four-membered ring cyclodisilazane having at least one Si-H bond for depositing silicon-containing films by thermal ALD or PEALD processes. U.S. Patent No. 8,575,033 describes a method for depositing silicon carbide films onto a substrate surface. The method involves the use of a gas-phase carbosilane precursor and may utilize a plasma-enhanced atomic layer deposition process. U.S. Patent Application Publication No. 2013/0224964 teaches a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), comprising the steps of (i) adsorbing a precursor onto the surface of the substrate; (ii) reacting the adsorbed precursor with a reactant gas on the substrate; and (iii) repeating steps (i) and (ii) to form a dielectric film having at least Si-C bonds on the substrate. U.S. Patent Application Publication No. 2014/302688 describes a method for forming a dielectric layer on a patterned substrate, which may include bonding a silicon- and carbon-containing precursor with a radical oxygen precursor in a plasma-free substrate processing region of a chemical vapor deposition chamber. The silicon- and carbon-containing precursor and the radical oxygen precursor react to deposit a flowable silicon-carbon-oxygen layer on the patterned surface. U.S. Patent Application Publication No. 2014/302690 describes a method for forming a low-dielectric constant (low-k) dielectric material on a substrate. The method may include the steps of generating a radical precursor by flowing a non-excited precursor into a remote plasma region, and reacting the radical precursor with a gas-phase silicon precursor to deposit a flowable film on the substrate. The gas-phase silicon precursor may include a compound containing at least one silicon and oxygen, and at least one silicon and a carbon linker. The flowable f