[go: up one dir, main page]

WO2025229081A1 - Organoamino-carbosilanes and methods for depositing siliconcontaining films using same - Google Patents

Organoamino-carbosilanes and methods for depositing siliconcontaining films using same

Info

Publication number
WO2025229081A1
WO2025229081A1 PCT/EP2025/061871 EP2025061871W WO2025229081A1 WO 2025229081 A1 WO2025229081 A1 WO 2025229081A1 EP 2025061871 W EP2025061871 W EP 2025061871W WO 2025229081 A1 WO2025229081 A1 WO 2025229081A1
Authority
WO
WIPO (PCT)
Prior art keywords
disilapentane
methyl
bis
disilabutane
dimethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/061871
Other languages
French (fr)
Inventor
Xinjian Lei
Ming Li
Matthew R. Macdonald
Chandra HARIPIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of WO2025229081A1 publication Critical patent/WO2025229081A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Definitions

  • Described herein are a composition and a method for the formation of a silicon containing film. More specifically, described herein are a composition and a method for formation of a film comprising silicon and oxygen at one or more deposition temperatures of about 700 °C or lower and using an atomic layer deposition (ALD) process.
  • ALD atomic layer deposition
  • Thermal oxidation is a process commonly used when depositing high purity and highly conformal silicon oxide films such as silicon dioxide (SiO2) in semiconductor applications.
  • SiO2 silicon dioxide
  • the thermal oxidation process has a very low deposition rate, e.g., less than 0.03 A/s at 700 °C, which makes it impractical for high volume manufacturing processes (see, for example, Wolf, S., “Silicon Processing for the VLSI Era Vol. 1 - Process Technology”, Lattice Press, CA, 1986).
  • Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes used to deposit silicon dioxide (SiO2) conformal films at low temperatures ( ⁇ 500 °C).
  • the precursor and reactive gas such as oxygen or ozone
  • SiO2 deposited at low temperatures using these processes may contain levels of impurities such as carbon (C), nitrogen (N), or both, which in some cases may be detrimental to semiconductor applications.
  • impurities such as carbon (C), nitrogen (N), or both, which in some cases may be detrimental to semiconductor applications.
  • C carbon
  • N nitrogen
  • JP2010275602 and JP2010225663 disclose the use of a raw material to form a Si containing thin film such as silicon oxide by a chemical vapor deposition (CVD) process at a temperature range of from 300-500 °C.
  • the raw material is an organic silicon compound, represented by formula: (a) HSi(CH3)(R 1 )(NR 2 R 3 ), wherein R 1 represents NR 4 R 5 or a 1C-5C alkyl group; R 2 and R 4 each represent a 1C- 5C alkyl group or hydrogen atom; and R 3 and R 5 each represent a 1C-5C alkyl group; or formula (b) HSiCI(NR 1 R 2 )(NR 3 R 4 ), wherein R 1 and R 3 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom; and R 2 and R 4 independently represent an alkyl group having 1 to 4 carbon atoms.
  • the organic silicon compounds contained H-Si bonds
  • US Pat. No. 7,084,076 discloses a halogenated siloxane such as hexachlorodisiloxane (HCDSO) that is used in conjunction with pyridine as a catalyst for ALD deposition below 500 °C to form silicon dioxide.
  • HCDSO hexachlorodisiloxane
  • US Pat. No. 6,992,019 discloses a method for catalyst-assisted atomic layer deposition (ALD) to form a silicon dioxide layer having superior properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using a tertiary aliphatic amine, as the catalyst component, or both in combination, together with related purging methods and sequencing.
  • ALD catalyst-assisted atomic layer deposition
  • the precursor used is hexachlorodisilane.
  • the deposition temperature is between 25 -150 °C.
  • ALD atomic layer deposition
  • ALD-like process such as, without limitation, a cyclic chemical vapor deposition process
  • it is desirable to develop a low temperature deposition method e.g., deposition at one or more temperatures of 700 °C or lower
  • a low temperature deposition method e.g., deposition at one or more temperatures of 700 °C or lower
  • film properties such as purity and/or density
  • Described herein is a process for the deposition of a silicon-containing material or film at high temperatures, e.g., at one or more temperatures of 700 °C or lower, in an atomic layer deposition (ALD) or an ALD-like process.
  • ALD atomic layer deposition
  • This invention is related to organoamino-carbosilane precursor compounds having a Si-C-Si linkage and selected from the group consisting of Formulae I A, IB and IC: wherein R 1 and R 2 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group; R 3-6 are each independently selected from hydrogen and methyl; R 7 is selected from hydrogen, methyl, and NR 8 R 9 wherein R 8 and R 9 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, and a Ce to C10 aryl group with a provisos that R 3-7 cannot be all hydrogen for IA, R 3 ' 6 cannot be all hydrogen if R 7 is NR 8 R 9 in IA, R 3 ' 6 cannot be all methyl if R 7 is NR 8 R 9
  • One embodiment provides a process to deposit a silicon-containing film, which comprises the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e.
  • Another embodiment provides a process to a deposit silicon-containing film, which comprises the steps of: a. providing a substrate in a reactor; b.
  • mTorr millitorr
  • the oxygen source may include, for example, water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.
  • H2O water
  • O2O hydrogen peroxide
  • O2 oxygen
  • O3 oxygen plasma
  • NO2 plasma NO2 plasma
  • CO carbon monoxide
  • CO2 plasma carbon dioxide plasma
  • Figure 1 is an infrared spectrum for an as-deposited silicon-containing film deposited using 2-dimethylamino-2,4,4-trimethyl-2,4-disilapentane and ozone at 300 o/ ⁇ DETAILED DESCRIPTION OF THE INVENTION
  • compositions and processes related to the formation of a silicon-containing film such as a silicon oxynitride film, a stoichiometric or non- stoichiometric silicon oxide film, a carbon doped silicon oxide film or combinations thereof with one or more process temperatures of 700°C or lower , in an atomic layer deposition (ALD) or in an ALD-like process, such as, without limitation, a cyclic chemical vapor deposition process (CCVD).
  • ALD atomic layer deposition
  • CCVD cyclic chemical vapor deposition process
  • the silicon-containing film is expected to have at least one of the following characteristics: a density of at least about 2.0 g/cm 3 ; a wet etch rate that is less than about 2.5 A/s as measured in a solution of 1 :100 of HF to water (0.5 wt. % dHF) acid; an electrical leakage of less than about 1 x 10' 8 A/cm2 up to 6 MV/cm; and a hydrogen impurity of less than about 4 x 10 21 at/cc as measured by SIMS.
  • the at least one organoamino-carbosilane having Si-C- Si linkage precursor described herein is selected from the group consisting of Formulae IA, IB and IC: wherein R 1 and R 2 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group; R 3-6 are each independently selected from hydrogen and methyl; R 7 is selected from hydrogen, methyl, and NR 8 R 9 wherein R 8 and R 9 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, and a Ce to C10 aryl group with a provisos that R 3 ' 7 cannot be all hydrogen for IA, R 3 ' 6 cannot be all hydrogen if R 7 is NR 8 R 9 in IA, R 3 ' 6 cannot be all methyl if R 7 is
  • Tables 1 to 3 list preferred organoamino-carbosilanes having Si-C-Si linkage precursor having Formulae IA, IB and IC. [0017] Table 1. Organoamino-carbosilanes having Si-C-Si linkage precursors having Formula IA wherein R 3 ' 6 are selected from hydrogen and methyl and R 7 is selected from hydrogen, methyl, or NR 8 R 9 which provide organoamino-carbosilanes precursors having lower boiling points and more suitable for vapor deposition. -
  • One embodiment of the invention provides a process to deposit a silicon- containing film comprising steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with purge gas, wherein steps b through e are repeated until a desired thickness of film is deposited.
  • the oxygen source is selected from water (H2O) (e.g., deionized water, purifier water, and/or distilled water), oxygen (O2), oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.
  • H2O water
  • O2O oxygen
  • O3 oxygen
  • N2O plasma ozone
  • NO2 plasma NO2 plasma
  • CO carbon monoxide
  • CO2 plasma carbon dioxide
  • the organoamino-carbosilane precursor compound having a Si-C-Si linkage should have at least one anchoring functionality, which reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon species.
  • the anchoring functionality of a smaller organoamino group such as dimethylamino, ethylmethylamino or diethylamino allow the organoaminodisilazane to have a relatively low boiling point and a relatively high reactivity.
  • the organoamino-carbosilane precursor compound having a Si-C-Si linkage should also have a passive functionality in that it is chemically stable to prevent further surface reaction, leading to a self-limiting process.
  • the passivating functionality is selected from different alkyl groups such as hydrogen or a methyl group. The remaining groups on the surface can then be oxidized to form a Si-O-Si linkage as well as hydroxyl groups.
  • hydroxyl sources such as H2O or water plasma can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle.
  • One particular embodiment of the method described herein to deposit a silicon-containing film on a substrate comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with purge gas, wherein steps b through e are repeated until a desired thickness of the silicon oxide film is deposited.
  • Another embodiment of the method described herein introduces a hydroxyl or OH source such as H2O vapor after the oxidizing step to repopulate the anchoring functionality or reactive sites for organoamino-carbosilane having Si-C-Si linkage to anchor on the surface to form the monolayer.
  • the deposition steps comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; e. purging the reactor with purge gas; f. introducing water vapor or hydroxyl source into the reactor; and g. purging the reactor with purge gas, wherein steps b through g are repeated until a film of desired thickness is deposited.
  • deposition steps are as follows: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing a mild oxidant into the reactor; e. purging the reactor with purge gas; and f. optionally treating the film with a plasma comprising hydrogen, wherein steps b through e are repeated until a film of desired thickness is deposited. Step f is optionally performed on deposited films to improve the film properties.
  • the mild oxidant is used in order to keep some of the carbon in the film.
  • the mild oxidant can be selected from sources other than oxygen plasma, including water (H2O) (e.g., deionized water, purifier water, and/or distilled water), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.
  • H2O water
  • N2O plasma e.g., deionized water, purifier water, and/or distilled water
  • NO2 plasma e.g., NO2 plasma
  • CO carbon monoxide
  • CO2 carbon dioxide
  • the carbon content of the film is 0.5 atomic weight percent (at. %) or greater as measured by x-ray photospectroscopy.
  • a method of depositing carbon doped silicon oxide films comprises steps as below: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing oxidant into the reactor; e. purging the reactor with purge gas; f. exposing the resulting film to a plasma comprising hydrogen; g. purging the reactor with purge gas. wherein step b to g are repeated to achieved desired film thickness.
  • steps b to e are repeated to provide a desired thickness of carbon doped silicon oxide film before steps f to g are conducted. In other embodiments, steps f to g are conducted before steps d to e are performed.
  • the carbon content of the film is 0.5 atomic weight percent (at. %) or greater as measured by x-ray photospectroscopy.
  • alkyl denotes a linear or branched functional group having from 1 to 10, 3 to 10, or 1 to 6 carbon atoms.
  • exemplary linear alkyl groups include, but are not limited to, methyl, ethyl, n-propyl (n-Pr or Pr n ), n-butyl, n-pentyl, and n-hexyl groups.
  • Exemplary branched alkyl groups include, but are not limited to, iso-propyl (i-Pr or Pr'), isobutyl (i-Bu or Bu'), sec-butyl (s-Bu or Bu s , tert-butyl (t-Bu or Bu‘, iso-pentyl, tert-pentyl, isohexyl, and neohexyl.
  • the alkyl group may have one or more functional groups such as, but not limited to, an alkoxy group, a dialkylamino group or combinations thereof, attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto.
  • the alkyl group may be saturated or unsaturated.
  • aryl denotes an aromatic cyclic functional group having from 3 to 10 carbon atoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms.
  • exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.
  • organoamino denotes a primary or secondary organic amino group having at least one carbon-based substituent on the nitrogen atom selected from the group of a linear or branched Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group.
  • Secondary amino groups have the option for the organic substituents to either be linked to form a ring, or not to be linked to form a ring.
  • organoamino groups include, but are not limited to, methylamino, ethylamino, n-propylamino, iso-propylamino, sec-butylamino, tertbutylamino, iso-butylamino, tert-amylamino, cyclopentylamino, cyclohexylamino, phenylamino, dimethylamino, diethylamino, ethylmethylamino, di-n-propylamino, di- iso-propylamino, di-sec-butylamino, pyrrolidino, pyrrolyl, imidazolyl, piperidino, and 2,6-dimethylpiperidino.
  • silicon-containing film denotes a film comprising silicon and oxygen atoms.
  • examples of such films include, but not limited to, silicon oxide, carbon doped silicon oxide, carbon doped silicon oxynitride.
  • purge gas refers to an inert gas which is not reactive and can be selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), neon (Ne), hydrogen (H2), and mixtures thereof.
  • substituents R 1 and R 2 in Formulae I A or IB can be linked together to form a ring structure.
  • R 3 and R 4 are linked together to form a ring R 3 will include a bond for linking to R 4 and vice versa.
  • the ring structure can be unsaturated such as, for example, a cyclic alkyl ring, or saturated, for example, an aryl ring. Further, in these embodiments, the ring structure can also be substituted or substituted.
  • Exemplary cyclic ring groups include, but not limited to, pyrrolidino, 2-methylpyrrolidino, 2,5- dimethylpyrrolidino, piperidino, and 2,6-dimethylpiperidino groups. In other embodiments, however, substituents R 1 and R 2 are not linked.
  • the silicon-containing films deposited using the methods described herein are formed in the presence of oxygen using an oxygen source, reagent or precursor comprising oxygen.
  • An oxygen source may be introduced into the reactor in the form of at least one oxygen source and/or may be present incidentally in the other precursors used in the deposition process.
  • Suitable oxygen source gases may include, for example, water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), hydrogen peroxide, oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.
  • the oxygen source comprises an oxygen source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters (seem) or from about 1 to about 1000 seem.
  • the oxygen source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
  • the oxygen source comprises water having a temperature of 10°C or lower.
  • the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the oxygen source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds.
  • the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge inbetween.
  • the oxygen source or reagent is provided in a molecular amount less than a 1 :1 ratio to the silicon precursor, so that at least some carbon is retained in the as deposited dielectric film.
  • the silicon oxide films further comprise nitrogen.
  • the films are deposited using the methods described herein and formed in the presence of a nitrogen-containing source.
  • a nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and/or may be present incidentally in the other precursors used in the deposition process.
  • Suitable nitrogen-containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixture thereof.
  • the nitrogen-containing source comprises an ammonia plasma or hydrogen/nitrogen plasma source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (seem) or from about 1 to about 1000 seem.
  • the nitrogen- containing source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
  • the precursor pulse can have a pulse duration that is greater than 0.01 seconds
  • the nitrogen-containing source can have a pulse duration that is less than 0.01 seconds
  • the water pulse duration can have a pulse duration that is less than 0.01 seconds.
  • the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge inbetween.
  • the deposition methods disclosed herein may involve one or more purge gases.
  • the purge gas which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors.
  • Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon (Ne), hydrogen (H2), and mixtures thereof.
  • a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 seem for about 0.1 to 1000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.
  • the respective step of supplying the precursors, oxygen source, the nitrogen-containing source, and/or other precursors, source gases, and/or reagents may be performed by changing the time for supplying them to change the stoichiometric composition of the resulting dielectric film.
  • Energy is applied to the at least one of the silicon precursor, oxygen containing source, or combination thereof to induce reaction and to form the dielectric film or coating on the substrate.
  • energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof.
  • a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface.
  • the plasma-generated process may comprise a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.
  • the at least one organoamino-carbosilane precursors may be delivered to the reaction chamber such as a cyclic CVD or ALD reactor in a variety of ways.
  • a liquid delivery system may be utilized.
  • a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor.
  • the precursors described herein may be delivered in neat liquid form, or alternatively, may be employed in solvent formulations or compositions comprising same.
  • the precursor formulations may include solvent component(s) of suitable character as may be desirable and advantageous in each end use application to form a film on a substrate.
  • the solvent or mixture thereof selected does not react with the silicon precursor.
  • the amount of solvent by weight percentage in the composition ranges from 0.5% by weight to 99.5% or from 10% by weight to 75%.
  • the solvent has a boiling point (b.p.) similar to the b.p.
  • the difference between the b.p. of the solvent and the b.p. of the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC is 40 C or less, 30 °C or less, or 20°C or less, or 10°C or less.
  • the difference between the boiling points ranges from any one or more of the following end-points: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of b.p.
  • suitable solvents in the compositions include, but are not limited to, an ether (such as 1,4-dioxane, dibutyl ether), a tertiary amine (such as pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'- Dimethylpiperazine, N,N,N',N'-Tetramethylethylenediamine), a nitrile (such as benzonitrile), an alkane (such as octane, nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene, mesitylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.
  • an ether such as 1,4-dioxane, dibutyl ether
  • a tertiary amine such as pyridine, 1-methylpiperidine, 1-ethylpiper
  • the purity level of the at least one organoamino- carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC is sufficiently high enough to be acceptable for reliable semiconductor manufacturing.
  • the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC described herein comprise less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight of one or more of the following impurities: free amines, free halides or halogen ions, and higher molecular weight species.
  • Higher purity levels of the organoamino-carbosilane having Si-C-Si linkage described herein can be obtained through one or more of the following processes: purification, adsorption, and/or distillation.
  • a cyclic deposition process such as ALD-like, ALD, or PEALD may be used wherein the deposition is conducted using the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC and an oxygen source.
  • the ALD-like process is defined as a cyclic CVD process but still provides high conformal silicon oxide films.
  • the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures depending upon the process requirements and the container of the at least one organoamino- carbosilane having Si-C-Si linkage precursor of Formula IA or IB or IC is kept at one or more temperatures for bubbling.
  • a solution comprising the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formula IA or IB or IC is injected into a vaporizer kept at one or more temperatures for direct liquid injection.
  • a flow of argon and/or other gas may be employed as a carrier gas to help deliver the vapor of the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC to the reaction chamber during the precursor pulsing.
  • the reaction chamber process pressure is about 1 Torr.
  • the substrate such as a silicon oxide substrate is heated on a heater stage in a reaction chamber that is exposed to the organoamino-carbosilane having Si-C-Si linkage initially to allow the complex to chemically adsorb onto the surface of the substrate.
  • a purge gas such as argon purges away unabsorbed excess complex from the process chamber.
  • an oxygen source may be introduced into reaction chamber to react with the absorbed surface followed by another gas purge to remove reaction by-products from the chamber.
  • the process cycle can be repeated to achieve the desired film thickness.
  • pumping can replace a purge with inert gas or both can be employed to remove unreacted organoamino- carbosilane precursors.
  • the steps of the methods described herein may be performed in a variety of orders, may be performed sequentially, may be performed concurrently (e.g., during at least a portion of another step), and any combination thereof.
  • the respective step of supplying the precursors and the oxygen source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting dielectric film.
  • a PEALD process for this or other embodiments may include a hydrogen and inert gas combination in plasma.
  • the inert gas may be selected from argon, neon, helium, and combinations thereof.
  • Process temperature for the method described herein are one or more temperatures ranging from 20 °C to 600 °C; or 50 °C to 500 °C; or 100 °C to 500 °C; or 100 °C to 600 °C; or 100 °C to 700 °C;
  • Deposition pressure ranges are one or more pressures ranging from 50 miliTorr (mT) to 760 Torr, or from 500 mT - 100 Torr.
  • Purge gases can be selected from inert gases such as nitrogen, helium or argon as well as other non-reactive gases.
  • An oxygen source may be selected from oxygen, a composition comprising oxygen and hydrogen, hydrogen peroxide, ozone or molecular oxygen from plasma process.
  • the catalyst employed in the method of the present invention in equation (1) or (3) is one that promotes the formation of a silicon-nitrogen bond.
  • Exemplary catalysts that can be used with the method described herein include but are not limited to the following: alkaline earth metal catalysts; halide-free main group, transition metal, lanthanide, and actinide catalysts; and halide-containing main group, transition metal, lanthanide, actinide catalysts, pure noble metals such as ruthenium platinum, palladium, rhodium, osmium can also be affixed to a support.
  • the support is a solid with a high surface area.
  • Typical support materials include but are not limited to: alumina, MgO, zeolites, carbon, Monolith cordierite, diatomaceous earth, silica gel, silica/alumina, ZrO and TiC>2.
  • Preferred supports are carbon (for examples, platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon) alumina, silica and MgO.
  • the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC according to the present invention and compositions comprising the silicon precursor compounds having Formulae IA or IB or IC according to the present invention are preferably substantially free of halide ions.
  • halide ions or halides
  • chlorides i.e.
  • chloride-containing species such as HCI or silicon compounds having at least one Si-CI bond
  • fluorides, bromides, and iodides means less than 5 ppm (by weight) measured by ion chromatography (IC), preferably less than 3 ppm measured by IC, and more preferably less than 1 ppm measured by IC, and most preferably 0 ppm measured by ICP-MS.
  • Chlorides are known to act as decomposition catalysts for the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC. Significant levels of chloride in the final product can cause the silicon precursor compounds to degrade.
  • the gradual degradation of the organoamino-carbosilane having Si-C-Si linkage compounds may directly impact the film deposition process making it difficult for the semiconductor manufacturer to meet film specifications.
  • the shelf-life or stability is negatively impacted by the higher degradation rate of the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC thereby making it difficult to guarantee a 1-2 year shelf-life. Therefore, the accelerated decomposition of the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae I A or IB or I C presents safety and performance concerns related to the formation of these flammable and/or pyrophoric gaseous byproducts.
  • the organoamino- carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC are preferably substantially free of metal ions such as, Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ .
  • metal ions such as, Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ .
  • the term “substantially free” as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS.
  • the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC are free of metal ions such as, Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ .
  • the term “free of” metal impurities as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, noble metal such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis means less than 1 ppm, preferably 0.1 ppm (by weight) as measured by ICP-MS or other analytical method for measuring metals.
  • the organoamino- carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC according to the present invention and compositions comprising the silicon precursor compounds having Formulae IA or IB or IC according to the present invention are having purity of 98% or higher, preferably 99% or higher, most preferably 99.5% or higher based on Gas Chromatography (GC) analysis.
  • GC Gas Chromatography
  • Example 1 Synthesis of 2-dimethylamino-2, 4, 4-trimethyl-2,4-disilapentane
  • Example 6 Atomic layer deposition of silicon-containing film using 2- dimethylamino-2,4,4-trimethyl-2,4-disilapentane
  • Atomic layer deposition of silicon-containing films was conducted using 2- dimethylamino-2,4,4-trimethyl-2,4-disilapentane as a silicon precursor.
  • the depositions were performed on a laboratory scale ALD processing tool.
  • the organoamino-carbosilane having a Si-C-Si linkage is delivered to the chamber by vapor draw.
  • the Si precursor container was heated to 38 °C to reach vapor pressure of about 3 torr. All gases (e.g., purge and reactant gas or precursor and oxygen source) were preheated to 100°C prior to entering the deposition zone. Gases and precursor flow rates were controlled with ALD diaphragm valves with high-speed actuation.
  • Steps 6 to 14 were repeated multiple times to get desired thickness.
  • Film growth per cycle (GPC) was calculated by dividing film thickness with the number of repeated steps.
  • the deposited silicon-containing film has GPC of 1.3 A/cycle with refractive index of 1.5.
  • the infrared spectrum (FTIR) in Figure 1 represents a Si-containing film composition as evidenced by Si-0 related absorbance bands at 810 cm-1 and 1055 cm-1 , as well as a Si-CHs band at 1250 cm -1 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Atomic layer deposition (ALD) process formation of silicon-containing film at temperature of about 700⁰C or lower is disclosed, wherein at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formulae (IA), (IB) and (IC) is used, wherein R1 and R2 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R3-6 are each independently selected from hydrogen and methyl; R7 is selected from hydrogen, methyl, and NR8R9 wherein R8 and R9 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group with a provisos that R3-7 cannot be all hydrogen for IA, R3-6 cannot be all hydrogen if R7 is NR8R9 in IA, R3-6 cannot be all methyl if R7 is NR8R9 in IB, R1-2 cannot both be hydrogen, and R8-9 cannot both be hydrogen, and wherein R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.

Description

TITLE OF THE INVENTION
ORGANOAMINO-CARBOSILANES AND METHODS FOR DEPOSITING SILICON- CONTAINING FILMS USING SAME
BACKGROUND OF THE INVENTION
[0001] Described herein are a composition and a method for the formation of a silicon containing film. More specifically, described herein are a composition and a method for formation of a film comprising silicon and oxygen at one or more deposition temperatures of about 700 °C or lower and using an atomic layer deposition (ALD) process.
[0002] Thermal oxidation is a process commonly used when depositing high purity and highly conformal silicon oxide films such as silicon dioxide (SiO2) in semiconductor applications. However, the thermal oxidation process has a very low deposition rate, e.g., less than 0.03 A/s at 700 °C, which makes it impractical for high volume manufacturing processes (see, for example, Wolf, S., “Silicon Processing for the VLSI Era Vol. 1 - Process Technology”, Lattice Press, CA, 1986).
[0003] Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes used to deposit silicon dioxide (SiO2) conformal films at low temperatures (<500 °C). In both ALD and PEALD processes, the precursor and reactive gas (such as oxygen or ozone) are separately pulsed in a certain number of cycles to form a monolayer of silicon dioxide (SiO2) at each cycle. However, silicon dioxide (SiO2) deposited at low temperatures using these processes may contain levels of impurities such as carbon (C), nitrogen (N), or both, which in some cases may be detrimental to semiconductor applications. To remedy this, one possible solution would be to increase deposition temperatures above 500 °C. However, at these higher temperatures, conventional precursors employed by semiconductor industries tend to self-react, thermally decompose, and deposit in chemical vapor deposition (CVD) mode rather than ALD mode. The CVD mode deposition typically has reduced conformality compared to ALD deposition, especially in high aspect ratio structures in semiconductor applications. In addition, when depositing thin films in CVD mode it is less easy to control the film or material thickness compared to ALD mode deposition. [0004] JP2010275602 and JP2010225663 disclose the use of a raw material to form a Si containing thin film such as silicon oxide by a chemical vapor deposition (CVD) process at a temperature range of from 300-500 °C. The raw material is an organic silicon compound, represented by formula: (a) HSi(CH3)(R1)(NR2R3), wherein R1 represents NR4R5 or a 1C-5C alkyl group; R2and R4 each represent a 1C- 5C alkyl group or hydrogen atom; and R3 and R5 each represent a 1C-5C alkyl group; or formula (b) HSiCI(NR1R2)(NR3R4), wherein R1 and R3 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom; and R2 and R4 independently represent an alkyl group having 1 to 4 carbon atoms. The organic silicon compounds contained H-Si bonds
[0005] US Pat. No. 7,084,076 discloses a halogenated siloxane such as hexachlorodisiloxane (HCDSO) that is used in conjunction with pyridine as a catalyst for ALD deposition below 500 °C to form silicon dioxide.
[0006] US Pat. No. 6,992,019 discloses a method for catalyst-assisted atomic layer deposition (ALD) to form a silicon dioxide layer having superior properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using a tertiary aliphatic amine, as the catalyst component, or both in combination, together with related purging methods and sequencing. The precursor used is hexachlorodisilane. The deposition temperature is between 25 -150 °C.
[0007] There is a need for a process for forming a high quality, low impurity, high conformal silicon oxide film using an atomic layer deposition (ALD) process or an ALD-like process such as, without limitation, a cyclic chemical vapor deposition process, to replace thermal-based deposition processes. Further, it is desirable to develop a low temperature deposition method (e.g., deposition at one or more temperatures of 700 °C or lower) to improve one or more film properties, such as purity and/or density, in an ALD or ALD-like process.
BRIEF SUMMARY OF THE INVENTION
[0008] Described herein is a process for the deposition of a silicon-containing material or film at high temperatures, e.g., at one or more temperatures of 700 °C or lower, in an atomic layer deposition (ALD) or an ALD-like process. [0009] This invention is related to organoamino-carbosilane precursor compounds having a Si-C-Si linkage and selected from the group consisting of Formulae I A, IB and IC: wherein R1 and R2 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group; R3-6 are each independently selected from hydrogen and methyl; R7 is selected from hydrogen, methyl, and NR8R9 wherein R8 and R9 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, and a Ce to C10 aryl group with a provisos that R3-7 cannot be all hydrogen for IA, R3'6 cannot be all hydrogen if R7 is NR8R9 in IA, R3'6 cannot be all methyl if R7 is NR8R9 in IB, R1'2 cannot both be hydrogen, and R8'9 cannot both be hydrogen, and wherein R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.
[0010] One embodiment provides a process to deposit a silicon-containing film, which comprises the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with purge gas; wherein steps b through e are repeated until a desired thickness of silicon oxide is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 millitorr (mTorr) to 760 Torr. In one or more embodiments the purge gas is selected from the group consisting of nitrogen, helium, argon and combination thereof. [0011] Another embodiment provides a process to a deposit silicon-containing film, which comprises the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; e. purging the reactor with purge gas; f. introducing water vapor or a hydroxyl source into the reactor; and g. purging the reactor with purge gas; wherein steps b through g are repeated until a desired thickness of silicon oxide is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 millitorr (mTorr) to 760 Torr.
[0012] In one or more embodiments described above, the oxygen source may include, for example, water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.
BRIEF DESCRIPTION OF DRAWINGS
[0013] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawing:
[0014] Figure 1 is an infrared spectrum for an as-deposited silicon-containing film deposited using 2-dimethylamino-2,4,4-trimethyl-2,4-disilapentane and ozone at 300 o/^ DETAILED DESCRIPTION OF THE INVENTION
[0015] Described herein are compositions and processes related to the formation of a silicon-containing film, such as a silicon oxynitride film, a stoichiometric or non- stoichiometric silicon oxide film, a carbon doped silicon oxide film or combinations thereof with one or more process temperatures of 700°C or lower , in an atomic layer deposition (ALD) or in an ALD-like process, such as, without limitation, a cyclic chemical vapor deposition process (CCVD). The silicon-containing film is expected to have at least one of the following characteristics: a density of at least about 2.0 g/cm3; a wet etch rate that is less than about 2.5 A/s as measured in a solution of 1 :100 of HF to water (0.5 wt. % dHF) acid; an electrical leakage of less than about 1 x 10'8 A/cm2 up to 6 MV/cm; and a hydrogen impurity of less than about 4 x 1021 at/cc as measured by SIMS.
[0016] In one embodiment, the at least one organoamino-carbosilane having Si-C- Si linkage precursor described herein is selected from the group consisting of Formulae IA, IB and IC: wherein R1 and R2 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group; R3-6 are each independently selected from hydrogen and methyl; R7 is selected from hydrogen, methyl, and NR8R9 wherein R8 and R9 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, and a Ce to C10 aryl group with a provisos that R3'7 cannot be all hydrogen for IA, R3'6 cannot be all hydrogen if R7 is NR8R9 in IA, R3'6 cannot be all methyl if R7 is NR8R9 in IB, R1'2 cannot both be hydrogen, and R8'9 cannot both be hydrogen, and wherein R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure. Tables 1 to 3 list preferred organoamino-carbosilanes having Si-C-Si linkage precursor having Formulae IA, IB and IC. [0017] Table 1. Organoamino-carbosilanes having Si-C-Si linkage precursors having Formula IA wherein R3'6 are selected from hydrogen and methyl and R7 is selected from hydrogen, methyl, or NR8R9 which provide organoamino-carbosilanes precursors having lower boiling points and more suitable for vapor deposition. -
1 , ,
[0018] Table 2. Organoamino-carbosilanes having Si-C-Si linkage precursors having Formula IB wherein R3'6 are selected from hydrogen and methyl and R7 is selected from hydrogen, methyl, or NR8R9 which provide organoamino-carbosilanes precursors having lower boiling points and more suitable for vapor deposition.
[0019] Table 3. Organoamino-carbosilanes having Si-C-Si linkage precursors having Formula IC wherein R3-6 are selected from hydrogen and methyl and R7 is selected from hydrogen, methyl, or NR8R9 which provide organoamino-carbosilanes precursors having lower boiling points and more suitable for vapor deposition. - ,
[0020] One embodiment of the invention provides a process to deposit a silicon- containing film comprising steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with purge gas, wherein steps b through e are repeated until a desired thickness of film is deposited. The oxygen source is selected from water (H2O) (e.g., deionized water, purifier water, and/or distilled water), oxygen (O2), oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof. Not being bound by theory, for ALD or ALD-like deposition process at one or more temperatures less than 700°C, the organoamino-carbosilane precursor compound having a Si-C-Si linkage should have at least one anchoring functionality, which reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon species. The anchoring functionality of a smaller organoamino group such as dimethylamino, ethylmethylamino or diethylamino allow the organoaminodisilazane to have a relatively low boiling point and a relatively high reactivity. The organoamino-carbosilane precursor compound having a Si-C-Si linkage should also have a passive functionality in that it is chemically stable to prevent further surface reaction, leading to a self-limiting process. The passivating functionality is selected from different alkyl groups such as hydrogen or a methyl group. The remaining groups on the surface can then be oxidized to form a Si-O-Si linkage as well as hydroxyl groups. In addition, hydroxyl sources such as H2O or water plasma can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle.
[0021] One particular embodiment of the method described herein to deposit a silicon-containing film on a substrate comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; and e. purging the reactor with purge gas, wherein steps b through e are repeated until a desired thickness of the silicon oxide film is deposited.
[0022] Another embodiment of the method described herein introduces a hydroxyl or OH source such as H2O vapor after the oxidizing step to repopulate the anchoring functionality or reactive sites for organoamino-carbosilane having Si-C-Si linkage to anchor on the surface to form the monolayer. The deposition steps comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing an oxygen source into the reactor; e. purging the reactor with purge gas; f. introducing water vapor or hydroxyl source into the reactor; and g. purging the reactor with purge gas, wherein steps b through g are repeated until a film of desired thickness is deposited.
[0023] Another embodiment of the method described herein to deposit carbon doped silicon oxide film. The deposition steps are as follows: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing a mild oxidant into the reactor; e. purging the reactor with purge gas; and f. optionally treating the film with a plasma comprising hydrogen, wherein steps b through e are repeated until a film of desired thickness is deposited. Step f is optionally performed on deposited films to improve the film properties. The mild oxidant is used in order to keep some of the carbon in the film. The mild oxidant can be selected from sources other than oxygen plasma, including water (H2O) (e.g., deionized water, purifier water, and/or distilled water), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof. According to an exemplary embodiment the carbon content of the film is 0.5 atomic weight percent (at. %) or greater as measured by x-ray photospectroscopy.
[0024] According to yet another embodiment, a method of depositing carbon doped silicon oxide films comprises steps as below: a. providing a substrate in a reactor; b. introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IA or IB or IC; c. purging the reactor with purge gas; d. introducing oxidant into the reactor; e. purging the reactor with purge gas; f. exposing the resulting film to a plasma comprising hydrogen; g. purging the reactor with purge gas. wherein step b to g are repeated to achieved desired film thickness. In some embodiments, steps b to e are repeated to provide a desired thickness of carbon doped silicon oxide film before steps f to g are conducted. In other embodiments, steps f to g are conducted before steps d to e are performed. According to an exemplary embodiment the carbon content of the film is 0.5 atomic weight percent (at. %) or greater as measured by x-ray photospectroscopy.
[0025] In the formulas above and throughout the description, the term “alkyl” denotes a linear or branched functional group having from 1 to 10, 3 to 10, or 1 to 6 carbon atoms. Exemplary linear alkyl groups include, but are not limited to, methyl, ethyl, n-propyl (n-Pr or Prn), n-butyl, n-pentyl, and n-hexyl groups. Exemplary branched alkyl groups include, but are not limited to, iso-propyl (i-Pr or Pr'), isobutyl (i-Bu or Bu'), sec-butyl (s-Bu or Bus, tert-butyl (t-Bu or Bu‘, iso-pentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl group may have one or more functional groups such as, but not limited to, an alkoxy group, a dialkylamino group or combinations thereof, attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto. The alkyl group may be saturated or unsaturated.
[0026] In the formulas above and throughout the description, the term “aryl” denotes an aromatic cyclic functional group having from 3 to 10 carbon atoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.
[0027] In the formulas above and throughout the description, the term “organoamino” denotes a primary or secondary organic amino group having at least one carbon-based substituent on the nitrogen atom selected from the group of a linear or branched Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group. Secondary amino groups have the option for the organic substituents to either be linked to form a ring, or not to be linked to form a ring. Exemplary organoamino groups include, but are not limited to, methylamino, ethylamino, n-propylamino, iso-propylamino, sec-butylamino, tertbutylamino, iso-butylamino, tert-amylamino, cyclopentylamino, cyclohexylamino, phenylamino, dimethylamino, diethylamino, ethylmethylamino, di-n-propylamino, di- iso-propylamino, di-sec-butylamino, pyrrolidino, pyrrolyl, imidazolyl, piperidino, and 2,6-dimethylpiperidino.
[0028] Throughout the description, the term “silicon-containing film” denotes a film comprising silicon and oxygen atoms. Examples of such films include, but not limited to, silicon oxide, carbon doped silicon oxide, carbon doped silicon oxynitride.
[0029] Throughout the description, the term “purge gas” refers to an inert gas which is not reactive and can be selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), neon (Ne), hydrogen (H2), and mixtures thereof.
[0030] In certain embodiments, substituents R1 and R2 in Formulae I A or IB can be linked together to form a ring structure. As the skilled person will understand, where R3 and R4 are linked together to form a ring R3 will include a bond for linking to R4 and vice versa. In these embodiments, the ring structure can be unsaturated such as, for example, a cyclic alkyl ring, or saturated, for example, an aryl ring. Further, in these embodiments, the ring structure can also be substituted or substituted. Exemplary cyclic ring groups include, but not limited to, pyrrolidino, 2-methylpyrrolidino, 2,5- dimethylpyrrolidino, piperidino, and 2,6-dimethylpiperidino groups. In other embodiments, however, substituents R1 and R2 are not linked. [0031] In certain embodiments, the silicon-containing films deposited using the methods described herein are formed in the presence of oxygen using an oxygen source, reagent or precursor comprising oxygen. An oxygen source may be introduced into the reactor in the form of at least one oxygen source and/or may be present incidentally in the other precursors used in the deposition process. Suitable oxygen source gases may include, for example, water (H2O) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide, oxygen (O2), hydrogen peroxide, oxygen plasma, ozone (O3), N2O plasma, NO2 plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters (seem) or from about 1 to about 1000 seem. The oxygen source can be introduced for a time that ranges from about 0.1 to about 100 seconds. In one particular embodiment, the oxygen source comprises water having a temperature of 10°C or lower. In embodiments wherein the film is deposited by an ALD or a cyclic CVD process, the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the oxygen source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds. In yet another embodiment, the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge inbetween. The oxygen source or reagent is provided in a molecular amount less than a 1 :1 ratio to the silicon precursor, so that at least some carbon is retained in the as deposited dielectric film.
[0032] In certain embodiments, the silicon oxide films further comprise nitrogen. In these embodiments, the films are deposited using the methods described herein and formed in the presence of a nitrogen-containing source. A nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and/or may be present incidentally in the other precursors used in the deposition process. Suitable nitrogen-containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixture thereof. In certain embodiments, the nitrogen-containing source comprises an ammonia plasma or hydrogen/nitrogen plasma source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (seem) or from about 1 to about 1000 seem. The nitrogen- containing source can be introduced for a time that ranges from about 0.1 to about 100 seconds. In embodiments wherein the film is deposited by an ALD or a cyclic CVD process, the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the nitrogen-containing source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds. In yet another embodiment, the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge inbetween.
[0033] The deposition methods disclosed herein may involve one or more purge gases. The purge gas, which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon (Ne), hydrogen (H2), and mixtures thereof. In certain embodiments, a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 seem for about 0.1 to 1000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.
[0034] The respective step of supplying the precursors, oxygen source, the nitrogen-containing source, and/or other precursors, source gases, and/or reagents may be performed by changing the time for supplying them to change the stoichiometric composition of the resulting dielectric film.
[0035] Energy is applied to the at least one of the silicon precursor, oxygen containing source, or combination thereof to induce reaction and to form the dielectric film or coating on the substrate. Such energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments wherein the deposition involves plasma, the plasma-generated process may comprise a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.
[0036] The at least one organoamino-carbosilane precursors may be delivered to the reaction chamber such as a cyclic CVD or ALD reactor in a variety of ways. In one embodiment, a liquid delivery system may be utilized. In an alternative embodiment, a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein may be delivered in neat liquid form, or alternatively, may be employed in solvent formulations or compositions comprising same. Thus, in certain embodiments the precursor formulations may include solvent component(s) of suitable character as may be desirable and advantageous in each end use application to form a film on a substrate.
[0037] For those embodiments wherein the at least one having Si-C-Si linkage precursor(s) having Formulae IA or IB or IC is used in a composition comprising a solvent and an at least one organoamino-carbosilane having Si-C-Si linkage precursor following Formulae IA or IB or IC described herein, the solvent or mixture thereof selected does not react with the silicon precursor. The amount of solvent by weight percentage in the composition ranges from 0.5% by weight to 99.5% or from 10% by weight to 75%. In this or other embodiments, the solvent has a boiling point (b.p.) similar to the b.p. of the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC or the difference between the b.p. of the solvent and the b.p. of the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC is 40 C or less, 30 °C or less, or 20°C or less, or 10°C or less. Alternatively, the difference between the boiling points ranges from any one or more of the following end-points: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of b.p. difference include without limitation, 0 to 40°C, 20° to 30°C, or 10° to 30°C. Examples of suitable solvents in the compositions include, but are not limited to, an ether (such as 1,4-dioxane, dibutyl ether), a tertiary amine (such as pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'- Dimethylpiperazine, N,N,N',N'-Tetramethylethylenediamine), a nitrile (such as benzonitrile), an alkane (such as octane, nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene, mesitylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.
[0038] As previously mentioned, the purity level of the at least one organoamino- carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC is sufficiently high enough to be acceptable for reliable semiconductor manufacturing. In certain embodiments, the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC described herein comprise less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight of one or more of the following impurities: free amines, free halides or halogen ions, and higher molecular weight species. Higher purity levels of the organoamino-carbosilane having Si-C-Si linkage described herein can be obtained through one or more of the following processes: purification, adsorption, and/or distillation.
[0039] In one embodiment of the method described herein, a cyclic deposition process such as ALD-like, ALD, or PEALD may be used wherein the deposition is conducted using the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC and an oxygen source. The ALD-like process is defined as a cyclic CVD process but still provides high conformal silicon oxide films.
[0040] In certain embodiments, the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures depending upon the process requirements and the container of the at least one organoamino- carbosilane having Si-C-Si linkage precursor of Formula IA or IB or IC is kept at one or more temperatures for bubbling. In other embodiments, a solution comprising the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formula IA or IB or IC is injected into a vaporizer kept at one or more temperatures for direct liquid injection.
[0041] A flow of argon and/or other gas may be employed as a carrier gas to help deliver the vapor of the at least one organoamino-carbosilane having Si-C-Si linkage precursor of Formulae IA or IB or IC to the reaction chamber during the precursor pulsing. In certain embodiments, the reaction chamber process pressure is about 1 Torr.
[0042] In a typical ALD or an ALD-like process such as a CCVD process, the substrate such as a silicon oxide substrate is heated on a heater stage in a reaction chamber that is exposed to the organoamino-carbosilane having Si-C-Si linkage initially to allow the complex to chemically adsorb onto the surface of the substrate.
[0043] A purge gas such as argon purges away unabsorbed excess complex from the process chamber. After sufficient purging, an oxygen source may be introduced into reaction chamber to react with the absorbed surface followed by another gas purge to remove reaction by-products from the chamber. The process cycle can be repeated to achieve the desired film thickness. In some cases, pumping can replace a purge with inert gas or both can be employed to remove unreacted organoamino- carbosilane precursors.
[0044] In this or other embodiments, it is understood that the steps of the methods described herein may be performed in a variety of orders, may be performed sequentially, may be performed concurrently (e.g., during at least a portion of another step), and any combination thereof. The respective step of supplying the precursors and the oxygen source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting dielectric film.
[0045] A PEALD process for this or other embodiments may include a hydrogen and inert gas combination in plasma. The inert gas may be selected from argon, neon, helium, and combinations thereof.
[0046] Process temperature for the method described herein are one or more temperatures ranging from 20 °C to 600 °C; or 50 °C to 500 °C; or 100 °C to 500 °C; or 100 °C to 600 °C; or 100 °C to 700 °C;
[0047] Deposition pressure ranges are one or more pressures ranging from 50 miliTorr (mT) to 760 Torr, or from 500 mT - 100 Torr. Purge gases can be selected from inert gases such as nitrogen, helium or argon as well as other non-reactive gases. An oxygen source may be selected from oxygen, a composition comprising oxygen and hydrogen, hydrogen peroxide, ozone or molecular oxygen from plasma process.
[0048] The organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC can be synthesized, for example, by catalytic dehydrocoupling of an organoamine with a carbosilane having at least one Si-H bond, or by reaction of organoamine or metallated organoamide with halogenated carbosilane having at least one Si-X bond (X = Cl, Br, I), or by reduction of organoamino-halido-carbosilanes by metal hydrides (for example, Equations 1 to 6 for IB).
The catalyst employed in the method of the present invention in equation (1) or (3) is one that promotes the formation of a silicon-nitrogen bond. Exemplary catalysts that can be used with the method described herein include but are not limited to the following: alkaline earth metal catalysts; halide-free main group, transition metal, lanthanide, and actinide catalysts; and halide-containing main group, transition metal, lanthanide, actinide catalysts, pure noble metals such as ruthenium platinum, palladium, rhodium, osmium can also be affixed to a support. The support is a solid with a high surface area. Typical support materials include but are not limited to: alumina, MgO, zeolites, carbon, Monolith cordierite, diatomaceous earth, silica gel, silica/alumina, ZrO and TiC>2. Preferred supports are carbon (for examples, platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon) alumina, silica and MgO.
[0049] The organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC according to the present invention and compositions comprising the silicon precursor compounds having Formulae IA or IB or IC according to the present invention are preferably substantially free of halide ions. As used herein, the term “substantially free” as it relates to halide ions (or halides) such as, for example, chlorides (i.e. chloride-containing species such as HCI or silicon compounds having at least one Si-CI bond) and fluorides, bromides, and iodides, means less than 5 ppm (by weight) measured by ion chromatography (IC), preferably less than 3 ppm measured by IC, and more preferably less than 1 ppm measured by IC, and most preferably 0 ppm measured by ICP-MS. Chlorides are known to act as decomposition catalysts for the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC. Significant levels of chloride in the final product can cause the silicon precursor compounds to degrade. The gradual degradation of the organoamino-carbosilane having Si-C-Si linkage compounds may directly impact the film deposition process making it difficult for the semiconductor manufacturer to meet film specifications. In addition, the shelf-life or stability is negatively impacted by the higher degradation rate of the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC thereby making it difficult to guarantee a 1-2 year shelf-life. Therefore, the accelerated decomposition of the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae I A or IB or I C presents safety and performance concerns related to the formation of these flammable and/or pyrophoric gaseous byproducts. The organoamino- carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC are preferably substantially free of metal ions such as, Li+, Na+, K+, Mg2+, Ca2+, Al3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+. As used herein, the term “substantially free” as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS. In some embodiments, the organoamino-carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC are free of metal ions such as, Li+, Na+, K+, Mg2+, Ca2+, Al3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+. As used herein, the term “free of” metal impurities as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, noble metal such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis, means less than 1 ppm, preferably 0.1 ppm (by weight) as measured by ICP-MS or other analytical method for measuring metals. The organoamino- carbosilane having Si-C-Si linkage compounds having Formulae IA or IB or IC according to the present invention and compositions comprising the silicon precursor compounds having Formulae IA or IB or IC according to the present invention are having purity of 98% or higher, preferably 99% or higher, most preferably 99.5% or higher based on Gas Chromatography (GC) analysis.
EXAMPLES
[0050] Example 1 : Synthesis of 2-dimethylamino-2, 4, 4-trimethyl-2,4-disilapentane
[0051] Under the protection of a nitrogen atmosphere, 2,2,4-trimethyl-2,4- disilapentane was added dropwise to a stirred mixture of dimethylamine (512 mL of 2.0 M solution in THF, 1.03 mol) and 30 wt% palladium on carbon powder (2.00 g, 0.00564 mol) in a 1 liter 3-neck flask equipped with a dry ice condenser while heating to reflux. The resulting reaction mixture was allowed to cool to room temperature and stir overnight. The desired product was identified by GC-MS. GC-MS showed the following peaks: 189 (M+), 174 (M-15), 158, 145, 131 , 115, 102, 85, 73, 59, 45. Removal of solvent under reduced pressure followed by vacuum-transfer of the product from the catalyst solids yielded crude product with a purity of 93% as measured by GC. This was subjected to vacuum-distillation to obtain pure 2- dimethylamino-2,4,4-trimethyl-2,4-disilapentane.
[0052] Example 2. Synthesis of 2,4-bis(diethylamino)-2,4-disilapentane
[0053] [0049] Under the protection of nitrogen, diethylamine (21 .9 g, 300 mmol) was added dropwise to a mixture of 2,4-disilapentane (15.6 g, 150 mmol) and ruthenium dodecacarbonyl (0.13 g, 0.20 mmol) at room temperature while stirring in a 100 mL two-necked round bottom flask equipped with a magnetic stir bar. The reaction was allowed to stir for 1 week while being vented to allow for hydrogen byproduct to escape. 2,4-bis(diethylamino)-2,4-disilapentane was detected by GC and GC-MS as the major product. GC-MS showed the following mass peaks: m/z = 246 (M+), 174, 158, 144, 130, 116, 103, 94, 86, 73, 59, 43.
[0054] Example 3. Synthesis of 2,4-bis(dimethylamino)-2,4-disilapentane [0055] [0050] Under the protection of nitrogen, a 2.0 M solution of dimethylamine in THF (3.0 mL, 6 mmol) was added to 2,4-disilapentane (0.31 g, 3 mmol) in a scintillation vial. To this stirred mixture was added a THF solution of ruthenium dodecacarbonyl
[0056] (0.004 g, 0.006 mmol, dissolved in 1 mL THF). The reaction was allowed to stir at room temperature for 1 day while being vented to allow the hydrogen byproduct to escape. 2,4-bis(dimethylamino)-2,4-disilapentane was detected by GC and GC-MS to be the major product. GC-MS showed the following mass peaks: m/z = 190 (M+), 146, 130, 116, 103, 88, 73, 59, 45.
[0057] Example 4. Synthesis of 2,4-bis(dimethylamino)-2,4-dimethyl-2,4- disilapentane
[0058] Under the protection of nitrogen, dimethylamine (0.84 g, 18.7 mmol) was added dropwise as a 2M solution in THF to a solution of bis(chlorodimethylsilyl)methane (0.94 g, 4.7 mmol) in 5mL hexanes at room temperature while stirring in a 20 mL scintillation vial equipped with a magnetic stir bar. The reaction was allowed to stir for one hour and bis(dimethylaminodimethylsilyl)methane was detected by GC and GC-MS as the major product. GC-MS showed the following mass peaks: m/z = 218 (M+), 173, 158, 144, 131, 117, 102, 94, 86, 73, 59, 45.
[0059] Example s. Synthesis of 2-dimethylamino-2,4-disilapentane
[0060] Under the protection of nitrogen, dimethylamine (4.02 g, 89.2 mmol) was added dropwise as a 2M solution in THF to a mixture of 2,4-disilapentane (4.65 g, 44.6 mmol) and ruthenium dodecacarbonyl (0.06 g, 0.09 mmol) in hexanes and THF at room temperature while stirring in a 250 mL two-necked round bottom flask equipped with a magnetic stir bar. The reaction was allowed to stir for three days and 2-dimethylamino-2,4-disilapentane was detected by GC and GC-MS as the major product. GC-MS showed the following mass peaks: m/z = 147 (M+), 132, 116, 103, 88, 73, 59, 44.
[0061] Example 6: Atomic layer deposition of silicon-containing film using 2- dimethylamino-2,4,4-trimethyl-2,4-disilapentane
[0062] Atomic layer deposition of silicon-containing films was conducted using 2- dimethylamino-2,4,4-trimethyl-2,4-disilapentane as a silicon precursor. The depositions were performed on a laboratory scale ALD processing tool. The organoamino-carbosilane having a Si-C-Si linkage is delivered to the chamber by vapor draw. The Si precursor container was heated to 38 °C to reach vapor pressure of about 3 torr. All gases (e.g., purge and reactant gas or precursor and oxygen source) were preheated to 100°C prior to entering the deposition zone. Gases and precursor flow rates were controlled with ALD diaphragm valves with high-speed actuation. The substrates used in the deposition were 12-inch-long silicon strips. A thermocouple attached on the sample holder to confirm substrate temperature. Depositions were performed using ozone as oxygen source gas. Deposition parameters are provided in Table 4. [0063] Table 4: Process for Atomic Layer Deposition of Silicon Oxide Films with
Ozone Using 2-dimethylamino-2,4,4-trimethyl-2,4-disilapentane
Steps 6 to 14 were repeated multiple times to get desired thickness. Film growth per cycle (GPC) was calculated by dividing film thickness with the number of repeated steps. The deposited silicon-containing film has GPC of 1.3 A/cycle with refractive index of 1.5. The infrared spectrum (FTIR) in Figure 1 represents a Si-containing film composition as evidenced by Si-0 related absorbance bands at 810 cm-1 and 1055 cm-1 , as well as a Si-CHs band at 1250 cm-1.

Claims

1. A process to deposit a silicon oxide film onto a substrate comprises steps of: a) providing a substrate in a reactor; b) introducing into the reactor at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formulae IA, wherein R1 and R2 are each independently selected from hydrogen, a linear or branched Ci to Cw alkyl group, a C3 to C10 cyclic alkyl group, a C2 to C10 alkenyl group, and a Ce to C10 aryl group; R3-6 are each independently selected from hydrogen and methyl; R7 is selected from hydrogen, methyl, and NR8R9 wherein R8 and R9 are each independently selected from hydrogen, a linear or branched Ci to Cw alkyl group, and a Ce to Cw aryl group with a provisos that R3'7 cannot be all hydrogen for IA, R3'6 cannot be all hydrogen if R7 is NR8R9 in IA, R3'6 cannot be all methyl if R7 is NR8R9 in IB, R1'2 cannot both be hydrogen, and R8'9 cannot both be hydrogen, and wherein R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure; c) purging the reactor with purge gas; d) introducing an oxygen source into the reactor; and e) purging the reactor with purge gas; wherein steps b through e are repeated until a desired thickness of silicon oxide is deposited, wherein the process in conducted at one or more temperatures ranging from 20 to 700°C and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.
2. The process of claim 1 , wherein the at least one organoamino-carbosilane precursor compound according to Formula IA is selected from the group consisting of 2-dimethylamino-2,4,4-trimethyl-2,4-disilapentane, 2-dimethylamino-2,4-disilabutane, 2-diethylamino-2,4,4-trimethyl-2,4-disilapentane, 2-diethylamino-2,4-disilabutane, 2- ethylmethylamino-2,4,4-trimethyl-2,4-disilapentane, 2-ethylmethylamino-2,4- disilabutane, 2-di-iso-propylamino-2,4,4-trimethyl-2,4-disilapentane, 2-di-iso- propylamino-2,4-disilabutane, 2-di-n-propylamino-2,4,4-trimethyl-2,4-disilapentane, 2-di-n-propylamino-2,4-disilabutane, 1-dimethylamino-1 ,3-disilabutane, 2- dimethylamino-2,4-disilapentane, 1-diethylamino-1 ,3-disilabutane, 2-diethylamino-
2,4-disilapentane, 1 -ethylmethylamino- 1 ,3-disilabutane, 2-ethylmethylamino-2,4- disilapentane, 1-di-iso-propylamino-1 ,3-disilabutane, 2-di-iso-propylamino-2,4- disilapentane, 1-di-n-propylamino-1 ,3-disilabutane, 2-di-n-propylamino-2,4- disilapentane, 1-dimethylamino-3-methyl-1 ,3-disilabutane, 2-dimethylamino-4-methyl-
2.4-disilapentane, 1-diethylamino-3-methyl-1 ,3-disilabutane, 2-diethylamino-4- methyl-2,4-disilapentane, 1-ethylmethylamino-3-methyl-1 ,3-disilabutane, 2- ethylmethylamino-4-methyl-2,4-disilapentane, 1-di-iso-propylamino-3-methyl-1,3- disilabutane, 2-di-iso-propylamino-4-methyl-2,4-disilapentane, 1-di-n-propylamino-3- methyl-1 ,3-disilabutane, 2-di-n-propylamino-4-methyl-2,4-disilapentane, 1- dimethylamino-3,3-dimethyl-1,3-disilabutane, 2-dimethylamino-4,4-dimethyl-2,4- disilapentane, 1-diethylamino-3,3-dimethyl-1 ,3-disilabutane, 2-diethylamino-4,4- dimethyl-2,4-disilapentane, 2-pyrrolidino-2,4-disilabutane, 2-(2-methylpyrrolidino)-2,4- disilabutane, 2-pyrrolyl-2,4-disilabutane, 2-imidazolyl-2,4-disilabutane, 2-pyrollyl-
2.4.4-trimethyl-2,4-disilapentane, 2-pyrrolidino-2,4,4-trimethyl-2,4-disilapentane, 2- piperidino-2,4,4-trimethyl-2,4-disilapentane, 2-(2,6-dimethylpiperidino)-2,4,4- trimethyl-2,4-disilapentane, 2,4-bis(dimethylamino)-2,4-dimethyl-2,4-disilapentane,
2.4-bis(ethylmethylamino)-2,4-dimethyl-2,4-disilapentane, 2,4-bis(diethylamino)-2,4- dimethyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,4-dimethyl-2,4- disilapentane, 2,4-bis(dimethylamino)-2,4-disilapentane, 2,4-bis(ethylmethylamino)-
2.4-disilapentane, 2,4-bis(diethylamino)-2,4-disilapentane, 2,4-bis(di-iso- propylamino)-2,4-disilapentane, 2,4-bis(di-n-propylamino)-2,4-disilapentane, 2,4- bis(di-sec-butylamino)-2,4-disilapentane, 2,4-bis(pyrrolyl)-2,4-disilapentane, 2,4- bis(pyrrolidino)-2,4-disilapentane, 2,4-bis(imidazolyl)-2,4-disilapentane, 2,4-bis(2- methylpyrrolidino)-2,4-disilapentane, 2,4-bis(piperidino)-2,4-disilapentane, 2,4- bis(2,6-dimethylpiperidino)-2,4-disilapentane, and combinations thereof.
3. The process of claim 1, wherein the at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IB is selected from the group consisting of 1-dimethylamino-2-methyl-1,3-disilapropane, 2- dimethylamino-3-methyl-2,4-disilabutane, 1-diethylamino-2-methyl-1 ,3-disilapropane, 2-diethylamino-3-methyl-2,4-disilabutane, 1-ethylmethylamino-2-methyl-1 ,3- disilapropane, 2-ethylmethylamino-3-methyl-2,4-disilabutane, 1-di-iso-propylamino-2- methyl-1 ,3-disilapropane, 2-di-iso-propylamino-3-methyl-2,4-disilabutane, 1-di-n- propylamino-2-methyl-1 ,3-disilapropane, 2-di-n-propylamino-3-methyl-2,4- disilabutane, 1-dimethylamino-2-methyl-1 ,3-disilabutane, 2-dimethylamino-3-methyl- 2,4-disilapentane, 1-diethylamino-2-methyl-1 ,3-disilabutane, 2-diethylamino-3- methyl-2,4-disilapentane, 1-ethylmethylamino-2-methyl-1 ,3-disilabutane, 2- ethylmethylamino-3-methyl-2,4-disilapentane, 1-di-iso-propylamino-2-methyl-1 ,3- disilabutane, 2-di-iso-propylamino-3-methyl-2,4-disilapentane, 1-di-n-propylamino-2- methyl-1 ,3-disilabutane, 2-di-n-propylamino-3-methyl-2,4-disilapentane, 1- dimethylamino-2,3-dimethyl-1 ,3-disilabutane, 2-dimethylamino-3,4-dimethyl-2,4- disilapentane, 1-diethylamino-2,3-dimethyl-1 ,3-disilabutane, 2-diethylamino-3,4- dimethyl-2,4-disilapentane, 1-ethylmethylamino-2,3-dimethyl-1 ,3-disilabutane, 2- ethylmethylamino-3,4-dimethyl-2,4-disilapentane, 1-di-iso-propylamino-2,3-dimethyl-
1.3-disilabutane, 2-di-iso-propylamino-3,4-dimethyl-2,4-disilapentane, 1-di-n- propylamino-2,3-dimethyl-1 ,3-disilabutane, 2-di-n-propylamino-3,4-dimethyl-2,4- disilapentane, 1-dimethylamino-2-methyl-3,3-dimethyl-1 ,3-disilabutane, 2- dimethylamino-3,4,4-trimethyl-2,4-disilapentane, 1-diethylamino-2,3,3-trimethyl-1 ,3- disilabutane, 2-diethylamino-3,4,4-trimethyl-2,4-disilapentane, 1-pyrrolidino-2-methyl-
1.3-disilapropane, 1-(2-methylpyrrolidino)-2-methyl-1 ,3-disilapropane, 2-pyrrolidino-3- methyl-2,4-disilabutane, 2-(2-methylpyrrolidino)-3-methyl-2,4-disilabutane, 1- piperidino-2-methyl-1 ,3-disilapropane, 1-(2,6-dimethylpiperidino)-2-methyl-1 ,3- disilapropane, 1-pyrrolyl-2-methyl-1 ,3-disilapropane , 1-imidazolyl-2-methyl-1 ,3- disilapropane, 2-pyrrolyl-3-methyl-2,4-disilabutane, 2-imidazolyl-3-methyl-2,4- disilabutane, 2-dimethylamino-2,3,4,4-tetramethyl-2,4-disilapentane, 2- ethylmethylamino-2,3,4,4-tetramethyl-2,4-disilapentane, 2-di-n-propylamino-2, 3,4,4- tetramethyl-2,4-disilapentane, 2-di-iso-propylamino-2,3,4,4-tetramethyl-2,4- disilapentane, 2-pyrrolyl-2,3,4,4-tetramethyl-2,4-disilapentane, 2-pyrrolidino-2, 3,4,4- tetramethyl-2,4-disilapentane, 1 ,3-bis(dimethylamino)-2-methyl-1 ,3-disilapropane,
2.4-bis(dimethylamino)-3-methyl-2,4-disilapentane, 1 ,3-bis(diethylamino)-2-methyl-
1 ,3-disilapropane, 2,4-bis(diethylamino)-3-methyl-2,4-disilapentane, 2,4- bis(diethylamino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3-bis(methylethylamino)-2- methyl-1 ,3-disilapropane, 2,4-bis(methylethylamino)-3-methyl-2,4-disilapentane, 2,4- bis(methylethylamino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3-bis(di-iso-propylamino)- 2-methyl-1 ,3-disilapropane, 2,4-bis(di-iso-propylamino)-3-methyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,3,4-trimethyl-2,4-disilapentane, 1,3-bis(n-propylamino)- 2-methyl-1 ,3-disilapropane, 2,4-bis(n-propylamino)-3-methyl-2,4-disilapentane, 2,4- bis(n-propylamino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3-bis(pyrrolyl)-2-methyl-1 ,3- disilapropane, 2,4-bis(pyrrolyl)-3-methyl-2,4-disilapentane, 2,4-bis(pyrrolyl)-2,3,4- trimethyl-2,4-disilapentane, 1 ,3-bis(pyrrolidino)-2-methyl-1 ,3-disilapropane, 2,4- bis(pyrrolidino)-3-methyl-2,4-disilapentane, 2,4-bis(pyrrolidino)-2,3,4-trimethyl-2,4- disilapentane, 1 ,3-bis(piperidino)-2-methyl-1 ,3-disilapropane, 2,4-bis(piperidino)-3- methyl-2,4-disilapentane, 2,4-bis(piperidino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3- bis(2,6-dimethylpiperidino)-2-methyl-1 ,3-disilapropane, 2,4-bis(2,6- dimethylpiperidino)-3-methyl-2,4-disilapentane, 2,4-bis(2,6-dimethylpiperidino)-2,3,4- trimethyl-2,4-disilapentane, and combinations thereof.
4. The process of claim 1, wherein the at least one organoamino-carbosilane precursor compound having a Si-C-Si linkage according to Formula IC is selected from the group consisting of 1-dimethylamino-2,2-dimethyl-1,3-disilapropane, 2- dimethylamino-3,3-dimethyl-2,4-disilabutane, 1-dimethylamino-2,2-dimethyl-1 ,3- disilabutane, 2-dimethylamino-3,3-dimethyl-2,4-disilapentane, 2-dimethylamino-3,3,4- trimethyl-2,4-disilapentane, 2-dimethylamino-2,3,3,4-tetramethyl-2,4-disilapentane, 2- dimethylamino-3,3,4,4-tetramethyl-2,4-disilapentane, 2-dimethylamino-2,3,3,4,4- pentamethyl-2,4-disilapentane, 1-diethylamino-2,2-dimethyl-1 ,3-disilapropane, 2- diethylamino-3,3-dimethyl-2,4-disilabutane, 1-diethylamino-2,2-dimethyl-1,3- disilabutane, 2-diethylamino-3,3-dimethyl-2,4-disilapentane, 2-diethylamino-3,3,4- trimethyl-2,4-disilapentane, 2-diethylamino-2,3,3,4-tetramethyl-2,4-disilapentane, 2- diethylamino-3,3,4,4-tetramethyl-2,4-disilapentane, 2-diethylamino-2,3,3,4,4- pentamethyl-2,4-disilapentane, 1-ethylmethylamino-2,2-dimethyl-1 ,3-disilapropane, 2-ethylmethylamino-3,3-dimethyl-2,4-disilabutane, 1-ethylmethylamino-2,2-dimethyl-
1.3-disilabutane, 2-ethylmethylamino-3,3-dimethyl-2,4-disilapentane, 2- ethylmethylamino-3,3,4-trimethyl-2,4-disilapentane, 2-ethylmethylamino-2, 3,3,4- tetramethyl-2,4-disilapentane, 2-ethylmethylamino-3,3,4,4-tetramethyl-2,4- disilapentane, 2-ethylmethylamino-2,3,3,4,4-pentamethyl-2,4-disilapentane, 1-di- isopropylamino-2,2-dimethyl-1,3-disilapropane, 2-di-isopropylamino-3,3-dimethyl-2,4- disilabutane, 1-di-isopropylamino-2,2-dimethyl-1 ,3-disilabutane, 2-di-isopropylamino-
3.3-dimethyl-2,4-disilapentane, 2-di-isopropylamino-3,3,4-trimethyl-2,4-disilapentane, 2-di-isopropylamino-2,3,3,4-tetramethyl-2,4-disilapentane, 2-di-isopropylamino- 3,3,4,4-tetramethyl-2,4-disilapentane, 2-di-isopropylamino-2,3,3,4,4-pentamethyl-2,4- disilapentane, 1-pyrrolidino-2,2-dimethyl-1 ,3-disilapropane, 2-pyrrolidino-3,3- dimethyl-2,4-disilabutane, 1-pyrrolidino-2,2-dimethyl-1 ,3-disilabutane, 2-pyrrolidino-
3.3-dimethyl-2,4-disilapentane, 2-pyrrolidino-3,3,4-trimethyl-2,4-disilapentane, 2- pyrrolidino-2,3,3,4-tetramethyl-2,4-disilapentane, 2-pyrrolidino-3,3,4,4-tetramethyl-
2.4-disilapentane, 2-pyrrolidino-2,3,3,4,4-pentamethyl-2,4-disilapentane, 1 -pyrrolyl-
2.2-dimethyl-1 ,3-disilapropane, 2-pyrrolyl-3,3-dimethyl-2,4-disilabutane, 1 -pyrrolyl-
2.2-dimethyl-1 ,3-disilabutane, 2-pyrrolyl-3,3-dimethyl-2,4-disilapentane, 2-pyrrolyl-
3.3.4-trimethyl-2,4-disilapentane, 2-pyrrolyl-2,3,3,4-tetramethyl-2,4-disilapentane, 2- pyrrolyl-3,3,4,4-tetramethyl-2,4-disilapentane, 2-pyrrolyl-2,3,3,4,4-pentamethyl-2,4- disilapentane, 1 ,3-bis(dimethylamino)-2,2-dimethyl-1 ,3-disilapropane, 2,4- bis(dimethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4-bis(dimethylamino)-2,3,3,4- tetramethyl-2,4-disilapentane, 1 ,3-bis(diethylamino)-2,2-dimethyl-1 ,3-disilapropane,
2.4-bis(diethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4-bis(diethylamino)-2,3,3,4- tetramethyl-2,4-disilapentane, 1 ,3-bis(ethylmethylamino)-2,2-dimethyl-1 ,3- disilapropane, 2,4-bis(ethylmethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4- bis(ethylmethylamino)-2,3,3,4-tetramethyl-2,4-disilapentane, 1 ,3-bis(di-iso- propylamino)-2,2-dimethyl-1 ,3-disilapropane, 2,4-bis(di-iso-propylamino)-3,3- dimethyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,3,3,4-tetramethyl-2,4- disilapentane, 2,4-bis(di-sec-butylamino)-2,3,3,4-tetramethyl-2,4-disilapentane, 2,4- bis(pyrrolidino)-2,3,3,4-tetramethyl-2,4-disilapentane, 2,4-bis(pyrrolyl)-2,3,3,4- tetramethyl-2,4-disilapentane, 2,4-bis(piperidino)-2,3,3,4-tetramethyl-2,4- disilapentane, and combinations thereof.
5. The process of claim 1, wherein the purge gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof.
6. The process of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide, ozone source, and mixtures thereof.
7. The method of claim 1 wherein the oxygen-containing source comprises a plasma.
8. The method of claim 7 wherein the plasma is generated in situ.
9. The method of claim 7 wherein the plasma is generated remotely.
10. The method of claim 1 wherein the film further comprises carbon wherein the carbon content of the film is 0.5 atomic weight percent (at. %) or greater as measured by x-ray photospectroscopy.
11. A composition for depositing a silicon-containing film using a vapor deposition process, wherein the composition comprises: at least one silicon precursor having a structure according to Formulae IA, IB, or IC: wherein R1 and R2 are each independently selected from hydrogen, a linear or branched Ci to Cw alkyl group, and a Ce to Cw aryl group; R3-6 are each independently selected from hydrogen and methyl; R7 is selected from hydrogen, methyl, and NR8R9 wherein R8 and R9 are each independently selected from hydrogen, a linear or branched Ci to C alkyl group, and a Ce to Cw aryl group with a provisos that R3'7 cannot be all hydrogen for I A, R3'6 cannot be all hydrogen if R7 is NR8R9 in IA, R3'6 cannot be all methyl if R7 is NR8R9 in IB, R1'2 cannot both be hydrogen, and R8'9 cannot both be hydrogen, and wherein R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.
12. The composition of claim 11 , wherein the at least one silicon precursor with Formula IA is selected from the group consisting of 2-dimethylamino-2,4,4-trimethyl- 2,4-disilapentane, 2-dimethylamino-2,4-disilabutane, 2-diethylamino-2,4,4-trimethyl- 2,4-disilapentane, 2-diethylamino-2,4-disilabutane, 2-ethylmethylamino-2,4,4- trimethyl-2,4-disilapentane, 2-ethylmethylamino-2,4-disilabutane, 2-di-iso- propylamino-2,4,4-trimethyl-2,4-disilapentane, 2-di-iso-propylamino-2,4-disilabutane, 2-di-n-propylamino-2,4,4-trimethyl-2,4-disilapentane, 2-di-n-propylamino-2,4- disilabutane, 1-dimethylamino-1,3-disilabutane, 2-dimethylamino-2,4-disilapentane, 1-diethylamino-1 ,3-disilabutane, 2-diethylamino-2,4-disilapentane, 1- ethylmethylamino-1 ,3-disilabutane, 2-ethylmethylamino-2,4-disilapentane, 1-di-iso- propylamino-1 ,3-disilabutane, 2-di-iso-propylamino-2,4-disilapentane, 1-di-n- propylamino-1 ,3-disilabutane, 2-di-n-propylamino-2,4-disilapentane, 1- dimethylamino-3-methyl-1,3-disilabutane, 2-dimethylamino-4-methyl-2,4- disilapentane, 1-diethylamino-3-methyl-1 ,3-disilabutane, 2-diethylamino-4-methyl-
2.4-disilapentane, 1-ethylmethylamino-3-methyl-1 ,3-disilabutane, 2- ethylmethylamino-4-methyl-2,4-disilapentane, 1-di-iso-propylamino-3-methyl-1,3- disilabutane, 2-di-iso-propylamino-4-methyl-2,4-disilapentane, 1-di-n-propylamino-3- methyl-1 ,3-disilabutane, 2-di-n-propylamino-4-methyl-2,4-disilapentane, 1- dimethylamino-3,3-dimethyl-1,3-disilabutane, 2-dimethylamino-4,4-dimethyl-2,4- disilapentane, 1-diethylamino-3,3-dimethyl-1 ,3-disilabutane, 2-diethylamino-4,4- dimethyl-2,4-disilapentane, 2-pyrrolidino-2,4-disilabutane, 2-(2-methylpyrrolidino)-2,4- disilabutane, 2-pyrrolyl-2,4-disilabutane, 2-imidazolyl-2,4-disilabutane, 2-pyrollyl-
2.4.4-trimethyl-2,4-disilapentane, 2-pyrrolidino-2,4,4-trimethyl-2,4-disilapentane, 2- piperidino-2,4,4-trimethyl-2,4-disilapentane, 2-(2,6-dimethylpiperidino)-2,4,4- trimethyl-2,4-disilapentane, 2,4-bis(dimethylamino)-2,4-dimethyl-2,4-disilapentane,
2.4-bis(ethylmethylamino)-2,4-dimethyl-2,4-disilapentane, 2,4-bis(diethylamino)-2,4- dimethyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,4-dimethyl-2,4- disilapentane, 2,4-bis(dimethylamino)-2,4-disilapentane, 2,4-bis(ethylmethylamino)-
2.4-disilapentane, 2,4-bis(diethylamino)-2,4-disilapentane, 2,4-bis(di-iso- propylamino)-2,4-disilapentane, 2,4-bis(di-n-propylamino)-2,4-disilapentane, 2,4- bis(di-sec-butylamino)-2,4-disilapentane, 2,4-bis(pyrrolyl)-2,4-disilapentane, 2,4- bis(pyrrolidino)-2,4-disilapentane, 2,4-bis(imidazolyl)-2,4-disilapentane, 2,4-bis(2- methylpyrrolidino)-2,4-disilapentane, 2,4-bis(piperidino)-2,4-disilapentane, 2,4- bis(2,6-dimethylpiperidino)-2,4-disilapentane, and combinations thereof.
13. The composition of claim 11 , wherein the at least one silicon precursor with Formula IB is selected from the group consisting of 1-dimethylamino-2-methyl-1 ,3- disilapropane, 2-dimethylamino-3-methyl-2,4-disilabutane, 1-diethylamino-2-methyl- 1 ,3-disilapropane, 2-diethylamino-3-methyl-2,4-disilabutane, 1-ethylmethylamino-2- methyl-1 ,3-disilapropane, 2-ethylmethylamino-3-methyl-2,4-disilabutane, 1-di-iso- propylamino-2-methyl-1,3-disilapropane, 2-di-iso-propylamino-3-methyl-2,4- disilabutane, 1-di-n-propylamino-2-methyl-1,3-disilapropane, 2-di-n-propylamino-3- methyl-2,4-disilabutane, 1-dimethylamino-2-methyl-1 ,3-disilabutane, 2- dimethylamino-3-methyl-2,4-disilapentane, 1-diethylamino-2-methyl-1 ,3-disilabutane, 2-diethylamino-3-methyl-2,4-disilapentane, 1-ethylmethylamino-2-methyl-1,3- disilabutane, 2-ethylmethylamino-3-methyl-2,4-disilapentane, 1-di-iso-propylamino-2- methyl-1,3-disilabutane, 2-di-iso-propylamino-3-methyl-2,4-disilapentane, 1-di-n- propylamino-2-methyl-1,3-disilabutane, 2-di-n-propylamino-3-methyl-2,4- disilapentane, 1-dimethylamino-2,3-dimethyl-1 ,3-disilabutane , 2-dimethylamino- 3,4-dimethyl-2,4-disilapentane, 1-diethylamino-2,3-dimethyl-1 ,3-disilabutane , 2- diethylamino-3,4-dimethyl-2,4-disilapentane, 1-ethylmethylamino-2,3-dimethyl-1,3- disilabutane, 2-ethylmethylamino-3,4-dimethyl-2,4-disilapentane, 1-di-iso- propylamino-2,3-dimethyl-1,3-disilabutane, 2-di-iso-propylamino-3,4-dimethyl-2,4- disilapentane, 1-di-n-propylamino-2,3-dimethyl-1 ,3-disilabutane, 2-di-n-propylamino- 3,4-dimethyl-2,4-disilapentane, 1-dimethylamino-2-methyl-3,3-dimethyl-1,3- disilabutane, 2-dimethylamino-3,4,4-trimethyl-2,4-disilapentane, 1 -diethylamino-
2.3.3-trimethyl-1,3-disilabutane, 2-diethylamino-3,4,4-trimethyl-2,4-disilapentane, 1- pyrrolidino-2-methyl-1 ,3-disilapropane, 1-(2-methylpyrrolidino)-2-methyl-1 ,3- disilapropane, 2-pyrrolidino-3-methyl-2,4-disilabutane, 2-(2-methylpyrrolidino)-3- methyl-2,4-disilabutane, 1-piperidino-2-methyl-1,3-disilapropane, 1-(2,6- dimethylpiperidino)-2-methyl-1 ,3-disilapropane, 1-pyrrolyl-2-methyl-1,3-disilapropane, 1-imidazolyl-2-methyl-1 ,3-disilapropane, 2-pyrrolyl-3-methyl-2,4-disilabutane, 2- imidazolyl-3-methyl-2,4-disilabutane, 2-dimethylamino-2,3,4,4-tetramethyl-2,4- disilapentane, 2-ethylmethylamino-2,3,4,4-tetramethyl-2,4-disilapentane, 2-di-n- propylamino-2,3,4,4-tetramethyl-2,4-disilapentane, 2-di-iso-propylamino-2, 3,4,4- tetramethyl-2,4-disilapentane, 2-pyrrolyl-2,3,4,4-tetramethyl-2,4-disilapentane, 2- pyrrolidino-2,3,4,4-tetramethyl-2,4-disilapentane, 1,3-bis(dimethylamino)-2-methyl-
1.3-disilapropane, 2,4-bis(dimethylamino)-3-methyl-2,4-disilapentane, 1 ,3- bis(diethylamino)-2-methyl-1,3-disilapropane, 2,4-bis(diethylamino)-3-methyl-2,4- disilapentane, 2,4-bis(diethylamino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3- bis(methylethylamino)-2-methyl-1,3-disilapropane, 2,4-bis(methylethylamino)-3- methyl-2,4-disilapentane, 2,4-bis(methylethylamino)-2,3,4-trimethyl-2,4- disilapentane, 1 ,3-bis(di-iso-propylamino)-2-methyl-1 ,3-disilapropane, 2,4-bis(di-iso- propylamino)-3-methyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,3,4-trimethyl- 2,4-disilapentane, 1 ,3-bis(n-propylamino)-2-methyl-1 ,3-disilapropane, 2,4-bis(n- propylamino)-3-methyl-2,4-disilapentane, 2,4-bis(n-propylamino)-2,3,4-trimethyl-2,4- disilapentane, 1 ,3-bis(pyrrolyl)-2-methyl-1 ,3-disilapropane, 2,4-bis(pyrrolyl)-3-methyl-
2.4-disilapentane, 2,4-bis(pyrrolyl)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3- bis(pyrrolidino)-2-methyl-1,3-disilapropane, 2,4-bis(pyrrolidino)-3-methyl-2,4- disilapentane, 2,4-bis(pyrrolidino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3- bis(piperidino)-2-methyl-1,3-disilapropane, 2,4-bis(piperidino)-3-methyl-2,4- disilapentane, 2,4-bis(piperidino)-2,3,4-trimethyl-2,4-disilapentane, 1 ,3-bis(2,6- dimethylpiperidino)-2-methyl-1 ,3-disilapropane, 2,4-bis(2,6-dimethylpiperidino)-3- methyl-2,4-disilapentane, 2,4-bis(2,6-dimethylpiperidino)-2,3,4-trimethyl-2,4- disilapentane, and combinations thereof.
14. The composition of claim 11 , wherein the at least one silicon precursor with Formula IC is selected from the group consisting of 1-dimethylamino-2,2-dimethyl- 1 ,3-disilapropane, 2-dimethylamino-3,3-dimethyl-2,4-disilabutane, 1-dimethylamino- 2,2-dimethyl-1 ,3-disilabutane, 2-dimethylamino-3,3-dimethyl-2,4-disilapentane, 2- dimethylamino-3,3,4-trimethyl-2,4-disilapentane, 2-dimethylamino-2, 3,3,4- tetramethyl-2,4-disilapentane, 2-dimethylamino-3,3,4,4-tetramethyl-2,4-disilapentane, 2-dimethylamino-2,3,3,4,4-pentamethyl-2,4-disilapentane, 1-diethylamino-2,2- dimethyl-1,3-disilapropane, 2-diethylamino-3,3-dimethyl-2,4-disilabutane, 1- diethylamino-2,2-dimethyl-1 ,3-disilabutane, 2-diethylamino-3,3-dimethyl-2,4- disilapentane, 2-diethylamino-3,3,4-trimethyl-2,4-disilapentane, 2-diethylamino-
2.3.3.4-tetramethyl-2,4-disilapentane, 2-diethylamino-3,3,4,4-tetramethyl-2,4- disilapentane, 2-diethylamino-2,3,3,4,4-pentamethyl-2,4-disilapentane, 1- ethylmethylamino-2,2-dimethyl-1,3-disilapropane, 2-ethylmethylamino-3,3-dimethyl-
2.4-disilabutane, 1-ethylmethylamino-2,2-dimethyl-1 ,3-disilabutane, 2- ethylmethylamino-3,3-dimethyl-2,4-disilapentane, 2-ethylmethylamino-3,3,4-trimethyl-
2.4-disilapentane, 2-ethylmethylamino-2,3,3,4-tetramethyl-2,4-disilapentane, 2- ethylmethylamino-3,3,4,4-tetramethyl-2,4-disilapentane, 2-ethylmethylamino-
2.3.3.4.4-pentamethyl-2,4-disilapentane, 1-di-isopropylamino-2,2-dimethyl-1 ,3- disilapropane, 2-di-isopropylamino-3,3-dimethyl-2,4-disilabutane, 1-di- isopropylamino-2,2-dimethyl-1,3-disilabutane, 2-di-isopropylamino-3,3-dimethyl-2,4- disilapentane, 2-di-isopropylamino-3,3,4-trimethyl-2,4-disilapentane, 2-di- isopropylamino-2,3,3,4-tetramethyl-2,4-disilapentane, 2-di-isopropylamino-3, 3,4,4- tetramethyl-2,4-disilapentane , 2-di-isopropylamino-2,3,3,4,4-pentamethyl-2,4- disilapentane, 1-pyrrolidino-2,2-dimethyl-1 ,3-disilapropane, 2-pyrrolidino-3,3- dimethyl-2,4-disilabutane, 1-pyrrolidino-2,2-dimethyl-1 ,3-disilabutane, 2-pyrrolidino-
3.3-dimethyl-2,4-disilapentane, 2-pyrrolidino-3,3,4-trimethyl-2,4-disilapentane, 2- pyrrolidino-2,3,3,4-tetramethyl-2,4-disilapentane, 2-pyrrolidino-3,3,4,4-tetramethyl-
2.4-disilapentane, 2-pyrrolidino-2,3,3,4,4-pentamethyl-2,4-disilapentane, 1 -pyrrolyl-
2.2-dimethyl-1 ,3-disilapropane, 2-pyrrolyl-3,3-dimethyl-2,4-disilabutane, 1 -pyrrolyl-
2.2-dimethyl-1 ,3-disilabutane, 2-pyrrolyl-3,3-dimethyl-2,4-disilapentane, 2-pyrrolyl-
3.3.4-trimethyl-2,4-disilapentane, 2-pyrrolyl-2,3,3,4-tetramethyl-2,4-disilapentane, 2- pyrrolyl-3,3,4,4-tetramethyl-2,4-disilapentane, 2-pyrrolyl-2,3,3,4,4-pentamethyl-2,4- disilapentane, 1 ,3-bis(dimethylamino)-2,2-dimethyl-1 ,3-disilapropane, 2,4- bis(dimethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4-bis(dimethylamino)-2,3,3,4- tetramethyl-2,4-disilapentane, 1 ,3-bis(diethylamino)-2,2-dimethyl-1 ,3-disilapropane,
2.4-bis(diethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4-bis(diethylamino)-2,3,3,4- tetramethyl-2,4-disilapentane, 1 ,3-bis(ethylmethylamino)-2,2-dimethyl-1 ,3- disilapropane, 2,4-bis(ethylmethylamino)-3,3-dimethyl-2,4-disilapentane, 2,4- bis(ethylmethylamino)-2,3,3,4-tetramethyl-2,4-disilapentane, 1 ,3-bis(di-iso- propylamino)-2,2-dimethyl-1 ,3-disilapropane, 2,4-bis(di-iso-propylamino)-3,3- dimethyl-2,4-disilapentane, 2,4-bis(di-iso-propylamino)-2,3,3,4-tetramethyl-2,4- disilapentane, 2,4-bis(di-sec-butylamino)-2,3,3,4-tetramethyl-2,4-disilapentane, 2,4- bis(pyrrolidino)-2,3,3,4-tetramethyl-2,4-disilapentane, 2,4-bis(pyrrolyl)-2,3,3,4- tetramethyl-2,4-disilapentane, 2,4-bis(piperidino)-2,3,3,4-tetramethyl-2,4- disilapentane, and combinations thereof.
15. The composition of claim 11 wherein the composition is substantially free of one or more impurities selected from the group consisting of halide compounds, metal ions, metal, and combinations thereof.
16. The composition of claim 15, wherein the chloride concentration is less than 5 ppm measured by IC.
17. A film obtained by the method of claim 1.
18. The film of claim 17 comprising at least one of the following characteristics: a density of at least about 2.0 g/cm3; a wet etch rate that is less than about 2.5 A/s as measured in a solution of 1:100 of HF to water (0.5 wt. % dHF) acid; an electrical leakage of less than about 1 x 10'8 A/cm2 up to 6 MV/cm; and a hydrogen impurity of less than about 4 x 1021 at/cc as measured by SIMS.
PCT/EP2025/061871 2024-04-30 2025-04-30 Organoamino-carbosilanes and methods for depositing siliconcontaining films using same Pending WO2025229081A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463640384P 2024-04-30 2024-04-30
US63/640,384 2024-04-30

Publications (1)

Publication Number Publication Date
WO2025229081A1 true WO2025229081A1 (en) 2025-11-06

Family

ID=95653781

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/061871 Pending WO2025229081A1 (en) 2024-04-30 2025-04-30 Organoamino-carbosilanes and methods for depositing siliconcontaining films using same

Country Status (1)

Country Link
WO (1) WO2025229081A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002158223A (en) * 2000-11-17 2002-05-31 Tri Chemical Laboratory Inc Material and method for forming film and element
US6992019B2 (en) 2002-07-08 2006-01-31 Samsung Electronics Co., Ltd. Methods for forming silicon dioxide layers on substrates using atomic layer deposition
US7084076B2 (en) 2003-02-27 2006-08-01 Samsung Electronics, Co., Ltd. Method for forming silicon dioxide film using siloxane
JP2010225663A (en) 2009-03-19 2010-10-07 Adeka Corp Raw material for chemical vapor deposition, and process for forming silicon-containing thin film using the same
JP2010275602A (en) 2009-05-29 2010-12-09 Adeka Corp Raw material for chemical vapor deposition and method for depositing silicon-containing thin film using the same
US20180105541A1 (en) * 2016-10-14 2018-04-19 Versum Materials Us, Llc Carbon Bridged Aminosilane Compounds for High Growth Rate Silicon-Containing Films
US20200051811A1 (en) * 2013-09-20 2020-02-13 Versum Materials Us, Llc Organoaminosilane Precursors And Methods For Depositing Films Comprising Same
US20220178028A1 (en) * 2019-04-25 2022-06-09 Versum Materials Us, Llc Organoaminodisilazanes for high temperature atomic layer deposition of silicon oxide thin films

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002158223A (en) * 2000-11-17 2002-05-31 Tri Chemical Laboratory Inc Material and method for forming film and element
US6992019B2 (en) 2002-07-08 2006-01-31 Samsung Electronics Co., Ltd. Methods for forming silicon dioxide layers on substrates using atomic layer deposition
US7084076B2 (en) 2003-02-27 2006-08-01 Samsung Electronics, Co., Ltd. Method for forming silicon dioxide film using siloxane
JP2010225663A (en) 2009-03-19 2010-10-07 Adeka Corp Raw material for chemical vapor deposition, and process for forming silicon-containing thin film using the same
JP2010275602A (en) 2009-05-29 2010-12-09 Adeka Corp Raw material for chemical vapor deposition and method for depositing silicon-containing thin film using the same
US20200051811A1 (en) * 2013-09-20 2020-02-13 Versum Materials Us, Llc Organoaminosilane Precursors And Methods For Depositing Films Comprising Same
US20180105541A1 (en) * 2016-10-14 2018-04-19 Versum Materials Us, Llc Carbon Bridged Aminosilane Compounds for High Growth Rate Silicon-Containing Films
US20220178028A1 (en) * 2019-04-25 2022-06-09 Versum Materials Us, Llc Organoaminodisilazanes for high temperature atomic layer deposition of silicon oxide thin films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WOLF, S.: "Silicon Processing for the VLSI Era Vol. 1 - Process Technology", 1986, LATTICE PRESS

Similar Documents

Publication Publication Date Title
KR102552319B1 (en) High temperature atomic layer deposition of silicon oxide thin film
EP2535343B1 (en) Organoaminosilane precursors and methods for making and using same
US10077364B2 (en) Organoaminodisilane precursors and methods for depositing films comprising same
EP2392691B1 (en) Organoaminosilane precursors and methods for depositing films comprising the same
JP7586837B2 (en) Organoaminodisilazanes for high-temperature atomic layer deposition of silicon oxide thin films
US20240395541A1 (en) Functionalized cyclosilazanes as precursors for high growth rate silicon-containing films
JP7554755B2 (en) Compositions for silicon-containing films and methods of using the compositions
US12421603B2 (en) Composition for high temperature atomic layer deposition of high quality silicon oxide thin films
EP2669249A1 (en) Organoaminodisilane precursors and methods for depositing films comprising same
EP4223903A1 (en) Organoamino-functionalized cyclic oligosiloxanes for deposition of silicon-containing films
EP3526366A1 (en) Carbon bridged aminosilane compounds for high growth rate silicon-containing films
EP3963122B1 (en) Method for thermal deposition of silicon-containing films
WO2025229081A1 (en) Organoamino-carbosilanes and methods for depositing siliconcontaining films using same
KR102899478B1 (en) Organoaminodisilazane for high-temperature atomic layer deposition of silicon oxide thin films
EP4288579A1 (en) Composition for atomic layer deposition of high quality silicon oxide thin films

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25723636

Country of ref document: EP

Kind code of ref document: A1