WO2021201910A1 - Organoamino-functionalized cyclic oligosiloxanes for deposition of silicon-containing films - Google Patents

Organoamino-functionalized cyclic oligosiloxanes for deposition of silicon-containing films Download PDF

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WO2021201910A1
WO2021201910A1 PCT/US2020/052635 US2020052635W WO2021201910A1 WO 2021201910 A1 WO2021201910 A1 WO 2021201910A1 US 2020052635 W US2020052635 W US 2020052635W WO 2021201910 A1 WO2021201910 A1 WO 2021201910A1
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bis
group
tetramethylcyclotetrasiloxane
dimethylamino
silicon
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PCT/US2020/052635
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English (en)
French (fr)
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Matthew R. Macdonald
John J. LEHMANN
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Versum Materials Us, Llc
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Priority claimed from US16/838,997 external-priority patent/US20200317702A1/en
Priority claimed from US17/030,187 external-priority patent/US20210017198A1/en
Application filed by Versum Materials Us, Llc filed Critical Versum Materials Us, Llc
Priority to JP2022560058A priority Critical patent/JP2023520226A/ja
Priority to CN202080100242.1A priority patent/CN115443347A/zh
Priority to EP20928695.4A priority patent/EP4110968A4/en
Priority to KR1020227037953A priority patent/KR20220163999A/ko
Publication of WO2021201910A1 publication Critical patent/WO2021201910A1/en

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    • 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
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • 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

Definitions

  • the invention relates to organosilicon compounds that can be used to deposit silicon and oxygen containing films (e.g., silicon oxide, silicon oxycarbonitride, silicon oxycarbide, carbon-doped silicon oxide, among other silicon and oxygen containing films), methods for using the compounds for depositing silicon oxide containing films as well as films obtained from the compounds and methods.
  • silicon and oxygen containing films e.g., silicon oxide, silicon oxycarbonitride, silicon oxycarbide, carbon-doped silicon oxide, among other silicon and oxygen containing films
  • Described herein are novel organoamino-functionalized cyclic oligosiloxane precursor compounds and compositions and methods comprising same to deposit a silicon-containing film such as, without limitation, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon- doped silicon oxide via a thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) process, or a combination thereof. More specifically, described herein is a composition and method for formation of a stoichiometric or a non-stoichiometric silicon- containing film or material at one or more deposition temperatures of about 600°C or less including, for example, from about 25°C to about 300°C.
  • ALD thermal atomic layer deposition
  • PEALD plasma enhanced atomic layer deposition
  • Atomic Layer Deposition ALD and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes used to deposit, for example, silicon oxide conformal films at low temperature ( ⁇ 500°C).
  • the precursor and reactive gas such as oxygen or ozone
  • the precursor and reactive gas are separately pulsed in certain number of cycles to form a monolayer of silicon oxide at each cycle.
  • silicon oxide deposited at low temperatures using these processes may contain levels of impurities such as, without limitation, carbon (C) or hydrogen (H), which may be detrimental in certain semiconductor applications.
  • C carbon
  • H hydrogen
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • Organoaminosilane and chlorosilane precursors are known in the art that can be used to deposit silicon-containing films via Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) processes at a relatively low temperature ( ⁇ 300 °C) and with relatively high Growth Per Cycle (GPC >1.5 A/cycle).
  • ALD Atomic Layer Deposition
  • PEALD Plasma Enhanced Atomic Layer Deposition
  • US Patent No. 7,084,076 B2 describes the use of a halogen- or NCO-substituted disiloxane precursor to deposit a silicon oxide film using in a base-catalyzed ALD process.
  • US Pub. No. 2015087139 AA describes the use of amino-functionalized carbosilanes to deposit silicon containing films via thermal ALD or PEALD processes.
  • US Patent No. 9,337,018 B2 describes the use of organoaminodisilanes to deposit silicon containing films via thermal ALD or PEALD processes.
  • US Patent Nos. 8,940,648 B2, 9,005,719 B2, and 8,912,353 B2 describe the use of organoaminosilanes to deposit silicon containing films via thermal ALD or PEALD processes.
  • US Pub. No. 2015275355 AA describes the use of mono- and bis(organoamino)alkylsilanes to deposit silicon containing films via thermal ALD or PEALD processes.
  • US Pub. No. 2015376211A describes the use of mono(organoamino)-, halido-, and pseudohalido-substituted trisilylamines to deposit silicon containing films via thermal ALD or PEALD processes.
  • Pub No. W015105337 and US Patent No. 9,245,740 B2 describe the use of alkylated trisilylamines to deposit silicon containing films via thermal ALD or PEALD processes.
  • Pub. No. W015105350 describes the use of 4-membered ring cyclodisilazanes having at least one Si-H bond to deposit silicon containing films via thermal ALD or PEALD processes.
  • US Patent No. 7,084,076 B2 describes the use of a halogen- or NCO-substituted disiloxane precursor to deposit a silicon oxide film using in a base-catalyzed ALD process.
  • Pub No. US2018223047A discloses amino-functionalized linear and cyclic oligosiloxanes, which have at least two silicon and two oxygen atoms as well as an organoamino group and methods for depositing silicon and oxygen containing films.
  • the present development solves problems associated with conventional precursors and processes by providing silicon- and oxygen-containing precursors, specifically organoamino-functionalized cyclic oligosiloxanes, which have at least three silicon and three oxygen atoms as well as at least one organoamino group that serves to anchor the cyclic oligosiloxane unit to the surface of a substrate as part of a process to deposit a silicon and oxygen containing film.
  • the multi-silicon precursors disclosed in this invention have novel structures compared to those described in the above background section and, therefore, may provide an advantage in one or more aspects with respect to either cost or convenience of precursor synthesis, physical properties of the precursor including thermal stability, reactivity, or volatility, the process of depositing a silicon-containing film, or the properties of the deposited silicon-containing film.
  • composition comprising at least one organoamino-functionalized cyclic oligosiloxane compound selected from the group consisting of Formulae A-D:
  • R1 is selected from the group consisting of a linear C1 to C10 alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkynyl group, and a C4 to C10 aryl group;
  • R2 is selected from the group consisting of hydrogen, a C1 to C10 linear alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkynyl group, and a C4 to C10 aryl group, wherein R1 and R2 are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure; R3
  • a stoichiometric or nonstoichiometric silicon and oxygen containing material or film such as without limitation, a silicon oxide, a carbon doped silicon oxide, a silicon oxynitride film, or a carbon doped silicon oxynitride film at relatively low temperatures, e.g., at one or more temperatures of 600°C or lower, in a plasma enhanced ALD (PEALD), plasma enhanced cyclic chemical vapor deposition (PECCVD), a flowable chemical vapor deposition (FCVD), a plasma enhanced flowable chemical vapor deposition (PEFCVD), a plasma enhanced ALD-like process, or an ALD process with oxygen-containing reactant source, a nitrogen-containing reactant source, or a combination thereof.
  • PEALD plasma enhanced ALD
  • PECCVD plasma enhanced cyclic chemical vapor deposition
  • FCVD flowable chemical vapor deposition
  • PEFCVD plasma enhanced flowable chemical vapor deposition
  • PEFCVD plasma enhanced ALD-like process
  • a method for depositing a film comprising silicon and oxygen onto a substrate comprising the steps of: (a) providing a substrate in a reactor; (b) introducing into the reactor at least one silicon precursor compound selected from the group consisting of Formulae A-D:
  • R1 is selected from the group consisting of a linear C1 to C10 alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkynyl group, and a C4 to C10 aryl group;
  • R2 is selected from the group consisting of hydrogen, a C1 to C10 linear alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkynyl group, and a C4 to C10 aryl group, wherein R1 and R2 are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure; R3
  • Figure 1 is a graph of saturation curves of GPC versus precursor pulse time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2-dimethylamino-2,4,6,8,10- pentamethylcyclopentasiloxane according to the present invention as well as BDEAS of the prior art.
  • Figure 2 shows the film GPC and WER versus 02 plasma power using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 300 °C deposition according to the present invention.
  • Figure 3 shows the film GPC and WER versus 02 plasma power using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 100 °C deposition according to the present invention.
  • Figure 4 shows the film GPC and WER versus 02 plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 300 °C deposition according to the present invention.
  • Figure 5 shows the film GPC and WER versus 02 plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 100 °C deposition according to the present invention.
  • compositions and methods related to the formation of a stoichiometric or nonstoichiometric film or material comprising silicon and oxygen such as, without limitation, a silicon oxide, a carbon-doped silicon oxide film, a silicon oxynitride, or a carbon-doped silicon oxynitride film or combinations thereof with one or more temperatures, of about 600°C or less, or from about 25°C to about 600°C and, in some embodiments, from 25°C to about 300°C.
  • the films described herein are deposited in a deposition process such as an atomic layer deposition (ALD) or in an ALD-like process such as, without limitation, a plasma enhanced ALD (PEALD) or a plasma enhanced cyclic chemical vapor deposition process (PECCVD), a flowable chemical vapor deposition (FCVD), or a plasma enhanced flowable chemical vapor deposition (PEFCVD).
  • ALD atomic layer deposition
  • PECCVD plasma enhanced cyclic chemical vapor deposition
  • FCVD flowable chemical vapor deposition
  • PEFCVD plasma enhanced flowable chemical vapor deposition
  • the low temperature deposition (e.g., one or more deposition temperatures ranging from about ambient temperature to 600°C) methods described herein provide films or materials that exhibit at least one or more of the following advantages: a density of about 2.1g/cc or greater, low chemical impurity, high conformality in a thermal atomic layer deposition, a plasma enhanced atomic layer deposition (ALD) process or a plasma enhanced ALD-like process, an ability to adjust carbon content in the resulting film; and/or films have an etching rate of 5 Angstroms per second (A/sec) or less when measured in 0.5 wt% dilute HF.
  • ALD plasma enhanced atomic layer deposition
  • etch rate For carbon-doped silicon oxide films, greater than 1% carbon is desired to tune the etch rate to values below 2 A/sec in 0.5 wt% dilute HF in addition to other characteristics such as, without limitation, a density of about 1.8 g/cc or greater or about 2.0 g/cc or greater.
  • Methods disclosed herein can be practiced using equipment known in the art.
  • methods can employ a reactor that is conventional in the semiconductor manufacturing art.
  • the effectiveness of the precursor compositions disclosed herein can vary as a function of the number of silicon atoms and, in particular, the silicon atom bonds.
  • the precursors disclosed herein typically have between 3 and 8 silicon atoms, and between 6 and 16 silicon-oxygen bonds.
  • the precursors disclosed herein have different structures than known in this art and, therefore, are able to perform better than conventional silicon-containing precursors and provide relatively high GPC, yielding a higher quality film, having a favorable wet etch rate, or having less elemental contaminations.
  • compositions for depositing a film selected from a silicon oxide, a carbon-doped silicon oxide, or a silicon carboxynitride film using a vapor deposition process comprising a compound having Formulae A-D:
  • R 1 is selected from the group consisting of a linear Ci to Cm alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group
  • At least one of R1-9 is a C1 to C4 alkyl group.
  • a preferred embodiment includes compounds of Formulae A-D, wherein each of R1-9 is either hydrogen or a C1 to C4 alkyl group.
  • oligosiloxane denotes a compound comprising at least two repeating -Si-O- siloxane units, preferably at least three repeating -Si-O- siloxane units, and may be a cyclic or linear structure, preferably a cyclic structure.
  • alkyl denotes a linear or branched functional group having from 1 to 10 carbon atoms.
  • Exemplary linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.
  • Exemplary branched alkyl groups include, but are not limited to, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl, and neo-hexyl.
  • the alkyl group may have one or more functional groups attached thereto 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, alternatively, unsaturated.
  • cyclic alkyl denotes a cyclic functional group having from 3 to 10 carbon atoms.
  • exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
  • alkenyl group denotes a group which has one or more carbon-carbon double bonds and has from 2 to 10 or from 2 to 6 carbon atoms.
  • dialkylamino group, “alkylamino” group, or “organoamino” group denotes a group R1R2N- wherein R1 is selected from the group consisting of a linear C1 to C10 alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkynyl group, and a C4 to C10 aryl group and R2 is selected from the group consisting of hydrogen, a C1 to C10 linear alkyl group, a branched C3 to C10 alkyl group, a C3 to C10 cyclic alkyl group, a C3 to C10 heterocyclic group, a C3 to C10 alkenyl group, a C3 to C10 alkyny
  • R1 and R2 are linked to form a cyclic ring structure, in other cases R1 and R2 are not linked to form a cyclic ring structure.
  • aryl denotes an aromatic cyclic functional group having from 4 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, o-xylyl, 1,2,3-triazolyl, pyrrrolyl, and furanyl.
  • alkyl hydrocarbon refers a linear or branched C1 to C20 hydrocarbon, cyclic C6 to C20 hydrocarbon.
  • exemplary hydrocarbons include, but not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.
  • alkoxy refers to a C1 to C10 -OR1 group, wherein R1 is defined as above.
  • exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, iso-propoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxide.
  • aromatic hydrocarbon refers a C6 to C20 aromatic hydrocarbon.
  • exemplary aromatic hydrocarbons include, but are not limited to, toluene, and mesitylene.
  • heterocyclic means a non-aromatic saturated monocyclic or multicyclic ring system of about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the atoms in the ring system is/are element(s) other than carbon, for example nitrogen, oxygen or sulfur.
  • Preferred heterocycles contain about 5 to about 6 ring atoms.
  • aza, oxo or thio before heterocycle means that at least a nitrogen, oxygen or sulfur atom respectively is present as a ring atom.
  • the heterocyclic group is optionally substituted.
  • Compounds having Formulae A-D can be synthesized, for example, by catalytic dehydrocoupling of cyclic oligosiloxanes having at least one Si-H bond with organoamines (e.g., Equation 1 for cyclotetrasiloxanes and Equation 3 for larger cyclic oligosiloxanes such as cyclopentasiloxanes), or reaction of chlorinated cyclic oligosiloxanes with organoamines or metal salt of organoamines (e.g., Equation 2 for cyclotetrasiloxanes), or catalytic hydrosilylation of imines by cyclic oligosiloxanes as described in US Patent No. 9,758,534 B2 for synthesis of organoaminosilanes and organoaminodisilanes, whereby cyclic oligosiloxanes are employed instead of silane or disilane.
  • organoamines e.g., Equation 1 for
  • the molar ratio of cyclic oligosiloxane to organoamine in the reaction mixture is from about 4 to 1 , 3 to 1 , 2 to 1 , 1.5 to 1 , 1 to 1.0, 1 to 1.5, 1 to 2, 1 to 3, 1 to 4, 1 to 8, or from 1 to 10.
  • the catalyst employed in the method of the present invention in Equations 1 and 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, and actinide catalysts.
  • Catalysts listed above as well as 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, Ti02, metal-organic frameworks (MOFs), and organic polymers such as polystyrene.
  • Preferred supports are carbon (for examples, platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon) alumina, silica and MgO.
  • Metal loading of the catalyst ranges between about 0.01 weight percent to about 50 weight percent. A preferred range is about 0.5 weight percent to about 20 weight percent. A more preferred range is about 0.5 weight percent to about 10 weight percent.
  • Catalysts requiring activation may be activated by a number of known methods. Heating the catalyst under vacuum is a preferred method. The catalyst may be activated before addition to the reaction vessel or in the reaction vessel prior adding the reactants.
  • the catalyst may contain a promoter.
  • Promoters are substances which themselves are not catalysts, but when mixed in small quantities with the active catalysts increase their efficiency (activity and/or selectivity). Promoters are usually metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu and Au and/or their oxides. They can be added separately to the reactor vessel or they can be part of the catalysts themselves. For example, Ru/Mn/C (ruthenium on carbon promoted by manganese) or Pt/Ce02/lr/Si02 (platinum on silica promoted by ceria and iridium). Some promoters can act as catalyst by themselves but their use in combination with the main catalyst can improve the main catalyst's activity.
  • metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu and Au and/or their oxides. They can be added separately to the reactor vessel or they can be part of the catalyst
  • a catalyst may act as a promoter for other catalysts.
  • the catalyst can be called a bimetallic (or polymetallic) catalyst.
  • Ru/Rh/C can be called either ruthenium and rhodium on carbon bimetallic catalyst or ruthenium on carbon promoted by rhodium.
  • An active catalyst is a material that acts as a catalyst in a specific chemical reaction.
  • the molar ratio of catalyst to cyclic oligosiloxane in the reaction mixture ranges from 0.1 to 1, 0.05 to 1, 0.01 to 1, 0.005 to 1, 0.001 to 1, 0.0005 to 1, 0.0001 to 1, 0.00005 to 1, or 0.00001 to 1.
  • 0.002 to 0.003 equivalents of catalyst are used per equivalent of cyclic oligosiloxane.
  • 0.001 equivalents of catalyst are used per equivalent of cyclic oligosiloxane.
  • the reaction mixture comprising the cyclic oligosiloxane, organoamine and catalyst(s) further comprises an anhydrous solvent.
  • exemplary solvents may include, but are not limited to linear-, branched-, cyclic- or poly-ethers (e.g., tetrahydrofuran (THF), diethyl ether, diglyme, and/or tetraglyme); linear-, branched-, or cyclic- alkanes, alkenes, aromatics and halocarbons (e.g. pentane, hexanes, toluene and dichloromethane).
  • the selection of one or more solvent, if added, may be influenced by its compatibility with reagents contained within the reaction mixture, the solubility of the catalyst, and/or the separation process for the intermediate product and/or the end product chosen.
  • the reaction mixture does not comprise a solvent.
  • the reaction between the cyclic oligosiloxane and the organoamine occurs at one or more temperatures ranging from about 0 oC to about 200 oC, preferably 0 oC to about 100 oC.
  • Exemplary temperatures for the reaction include ranges having any one or more of the following endpoints: 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 oC.
  • the suitable temperature range for this reaction may be dictated by the physical properties of the reagent, and optional solvent. Examples of particular reactor temperature ranges include but are not limited to, 0 oC to 80 oC or from 0 oC to 30 oC. In some embodiments, it is preferable to keep the reaction temperature between 20 °C and 60 °C.
  • the pressure of the reaction may range from about 1 to about 115 psia or from about 15 to about 45 psia.
  • the reaction is run at atmospheric pressure.
  • the reaction is run above 15 psia.
  • one or more reagents may be introduced to the reaction mixture as a liquid or a vapor.
  • a non-reactive gas such as nitrogen or an inert gas may be employed as a carrier gas to deliver the vapor to the reaction mixture.
  • the regent may be added neat, or alternatively diluted with a solvent.
  • the reagent is fed to the reaction mixture until the desired conversion to the crude mixture containing the organoaminosilane product, or crude liquid, has been achieved.
  • the reaction may be run in a continuous manner by replenishing the reactants and removing the reaction products and the crude liquid from the reactor.
  • the crude mixture comprising compounds of Formulae A-D, catalyst(s), and potentially residual organoamine, solvent(s), or undesired product(s) may require separation process(es).
  • suitable separation processes include, but are not limited to, distillation, evaporation, membrane separation, filtration, centrifugation, crystallization, vapor phase transfer, extraction, fractional distillation using an inverted column, and combinations thereof.
  • Equations 1-3 are exemplary preparative chemistries and are not meant to be limiting in any way as to the preparation of the Compounds having Formulae A-D.
  • the silicon precursor compounds having Formulae A-D according to the present invention and compositions comprising the silicon precursor compounds having Formulae A-D according to the present invention are preferably substantially free of halide ions.
  • 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), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0 ppm as measured by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Ion Chromatography (IC), or by any other analytical method.
  • Chlorides are known to act as decomposition catalysts for the silicon precursor compounds having Formulae A-D. Significant levels of chloride in the final product can cause the silicon precursor compounds to degrade. The gradual degradation of the silicon precursor compounds may directly impact the film deposition process making it difficult for the semiconductor manufacturer to meet film specifications.
  • the silicon precursor compounds having Formulae A-D are preferably substantially free of metal ions such as Li+, Na+, K+, Mg2+, Ca2+, AI3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+, as well as any other metal ions that may have originated from the catalyst(s) employed in the synthesis of those compounds.
  • the term “substantially free” as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and any other metal impurities 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 silicon precursor compounds having Formulae A-D are free of metal ions such as Li+, Na+, K+, Mg2+, Ca2+, AI3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+, and any other metals ions that may have originated from the catalyst(s) employed in the synthesis of those compounds.
  • the term “free of” metal impurities as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and noble metals such as Ru, Rh, Pd, or Pt from catalysts used in the synthesis means less than 1 ppm, preferably 0.1ppm (by weight) as measured by ICP-MS or other analytical method for measuring metals.
  • a method for depositing a film comprising silicon and oxygen onto a substrate comprising the steps of: a) providing a substrate in a reactor; b) introducing into the reactor at least one silicon precursor compound, wherein the at least one silicon precursor selected from the group consisting of Formulae A-D: wherein R 1 is selected from the group consisting of a linear Ci to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group; R 2 is selected from the group consisting of hydrogen, a Ci to C 10 linear alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocycl
  • the methods disclosed herein form a silicon oxide film comprising at least one of the following characteristics a density of at least about 2.1 g/cc; 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 dilute HF (0.5 wt. % dHF) acid; an electrical leakage of less than about 1 e-8 A/cm2 up to 6 MV/cm; and a hydrogen impurity of less than about 5 e20 at/cc as measured by Secondary Ion Mass Spectrometry (SIMS).
  • SIMS Secondary Ion Mass Spectrometry
  • a layer of silicon-containing dielectric material is deposited on at a least a portion of a substrate via a chemical vapor deposition (CVD) process employing a reaction chamber.
  • Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs”), silicon, and compositions containing silicon such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide (“Si02”), silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof.
  • the substrate may have additional layers such as, for example, silicon, Si02, organosilicate glass (OSG), fluorinated silicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boronitride, organic-inorganic composite materials, photoresists, organic polymers, porous organic and inorganic materials and composites, metal oxides such as aluminum oxide, and germanium oxide.
  • OSG organosilicate glass
  • FSG fluorinated silicate glass
  • Still further layers can also be germanosilicates, aluminosilicates, copper and aluminum, and diffusion barrier materials such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.
  • 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, 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.
  • 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 silicon precursors.
  • ALD or ALD-like refers to a process including, but not limited to, the following processes: a) each reactant including a silicon precursor and a reactive gas is introduced sequentially into a reactor such as a single wafer ALD reactor, semi batch ALD reactor, or batch furnace ALD reactor; b) each reactant including the silicon precursor and the reactive gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor and each section is separated by inert gas curtain, i.e. , spatial ALD reactor or roll to roll ALD reactor.
  • a reactor such as a single wafer ALD reactor, semi batch ALD reactor, or batch furnace ALD reactor
  • each reactant including the silicon precursor and the reactive gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor and each section is separated by inert gas curtain, i.e. , spatial ALD reactor or roll to roll ALD reactor.
  • the method of the present invention is conducted via an ALD process that uses ozone, or an oxygen-containing source which comprises a plasma wherein the plasma can further comprise an inert gas such as one or more of the following: an oxygen plasma with or without inert gas, a water vapor plasma with or without inert gas, a nitrogen oxide (e.g., N20, NO, N02) plasma with or without inert gas, a carbon oxide (e.g., C02, CO) plasma with or without inert gas, and combinations thereof.
  • the oxygen-containing plasma source can be generated in situ or, alternatively, remotely.
  • the oxygen-containing source comprises oxygen and is flowing, or introduced during method steps b through d, along with other reagents such as without limitation, the at least one silicon precursor and optionally an inert gas.
  • the compositions described herein - and which are employed in the disclosed methods - further comprises a solvent.
  • exemplary solvents can include, without limitation, ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, tertiary aminoether, and combinations thereof.
  • the difference between the boiling point of the silicon precursor and the boiling point of the solvent is 40°C or less.
  • the compositions can be delivered via direct liquid injection into a reactor chamber for silicon-containing film.
  • At least one silicon precursor(s) having Formulae A-D is (are) used in a composition comprising a solvent
  • 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 wt% by weight to 99.5 wt% or from 10 wt% by weight to 75 wt%.
  • the solvent has a boiling point (b.p.) similar to the b.p. of the silicon precursor of Formulae A-D or the difference between the b.p. of the solvent and the b.p. of the silicon precursor of Formulae A-D is 40oC or less, 30°C or less, or 200C or less, or 100C.
  • 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.
  • 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 alkyl hydrocarbon (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-ethylpipe
  • silicon oxide or carbon doped silicon oxide films deposited using the methods described herein are formed in the presence of oxygen-containing source comprising ozone, water (H20) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide (H202), oxygen (02), oxygen plasma, NO, N20, N02, carbon monoxide (CO), carbon dioxide (C02) and combinations thereof.
  • oxygen-containing source comprising ozone, water (H20) (e.g., deionized water, purifier water, and/or distilled water), hydrogen peroxide (H202), oxygen (02), oxygen plasma, NO, N20, N02, carbon monoxide (CO), carbon dioxide (C02) and combinations thereof.
  • the oxygen-containing source may be passed through, for example, either an in situ or remote plasma generator to provide oxygen- containing plasma source comprising oxygen such as an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, or a carbon dioxide plasma.
  • the oxygen- containing plasma 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-containing plasma source can be introduced for a time that ranges from about 0.1 to about 100 seconds.
  • the oxygen- containing plasma source comprises water having a temperature of 10°C or greater.
  • the precursor pulse can have a pulse duration that is greater than 0.01 seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 to about 10 seconds, about 0.5 to about 20 seconds, about 1 to about 100 seconds) depending on the ALD reactor’s volume, and the oxygen-containing plasma source can have a pulse duration that is less than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).
  • the oxygen-containing plasma source is selected from the group consisting of oxygen plasma with or without inert gas water vapor plasma with or without inert gas, nitrogen oxides (N20, NO, N02) plasma with or without inert gas, carbon oxides (C02, CO) plasma with or without inert gas, and combinations thereof.
  • the oxygen-containing plasma source further comprises an inert gas.
  • the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, or combinations thereof.
  • the oxygen- containing plasma source does not comprise an inert gas.
  • the respective step of supplying the precursors, oxygen 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 precursors of Formulae A-D, 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 silicon precursor may be delivered to the reaction chamber such as a plasma enhanced cyclic CVD or PEALD reactor or a batch furnace type 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 a given end use application to form a film on a substrate.
  • the purity level of the at least one silicon precursor is sufficiently high enough to be acceptable for reliable semiconductor manufacturing.
  • the at least one silicon precursor 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 silicon precursor described herein can be obtained through one or more of the following processes: purification, adsorption, and/or distillation.
  • a plasma enhanced cyclic deposition process such as PEALD-like or PEALD may be used wherein the deposition is conducted using the at least one silicon precursor and an oxygen plasma source.
  • the PEALD- like process is defined as a plasma enhanced cyclic CVD process but still provides high conformal silicon and oxygen-containing films.
  • a method for depositing a silicon and oxygen containing film on at least one surface of a substrate, wherein the method comprises the steps of: a. providing a substrate in a reactor; b. introducing into the reactor at least one silicon precursor having Formulae A-D as defined above; c. purging the reactor with purge gas; d. introducing oxygen-containing source comprising a plasma into the reactor; and e. purging the reactor with a purge gas. ln this method, steps b through e are repeated until a desired thickness of film is deposited on the substrate.
  • 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. Also, purge times after precursor or oxidant steps can be minimized to ⁇ 0.1 s so that throughput is improved.
  • the method described herein deposits a high quality silicon and oxygen containing film on a substrate.
  • the method comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one silicon precursor having the Formulae A-D described herein; c. purging reactor with purge gas to remove at least a portion of the unabsorbed precursors; d. introducing an oxygen-containing plasma source into the reactor and e. purging reactor with purge gas to remove at least a portion of the unreacted oxygen source, wherein steps b through e are repeated until a desired thickness of the silicon-containing film is deposited.
  • the method described herein deposits a high quality silicon and oxygen containing film on a substrate at temperatures greater than 600oC.
  • the method comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one silicon precursor having the Formulae A-D described herein; c. purging reactor with purge gas to remove at least a portion of the unabsorbed precursors; d. introducing an oxygen-containing plasma source into the reactor and e. purging reactor with purge gas to remove at least a portion of the unreacted oxygen source, wherein steps b through e are repeated until a desired thickness of the silicon-containing film is deposited.
  • organoamino-functionalized cyclic oligosiloxane precursors having Formulae A-D, especially wherein R3-R9 are not hydrogen are preferred for this method because they either do not comprise any Si-H groups, or the number of Si-H groups are limited, since Si-H groups can decompose at temperatures higher than 600 oC and can potentially cause undesired chemical vapor deposition.
  • this method can also be carried out using organoamino-functionalized cyclic oligosiloxane precursors having Formulae A-D, wherein any of R3-9 are hydrogen, at temperatures above 600 °C without significant undesirable chemical vapor deposition.
  • Another method disclosed herein forms a carbon doped silicon oxide film using a silicon precursor compound having the chemical structure represented by Formulae A-D as defined above plus an oxygen source.
  • Another exemplary process is described as follows: a. providing a substrate in a reactor; b. contacting vapors generated from at least one silicon precursor compound having a structure represented by Formulae A-D as defined above, with or without co-flowing an oxygen source to chemically absorb the precursors on the heated substrate; c. purging away any unabsorbed precursors; d. Introducing an oxygen source on the heated substrate to react with the absorbed precursors; and, e. purging away any unreacted oxygen source, wherein steps b through e are repeated until a desired thickness is achieved.
  • the method described herein deposits a high quality silicon oxynitride film, on a substrate.
  • the method comprises the following steps: a. providing a substrate in a reactor; b. introducing into the reactor at least one silicon precursor having the Formulae A-D described herein; c. purging reactor with purge gas to remove at least a portion of the unabsorbed precursors; d. introducing a nitrogen-containing plasma source into the reactor and e. purging reactor with purge gas to remove at least a portion of the unreacted nitrogen source, wherein steps b through e are repeated until a desired thickness of the silicon oxynitride containing film is deposited.
  • Another exemplary process is described as follows: a. providing a substrate in a reactor; b. contacting vapors generated from at least one silicon precursor compound having a structure represented by Formulae A-D as defined above, with or without co-flowing a nitrogen source to chemically absorb the precursors on the heated substrate; c. purging away any unabsorbed precursors; d. Introducing a nitrogen source on the heated substrate to react with the absorbed precursors; and, e. purging away any unreacted nitrogen source, wherein steps b through e are repeated until a desired thickness is achieved.
  • ALD reactors such as single wafer, semi-batch, batch furnace or roll to roll reactor can be employed for depositing the solid silicon oxide, silicon oxynitride, carbon doped silicon oxynitride, or carbon doped silicon oxide.
  • Process temperature for the method described herein use one or more of the following temperatures as endpoints: 0 °C, 25 °C, 50 °C, 75 °C, 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, 425 °C, 450 °C, 475 °C, 500 °C, 525 °C, 550 °C, 575 °C, 600 oC, 625 °C, 650 oC, 675 °C, 700 oC, 725 °C, 750 oC, 775 °C, and 800 oC.
  • Exemplary temperature ranges include, but are not limited to the following: from about 0 °C to about 300 °C; or from about 25 °C to about 300 °C; or from about 50 °C to about 290 °C; or from about 25 °C to about 250 °C, or from about 25 °C to about 200 °C.
  • a method for depositing a silicon and oxygen containing film via flowable chemical vapor deposition comprising: placing a substrate comprising a surface feature into a reactor wherein the substrate is maintained at one or more temperatures ranging from about -20 °C to about 400 °C and a pressure of the reactor is maintained at 100 torr or less; introducing at least one compound selected from the group consisting of Formulae A-D as defined herein; providing an oxygen source into the reactor to react with the at least one compound to form a film and cover at least a portion of the surface feature; annealing the film at one or more temperatures of about 100 °C to 1000 °C to coat at least a portion of the surface feature; and treating the substrate with an oxygen source at one or more temperatures ranging from about 20 °C to about 1000 °C to form the silicon-containing film on at least a portion of the surface feature.
  • FCVD flowable chemical vapor deposition
  • a method for depositing a silicon and oxygen containing film via flowable chemical vapor deposition comprising: placing a substrate comprising a surface feature into a reactor wherein the substrate is maintained at one or more temperatures ranging from about -20 °C to about 400 °C and a pressure of the reactor is maintained at 100 torr or less; introducing at least one compound selected from the group consisting of Formulae A-D as defined herein; providing a nitrogen and/or oxygen source into the reactor to react with the at least one compound to form a film and cover at least a portion of the surface feature; annealing the film at one or more temperatures of about 100 °C to 1000 °C to coat at least a portion of the surface feature; and treating the substrate with an oxygen source at one or more temperatures ranging from about 20 °C to about 1000 °C to form the silicon-containing film on at least a portion of the surface feature.
  • FCVD flowable chemical vapor deposition
  • the oxygen source is selected from the group consisting of water vapors, water plasma, ozone, oxygen, oxygen plasma, oxygen/helium plasma, oxygen/argon plasma, nitrogen oxides plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and mixtures thereof.
  • the nitrogen source is selected from the group consisting of for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/helium plasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, organic amines such as tert- butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and an alkoxyamine such as ethanolamine plasma, and mixtures thereof.
  • the nitrogen- containing source comprises an ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium or a plasma comprising hydrogen and nitrogen source gas.
  • the method steps are repeated until the surface features are filled with the silicon-containing film.
  • the substrate temperature ranges from about -20 °C to about 40 °C or from about -10°C to about 25°C.
  • the film or the as- deposited film deposited from ALD, ALD-like, PEALD, PEALD-like or FCVD is subjected to a treatment step (post deposition).
  • the treatment step can be conducted during at least a portion of the deposition step, after the deposition step, and combinations thereof.
  • Exemplary treatment steps include, without limitation, treatment via high temperature thermal annealing; plasma treatment; ultraviolet (UV) light treatment; laser; electron beam treatment and combinations thereof to affect one or more properties of the film.
  • a vessel or container for depositing a silicon-containing film comprising one or more silicon precursor compounds is described herein.
  • the vessel comprises at least one pressurizable vessel (preferably of stainless steel having a design such as disclosed in U.S. Patent Nos. US7334595; US6077356; US5069244; and US5465766 the disclosure of which is hereby incorporated by reference.
  • the container can comprise either glass (borosilicate or quartz glass) or type 316, 316L, 304 or 304L stainless steel alloys (UNS designation S31600, S31603, S30400 S30403) fitted with the proper valves and fittings to allow the delivery of one or more precursors to the reactor for a CVD or an ALD process.
  • the silicon precursor is provided in a pressurizable vessel comprised of stainless steel and the purity of the precursor is 98% by weight or greater or 99.5% or greater which is suitable for the majority of semiconductor applications.
  • the head- space of the vessel or container is filled with inert gases selected from helium, argon, nitrogen and combination thereof.
  • 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 silicon precursor is kept at one or more temperatures for bubbling.
  • a solution comprising the at least one silicon precursor 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 silicon precursor to the reaction chamber during the precursor pulsing.
  • the reaction chamber process pressure is about 50 mTorr to 10 Torr.
  • the reaction chamber process pressure can be up to 760 Torr (e.g., about 50 mtorr to about 100 Torr).
  • the substrate such as a silicon oxide substrate is heated on a heater stage in a reaction chamber that is exposed to the silicon precursor initially to allow the complex to chemically adsorb onto the surface of the substrate.
  • the films deposited with the silicon precursors having Formulae A-D described herein when compared to films deposited with previously disclosed silicon precursors under the same conditions, have improved properties such as, without limitation, a wet etch rate that is lower than the wet etch rate of the film before the treatment step or a density that is higher than the density prior to the treatment step.
  • as-deposited films are intermittently treated. These intermittent or mid-deposition treatments can be performed, for example, after each ALD cycle, after every a certain number of ALD cycles, such as, without limitation, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles.
  • the precursors of Formulae A-D exhibit a growth rate of 2.0 A/cycle or greater.
  • the annealing temperature is at least 100 °C or greater than the deposition temperature. In this or other embodiments, the annealing temperature ranges from about 400 oC to about 1000 oC. In this or other embodiments, the annealing treatment can be conducted in a vacuum ( ⁇ 760 Torr), inert environment or in oxygen containing environment (such as H20, N20, N02, 02, or ambient air).
  • film is exposed to broad band UV or, alternatively, an UV source having a wavelength ranging from about 150 nanometers (nm) to about 400 nm.
  • the as-deposited film is exposed to UV in a different chamber than the deposition chamber after a desired film thickness is reached.
  • passivation layer such as Si02 or carbon doped Si02 is deposited to prevent chlorine and nitrogen contamination to penetrate into film in the subsequent plasma treatment.
  • the passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.
  • the plasma source is selected from the group consisting of hydrogen plasma, plasma comprising hydrogen and helium, plasma comprising hydrogen and argon. Hydrogen plasma lowers film dielectric constant and boost the damage resistance to following plasma ashing process while still keeping the carbon content in the bulk almost unchanged.
  • the silicon precursor compound having a chemical structure represented by Formulae A-D as defined above can be anchored via reacting the at least one organoamino group with hydroxyl on substrate surface to provide multiple Si-O-Si fragments per molecule of precursor, thus boosting the growth rate of silicon oxide or carbon doped silicon oxide compared to conventional silicon precursors such as bis(tert-butylamino)silane or bis(diethylamino)silane having only one silicon atom.
  • silicon compounds having Formulae A-D which have two or more organoamino groups may be able to react with two or more neighboring hydroxyl group on the surface of a substrate, which may improve the final film properties. It is also believed that organoamino-functionalized cyclic oligosiloxanes disclosed herein will exhibit higher growth per cycle (GPC) values as the number of silicon atoms is increased.
  • GPC growth per cycle
  • Wthout intending to be bound by a particular theory, it is believed that functionalizing the cyclic oligosiloxane molecules such as 2,4,6-trimethylcyclotrisiloxane, 2, 4,6,8- tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethylcyclopentasiloxane and other cyclic oligosiloxanes with an organoamino group can increase the thermal stability of the cyclic oligosiloxane, giving it a longer shelf life and maintaining a high purity for longer periods of time by inhibiting decomposition. In some cases, more organoamino groups can provide even higher thermal stability to the molecule.
  • the improved stability of the silicon precursors described herein having Formulae A-D make them superior to the parent cyclic oligosiloxane precursors.
  • functionalizing the cyclic oligosiloxane molecules such as 2,4,6-trimethylcyclotrisiloxane, 2, 4,6,8- tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethylcyclopentasiloxane and other cyclic oligosiloxanes with multiple organoamino groups can provide a precursor that results in a greater level of networking in the resulting silicon-containing film, especially when the oxygen- containing reactant in the deposition process is a mild oxidant such as water or hydrogen peroxide.
  • the silicon precursors having Formulae A-D as defined above can also be used as a dopant for metal containing films, such as but not limited to, metal oxide films or metal oxynitride films.
  • metal containing films such as but not limited to, metal oxide films or metal oxynitride films.
  • the metal containing film is deposited using an ALD or CVD process such as those processes described herein using metal alkoxide, metal amide, or volatile organometallic precursors.
  • suitable metal alkoxide precursors include, but are not limited to, group 3 to 6 metal alkoxide, group 3 to 6 metal complexes having both alkoxy and alkyl substituted cyclopentadienyl ligands, group 3 to 6 metal complexes having both alkoxy and alkyl substituted pyrrolyl ligands, group 3 to 6 metal complexes having both alkoxy and diketonate ligands; group 3 to 6 metal complexes having both alkoxy and ketoester ligands.
  • suitable metal amide precursors that may be used with the method disclosed herein include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert- butylimino tri(diethylamin
  • organometallic precursors examples include, but are not limited to, group 3 metal cyclopentadienyls or alkyl cyclopentadienyls.
  • exemplary Group 3 to 6 metals herein include, but not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.
  • the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less.
  • the films can a dielectric constant of about 5 or below, or about 4 or below, or about 3.5 or below.
  • films having other dielectric constants e.g., higher or lower can be formed depending upon the desired end-use of the film.
  • silicon carbo-oxynitride wherein the carbon content is from 1 at% to 80 at% measured by XPS.
  • silicon containing film that is formed using the silicon precursors having Formulae A-D and processes described herein is amorphous silicon wherein both sum of nitrogen and carbon contents is ⁇ 10 at%, preferably ⁇ 5 at%, most preferably ⁇ 1 at% measured by XPS.
  • the method described herein may be used to deposit a silicon-containing film on at least a portion of a substrate.
  • suitable substrates include but are not limited to, silicon, Si02, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon oxycarbide, hydrogenated silicon oxynitride, silicon carbo-oxynitride, hydrogenated silicon carbo-oxynitride, anti reflective coatings, photoresists, germanium, germanium- containing, boron-containing, Ga/As, a flexible substrate, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.
  • the films are compatible with a variety of subsequent processing steps such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.
  • CMP chemical mechanical planarization
  • the deposited films have applications, which include, but are not limited to, computer chips, optical devices, magnetic information storages, coatings on a supporting material or substrate, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistor (TFT), light emitting diodes (LED), organic light emitting diodes (OLED), IGZO, and liquid crystal displays (LCD).
  • MEMS microelectromechanical systems
  • TFT thin film transistor
  • LED light emitting diodes
  • OLED organic light emitting diodes
  • IGZO liquid crystal displays
  • Potential use of resulting solid silicon oxide or carbon doped silicon oxide include, but not limited to, shallow trench insulation, inter layer dielectric, passivation layer, an etch stop layer, part of a dual spacer, and sacrificial layer for patterning.
  • the methods described herein provide a high quality silicon oxide, silicon oxynitride, carbon doped silicon oxynitride, or carbon-doped silicon oxide film.
  • the term “high quality” means a film that exhibits one or more of the following characteristics: a density of about 2.1 g/cc or greater, 2.2 g/cc or greater, 2.25 g/cc or greater; a wet etch rate that is 2.5 A/s or less, 2.0 A/s or less, 1.5 A/s or less, 1.0 A/s or less, 0.5 A/s or less, 0.1 A/s or less, 0.05 A/s or less, 0.01 A/s or less as measured in a solution of 1:100 of HF to water dilute HF ( 0.5 wt% dHF) acid, an electrical leakage of about 1 or less e-8 A/cm2 up to 6 MV/cm); a hydrogen impurity of about 5 e20 at/cc or less as measured by SIMS; and combinations thereof
  • one or more silicon precursors having Formulae A-D described herein can be used to form silicon and oxygen containing films that are solid and are non-porous or are substantially free of pores.
  • Example 1a Synthesis of 2, 4-bis(dimethylamino)-2, 4,6, 8-tetramethylcyclotetrasiloxane and 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.
  • Example 1b Thermal Stability of Bis(dimethylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane.
  • Example 2 Synthesis of 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.
  • Example 3 Synthesis of 2,4-bis(N-ethylmethylamino)-2,4,6,8- tetramethylcyclotetrasiloxane and 2,6-bis(N-ethylmethylamino)-2,4,6,8- tetramethylcyclotetrasiloxane.
  • Example 2 A similar procedure was followed as in Example 1, except that N-ethylmethylamine was used instead of dimethylamine to afford a mixture of 2,4-bis(N-ethylmethylamino)-2,4,6,8- tetramethylcyclotetrasiloxane and 2,6-bis(N-ethylmethylamino)-2,4,6,8- tetramethylcyclotetrasiloxane.
  • Example 4 Synthesis of 2, 4-bis(iso-propylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane and 2,6-bis(iso-propylamino)-2,4,6,8- tetra m ethyl cy cl otetras i I oxa ne .
  • Example 2 A similar procedure was followed as in Example 1 , except that iso-propylamine was used instead of dimethylamine to afford a mixture of 2,4-bis(iso-propylamino)-2,4,6,8- tetramethylcyclotetrasiloxane and 2,6-bis(N-iso-propylamino)-2,4,6,8- tetramethylcyclotetrasiloxane.
  • 356 (M+), 341 (M-15), 325, 313, 296, 282, 253, 240, 223, 208, 193, 180, 164, 150, 141, 134, 120, 112, 103, 87, 74, 59, 44.
  • Example 5 Synthesis of 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.
  • Example 6a Synthesis of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane.
  • THF 200 ml_
  • RU 3 (CO) I2 (1.12 g, 0.00172 mol
  • 2,4,6,8,10- pentamethylcyclopentasiloxane 240 g, 0.798 mol
  • dimethylamine solution in THF 176 ml_, 2.0 M solution
  • Example 6b Thermal Stability of 2-dimethylamino-2,4,6,8,10- pentamethylcyclopentasiloxane.
  • Example 7 Synthesis of 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane.
  • Example 9 Synthesis of 2,4,6, 8-tetrakis(methylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane from 2,4,6,8-tetrachloro-2,4,6,8-tetramethylcyclotetrasiloxane and methylamine.
  • GC-MS showed the following mass peaks: 355 (M+), 340 (M— 15), 326, 311, 296, 282, 267, 253, 240, 225, 209, 193, 179, 165, 147, 133, 120, 112, 105, 94, 82, 73, 59, 44.
  • Example 10 Synthesis of 2,4,6, 8-tetrakis(methylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane from 2,4,6,8-tetramethylcyclotetrasiloxane and methylamine (prophetic).
  • Example 11 Synthesis of 2,4,6, 8-tetrakis(dimethylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane from 2,4,6,8-tetrachloro-2,4,6,8-tetrachloro-2,4,6,8- tetramethylcyclotetrasiloxane and dimethylamine.
  • GC-MS showed the following mass peaks: 413 (M+), 398 (M— 15), 384, 369, 355, 339, 326, 310, 296, 283, 267, 253, 240, 225, 209, 194, 179, 163, 155, 141, 134, 119, 111, 103, 89, 73, 58, 44.
  • Example 12 PEALD Silicon Oxide Using bis(dimethylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane (comprising a mixture of 2,4- and 2,6- isomers) in laminar flow reactor with 27.1 MHz plasma
  • PEALD Plasma enhanced ALD
  • ASM lateral flow reactor
  • Precursors were liquids heated up to 62 °C in stainless steel bubblers and delivered to the chamber with Ar carrier gas. All depositions reported in this study were done on native oxide containing Si substrates. Thickness and refractive indices of the films were measured using a FilmTek 2000SE ellipsometer. Wet etch rate (WER) measurements were performed by using 1:99 (0.5 wt.%) diluted hydrofluoric (HF) acid solution.
  • WER wet etch rate
  • Thermal oxide wafers were used as standard for each set of experiments to confirm the etch solution’s activity. The samples were all etched for 15 seconds to remove any surface layer before starting to collect the bulk film’s WER. A typical thermal oxide wafer wet etch rate for 1 :99 (0.5 wt.%) dHF water solution was 0.5 A/s by this procedure.
  • Depositions were performed with bis(dimethylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane (comprising a mixture of 2,4- and 2,6- isomers) as the silicon precursor and 02 plasma under conditions as described above in Table 2.
  • the silicon precursor was delivered to chamber with carrier gas Ar flow of 200 seem. Steps b to e were repeated many times to get a desired thickness of silicon oxide for metrology.
  • the film deposition parameters and deposition GPC are shown in Table 3 for 100 °C deposition and Table 4 for 300 °C deposition.
  • Depositions 1-6 and 13-18 show the GPC as a function of precursor pulse time deposition at 100 °C and 300 °C.
  • Figure 1 shows the saturation curve of bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane GPC versus number of precursor pulses. It can be seen that GPC increases with precursor pulses and then saturates, indicating ALD behavior of the precursor.
  • 100 °C depositions show higher GPC than 300 °C depositions.
  • BDEAS bis(diethylamino)silane
  • the BDEAS container was heated to 28 °C and had a similar internal vapor pressure to the bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane container at 62 °C.
  • BDEAS was delivered to chamber with carrier gas Ar flow of 200 seem.
  • Bis(dimethylamino)-2, 4,6,8- tetramethylcyclotetrasiloxane shows much higher GPC than BDEAS.
  • Depositions 7-12 and 19 - 24 show GPC and film relative WER at varying deposition pressure, oxygen plasma time, or oxygen plasma power.
  • Figure 2 and Figure 3 show the film GPC and WER versus 02 plasma power at 300 °C and 100 °C deposition temperatures, respectively, when bis(dimethylamino)- 2,4,6,8-tetramethylcyclotetrasiloxane was used as the silicon precursor.
  • GPC slightly decreased with increased oxygen plasma power
  • WER decreased with increased oxygen plasma power.
  • Films deposited at high temperature give lower WER.
  • Figure 4 and Figure 5 shows film GPC and WER versus 02 plasma time at 300 °C and 100 °C deposition, respectively, when bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane was used as the silicon precursor.
  • Example 13 PEALD Silicon Oxide Using 2-dimethylamino-2,4,6,8,10- pentamethylcyclopentasiloxane in laminar flow reactor with 27.1 MHz plasma.
  • Depositions were performed with 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane as the silicon precursor and O2 plasma under conditions as described above in Table 2.
  • the precursor was delivered to the chamber with carrier gas Ar flow of 200 seem.
  • the container was heated to 50 °C.
  • Steps b to e were repeated many times to get a desired thickness of silicon oxide for metrology.
  • the film deposition parameters and deposition GPC, film Rl and relative WER to thermal oxide are shown in Table 7 and Table 8.
  • Figure 1 shows the saturation curve of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane GPC versus number of precursor pulses.
  • Example 14 Thermal ALD Silicon Oxide Using 2-dimethylamino-2,4,6,8,10- pentamethylcyclopentasiloxane and ozone (prophetic).
  • Thermal Atomic Layer Depositions of silicon oxide films are performed on a laboratory scale ALD processing tool.
  • the silicon precursor, 2-dimethylamino-2,4,6,8,10- pentamethylcyclopentasiloxane is delivered to the chamber by vapor draw. All gases (e.g., purge and reactant gas or precursor and oxygen source) are preheated to 100°C prior to entering the deposition zone. Gases and precursor flow rates are controlled with ALD diaphragm valves with high speed actuation.
  • the substrates used in the deposition are 12-inch- long silicon strips.
  • a thermocouple is attached on the sample holder to confirm substrate temperature.
  • Depositions are performed using ozone as oxygen source gas. Normal deposition process and parameters are shown in Table 9. Steps 1 to 6 are repeated until a desired thickness is reached. [00151] Table 9. Process for Thermal Atomic Layer Deposition of Silicon Oxide Films with Ozone as the Oxygen Source on the Laboratory Scale ALD Processing Tool.
  • the growth per cycle (GPC) of the deposited thin film is expected to be greater than 2.5 A/cycle.
  • a pure silicon oxide film is formed with ⁇ 0.1 at% carbon and ⁇ 0.1 at% nitrogen impurities as measured by XPS.
  • the film is expected to be a carbon-doped silicon oxide film with carbon content > 10 at% as measured by XPS, and film WER is expected to be less than thermal oxide film WER using 1:99 (0.5 wt.%) diluted hydrofluoric (HF) acid solution.
  • HF hydrofluoric

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