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  • 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
  • H01L21/02211—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 being a silane, e.g. disilane, methylsilane or chlorosilane
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  • 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
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  • 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
  • C23C16/34—Nitrides
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  • 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
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  • C23C16/402—Silicon dioxide
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  • 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
• • H—ELECTRICITY
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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  • 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
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  • 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
  • H01L21/0217—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 nitride not containing oxygen, e.g. SixNy or SixByNz
• • H—ELECTRICITY
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  • 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
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  • 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
• • H—ELECTRICITY
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  • 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
  • H01L21/02222—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 the compound being a silazane

Definitions

• Si-containing film forming compositions comprising Si-C free and volatile silazane-containing precursors are disclosed.
• the compositions may be used to deposit high purity thin films.
• US Pat App Pub No. 2015/047914 to Sanchez et al. discloses halogen free amine substituted trisilylamine and tndisilylamine compounds and a method of their preparation via dehydrogenative coupling between the corresponding unsubstituted trisilylamines and amines catalyzed by transition metal catalysts.
• Si-containing film forming compositions Si-containing film forming compositions.
• US2016/0049293 to Li et al. discloses a method and composition comprising same for sealing the pores of a porous low dielectric constant layer by providing an additional thin dielectric film.
• US2016/0225616 to Li et al. discloses an apparatus comprising a plurality of silicon-containing layers wherein the silicon-containing layers are selected from a silicon oxide and a silicon nitride layer or film.
• WO2016/065221 to Lei et al. discloses compositions and methods using same for forming a silicon-containing film or material.
• Molecules lacking Si-C direct bonds are known to yield purer films than molecules having such direct bonds, owing to the low reactivity and high thermal stability of the Si-C bond.
• silanes having alkoxy groups rarely exhibit proper self-limiting growth by atomic layer deposition, and do not allow the formation of silicon nitride films as the oxygen normally remains in the film, and hence are not as versatile as aminosilanes having Si-N bonds in terms of possible applications for thin film deposition.
• an alkoxy group doesn't appear as a suitable functional group for surface reaction in atomic layer deposition
• Si-C free molecules having a Si-O-Si (siloxane) bridge have been proposed and may be used.
• Typical Si-C-free silane precursors that have been proposed and used industrially for silicon oxide and silicon nitride thin film deposition are
• a- halosilanes such as dichlorosilane, monochlorosilane,
• c- Amino silanes having the general formula SiHx(NR1 R2)4-x such as bis-diethylaminosilanes, tris-dimethylaminosilane,
• d- Amino-disilanes such as hexakis(ethylamino)disilane
• e- Siloxane such as disiloxane, hexachlorodisiloxane
• f- Trisilylamine which may be used for a variety of deposition processes such as flowable CVD, thermal low pressure CVD, plasma enhanced CVD, ALD, and plasma enhanced ALD.
• TSA-CI silicon-rich molecules
• BDSASi for instance has been reported to yield high growth per cycle SiN by PEALD.
• molecules enabling higher growth rates at low temperature, whether by ALD, CVD, flowable CVD or other forms of vapor deposition, while maintaining high film purity are still sought to further gain process productivity, or enable depositing in lower temperature conditions than usual precursors.
• Silicon-containing film forming compositions are disclosed.
• the silicon- containing film forming compositions comprise a precursor selected from the group consisting of:
• each R is independently selected from H, a dialkylamino group having the formula -NR 1 R 2 , or an amidinate,
• Each R' is independently selected from H, a dialkylamino group having the formula -NR 1 R 2 , or an amidinate, with the provision that all R' are not H,
• R 1 and R 2 are independently selected from H or a C1 -C12 hydrocarbyl group, with the provision that R 1 and R 2 cannot be simultaneously equal to H, and that if R 1 is H, then R 2 is a C2 -C12 hydrocarbyl group, and NR 1 R 2 may together form an N-containing heterocyclic ligand, and
• - L is selected from H or a C1-C6 hydrocarbyl group.
• the disclosed Silicon-containing film forming compositions may comprise one or more of the following aspects:
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Ge;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Hf;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Zr;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw In;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Fe;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Pb;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Li;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Mg;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Mn;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw W;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Ni;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw K;
• the o Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Na;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Sr;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Th;
• the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Sn; • the Si-containing film forming composition comprising between approximately 0 ppbw and approximately 500 ppbw Ti;
• Si-containing film forming composition comprising between
• ROH approximately 0.0% w/w and 0.1 % w/w ROH, wherein R is C1 -C4 alkyl group
• R is a C1 -C4 alkyl group
• Methods of depositing silicon-containing films on a substrate by chemical vapor deposition methods are disclosed.
• the vapor of any of the Si-containing film forming compositions disclosed above is introduced into a reactor containing a substrate. At least part of the precursor is deposited onto the substrate to form the silicon-containing film on the substrate using a chemical vapor deposition process.
• the disclosed method may include one or more of the following aspects:
• the chemical vapor deposition method being a plasma enhanced atomic layer deposition process
• an element of the second precursor being selected from the group consisting of group 2, group 13, group 14, transition metal, lanthanides, and combinations thereof;
• the element of the second precursor being selected from As, B, P, Si, Ge, Al, Zr, Hf, Ti, Nb, Ta, or lanthanides;
• the reactant being selected from the group consisting of O2, O3, H2O, H2O2, NO, NO2, a carboxylic acid, an alcohol, a diol, radicals thereof, and combinations thereof;
• the silicon-containing film being a silicon oxide film
• the silicon-containing film being a silicon nitride film
• the substrate being a silicon wafer
• the substrate being glass
• the substrate being an organic material
• the indefinite article “a” or “an” means one or more.
• the terms “approximately” or “about” mean ⁇ 10% of the value stated.
• R groups independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group.
• the two or three R 1 groups may, but need not be identical to each other or to R 2 or to R 3 .
• values of R groups are independent of each other when used in different formulas.
• hydrocarbyl group refers to a functional group containing carbon and hydrogen; the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms.
• the hydrocarbyl group may be saturated or unsaturated.
• Either term refers to linear, branched, or cyclic groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
• C-free means starting reactant has no Si-C bond.
• the abbreviation "Me” refers to a methyl group
• the abbreviation “Et” refers to an ethyl group
• the abbreviation “Pr” refers to a propyl group
• the abbreviation “nPr” refers to a "normal” or linear propyl group
• the abbreviation “iPr” refers to an isopropyl group
• the abbreviation “Bu” refers to a butyl group
• the abbreviation “nBu” refers to a "normal” or linear butyl group
• the abbreviation “tBu” refers to a tert-butyl group, also known as 1 , 1 -dimethylethyl
• the abbreviation “sBu” refers to a sec-butyl group, also known as 1 -methylpropyl
• the abbreviation “iBu” refers to an iso-butyl group, also known as 2-methylpropy
• halide refers to the halogen anions F “ , CI “ , Br, and I " ; the term “silyl” refers to a R3S 1- ligand, wherein each R is independently H or a C1 -C4 alkyl group.
• halide salt refers to an ionic compound containing a halide ion.
• ALD a ligand selected in the amidinate family is abbreviated "AMD”.
• Group 3 refers to Group 3 of the Periodic Table (i.e., Sc, Y, La, or Ac).
• Group 4 refers to Group 4 of the Periodic Table (i.e., Ti, Zr, or Hf) and Group 5 refers to Group 5 of the Periodic Table (i.e., V, Nb, or Ta).
• the films or layers deposited such as silicon oxide or silicon nitride, may be listed throughout the specification and claims without reference to their proper stoichiometry (i.e., S1O2, S1O3, Si3N 4 ).
• the layers may include pure (Si) layers, carbide (SioCp) layers, nitride (SikNi) layers, oxide (SinOm) layers, or mixtures thereof, wherein k, I, m, n, o, and p inclusively range from 1 to 6.
• silicon oxide is SinOm, wherein n ranges from 0.5 to 1 .5 and m ranges from 1.5 to 3.5. More preferably, the silicon oxide layer is S1O2 or S 1O3.
• These films may also contain Hydrogen, typically from 0 at% to 15 at%. However, since not routinely measured, any film compositions given ignore their H content, unless explicitly stated otherwise.
• a substrate is understood as the main solid material on which the film is deposited. It is understood that the film may be deposited on a stack of layers that are themselves on the substrate.
• Substrates are typically but not limited to wafers of silicon, glass, quartz, sapphire, GaN, AsGa, Ge.
• Substrates may be sheets, typically of metal, glass, organic materials like polycarbonate, PET, ABS, PP, HDPE, PMMA, etc.
• Substrates may be three-dimensional (3D) objects of similar materials.
• typical layers over the substrate may be Ge, SiGe, silicon oxide, silicon nitride, metals (such as Cu, Co, Al, W, Ru, Ta, Ti, Ni), metal silicides and alloys, metal nitrides such as TaN, TiN, VN, NbN, HfN, VN; carbon doped silica films, whether dense or porous, silicon carbo-nitride, amorphous carbon, boron nitride, boron carbonitride, organic materials such as spin-on-carbon, polyimides, photoresists and anti-reflective layers; metal oxides such as oxides of Ti, Hf, Zr, Ta, Nb, V, Mo, W, Al, and lanthanides.
• metals such as Cu, Co, Al, W, Ru, Ta, Ti, Ni
• metal silicides and alloys metal nitrides such as TaN, TiN, VN, NbN, HfN, VN
• the substrates may have topographies like holes or trenches, typically having opening in the range of 5 nm to 100 pm, and usually between 20 nm and 1 pm, and aspect ratio of up to 1 : 1000, more usually in the range of 1 :2 to 1 : 100.
• FIG is a Gas Chromatographic spectrum of the perhydropolysilazane oil of the Example.
• Silicon-containing film forming compositions comprising short chain (Si ranging from 3 to 10) oligosilazanes having at least a trisilylamine backbone selected from the family of:
• each R is independently selected from H, a dialkylamino group having the formula -NR 1 R 2 , or an amidinate;
• each R' is independently selected from H, a dialkylamino group having the formula -NR 1 R 2 , or an amidinate, with the provision that all R' are not H - R 1 and R 2 are independently selected from H or a C1 -C12 hydrocarbyl group with the provision that R 1 and R 2 cannot be simultaneously equal to H, and that if R 1 is H, then R 2 is a C2 hydrocarbyl group or larger,
• - NR 1 R 2 may form a N-containing heterocyclic ligand
• - L is selected from H or a C1-C6 hydrocarbyl group
• NR 1 R 2 is pyrrole, pyrrolidine, piperidine, imidazole or azidrine
• the invention comprises the synthesis of compounds of families (1 ), (2), (3) and (4) from the following synthesis processes:
• reaction being preferably carried in an anhydrous and aprotic solvent or solvent mixture, such as but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or tetrahydrofuran (THF).
• anhydrous and aprotic solvent or solvent mixture such as but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or tetrahydrofuran (THF).
• reaction being carried at a temperature between -40°C and 100°C, preferably at room temperature.
• the formed salt being filtered from the reaction mixture and the components of the remaining liquid composition being separated by distillation.
• the compound of family (1 ) being purified by distillation to reach an assay of > 98%, more preferably or > 99%, and even more preferably > 99.5%, which is typical of semiconductor grade precursors
• the product of family (1 ) may be further treated to reduce the content of dissolved NH3LX salts, for instance by exposing the product to a solid adsorbent such as activated carbon, dried Amberlyst resin or other such ion exchange resin.
• a solid adsorbent such as activated carbon, dried Amberlyst resin or other such ion exchange resin.
• the product may be filtered to reach specifications that are
• dihalosilane [S1R2X2, wherein X is CI, Br, or I] and monohalosilane [S1R3X, wherein X is CI, Br, or I] may be introduced continuously in the gas phase in a 1/20 to 1 ⁇ 4 ratio and at room temperature with 400 seem of NH3 in a flow-through tubular reactor as described by Miller in U.S. Pat. No. US 8,669,387.
• DSA disilylamine
• X is CI, Br, or I.
• One of ordinary skill in the art would recognize that the reaction may take place in one or two steps (first forming DSA from the monohalosilane and NH3 and second adding dihalosilane) or in one step (combining the monohalosilane, dichlorosilane, and NH3 in one step).
• reaction being carried or neat or in an aprotic solvent such as, but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• an aprotic solvent such as, but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• reaction being carried at a temperature between room temperature and 150°C, preferably at 30-60°C.
• the catalyst being filtered from the reaction mixture and the components of the remaining liquid composition being separated by distillation.
• the compound of family (1 ) being purified by distillation to reach an assay of > 98%, more preferably or > 99%, and even more preferably > 99.5%, which is typical of semiconductor grade precursors
• the product may be filtered to reach specifications that are typical of products used in the semiconductor industry.
• reaction being preferably carried in an anhydrous or aprotic solvent or solvent mixture, such as but not limited to a C 3 -C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• anhydrous or aprotic solvent or solvent mixture such as but not limited to a C 3 -C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• reaction being carried at a temperature between -40°C and 100°C, preferably between -20°C to room temperature.
• the water being added diluted in a polar non protic solvent typically from 1 % to 50%, more preferably from 5% to 30% -
• the reaction mixture comprising a halide scavenger, such as but not limited to pyridine, trialkylamine, in a quantity higher than the HX expected release on a molar basis.
• the halide scavenger may be used as the solvent.
• the reaction mixture may then be filtered to remove the HX-scavenger salt formed prior to the final product separation.
• the compound of family (2) being purified by vacuum distillation to reach an assay of > 98%, more preferably or > 99%, and even more preferably > 99.5%, which is typical of semiconductor grade precursors -
• the product of family (2) may be further treated to reduce the content of dissolved salts, for instance by exposing the product to a solid adsorbent such as activated carbon, dried Amberlyst resin or other such ion exchange resin.
• the product may be filtered to reach specifications that are typical of products used in the semiconductor industry.
• Compounds of Family 3 are preferentially synthesized from the direct reaction of (SiH3)2N-SiH2-N(SiH3)2 (BDSASi) with an amine by dehydrogenative coupling, according to the same protocol as described in U.S. Pat. App. Pub. No. 2015/0094470.
• reaction being carried neat or in an aprotic solvent such as, but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• an aprotic solvent such as, but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• reaction being carried at a temperature between room temperature and 150°C, preferably at 30-60°C.
• the catalyst being filtered from the reaction mixture and the components of the remaining liquid composition being separated by distillation.
• the compound of family (3) being purified by distillation to reach an assay of > 98%, more preferably or > 99%, and even more preferably >
• the product may be filtered to reach specifications that are typical of products used in the semiconductor industry.
• the (SiR3)2NSiH2-X reactant may be synthesized as disclosed in co-pending US Pat. App. App. No. 62/432,592, more particularly by mixing trisilylamine with a catalyst, such as B(C6F 5 )3, BPhs, PdCfc, Co 2 (CO)8 , or Zeolite Y (H) Si: Al, without a Nhta reactant or heat.
• a catalyst such as B(C6F 5 )3, BPhs, PdCfc, Co 2 (CO)8 , or Zeolite Y (H) Si: Al, without a Nhta reactant or heat.
• reaction being preferably carried in an anhydrous and aprotic solvent or solvent mixture, such as but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• anhydrous and aprotic solvent or solvent mixture such as but not limited to a C3-C24 hydrocarbon solvent, toluene, benzene, diethylether, acetonitrile, or THF.
• reaction being carried at a temperature between -40°C and 100°C, preferably at room temperature.
• the formed salt being filtered from the reaction mixture and the components of the remaining liquid composition being separated by distillation.
• the compound of family (4) being purified by vacuum distillation to reach an assay of > 98%, more preferably or > 99%, and even more preferably > 99.5%, which is typical of semiconductor grade precursors -
• the product of family (4) may be further treated to reduce the content of dissolved XH3N-C ⁇ N salts, for instance by exposing the product to a solid adsorbent such as activated carbon, dried Amberlyst resin or other such ion exchange resin.
• the disclosed Si-containing film forming compositions may be purified by continuous or fractional batch distillation prior to use to a purity ranging from approximately 95% w/w to approximately 100% w/w, preferably ranging from approximately 98% w/w to approximately 100% w/w.
• the purity may be determined by H NMR or gas or liquid chromatography with mass spectrometry.
• the Si-containing film forming composition may contain any of the following impurities: halides (X2), trisilylamine, monohalotrisilylamine, dihalotrisilylamine, SiH 4 , S1H3X, SnX2, SnX 4 , HX, NH3, NH3X, monochlorosilane, dichlorosilane, alcohol, alkylamines, dialkylamines, alkylimines, THF, ether, pentane, cyclohexane, heptanes, or toluene, wherein X is CI, Br, or I.
• the total quantity of these impurities is below 0.1 % w/w.
• the purified composition may be produced by recrystallisation, sublimation, distillation, and/or passing the gas or liquid through a suitable adsorbent, such as a 4A molecular sieve or a carbon-based adsorbent (e.g., activated carbon).
• a suitable adsorbent such as a 4A molecular sieve or a carbon-based adsorbent (e.g., activated carbon).
• the concentration of each solvent (such as THF, ether, pentane, cyclohexane, heptanes, and/or toluene), in the purified mono-substituted TSA precursor composition may range from approximately 0% w/w to approximately 5% w/w, preferably from approximately 0% w/w to approximately 0.1 % w/w.
• Solvents may be used in the precursor composition's synthesis. Separation of the solvents from the precursor composition may be difficult if both have similar boiling points. Cooling the mixture may produce solid precursor in liquid solvent, which may be separated by filtration. Vacuum distillation may also be used, provided the precursor composition is not heated above approximately its decomposition point.
• the disclosed Si-containing film forming composition contains less than 5% v/v, preferably less than 1 % v/v, more preferably less than 0.1 % v/v, and even more preferably less than 0.01 % v/v of any of its mono-, dual- or tris-, analogs or other reaction products.
• This embodiment may provide better process repeatability.
• This embodiment may be produced by distillation of the Si-containing film forming composition.
• Purification of the disclosed Si-Containing film forming composition may also produce concentrations of trace metals and metalloids ranging from approximately 0 ppbw to approximately 500 ppbw, and more preferably from approximately 0 ppbw to approximately 100 ppbw.
• metal or metalloid impurities include, but are not limited to, Aluminum(AI), Arsenic(As), Barium(Ba), Beryllium(Be), Bismuth(Bi), Cadmium(Cd), Calcium(Ca), Chromium(Cr), Cobalt(Co), Copper(Cu), Gallium(Ga), Germanium(Ge), Hafnium(Hf), Zirconium(Zr), Indium(ln), Iron(Fe), Lead(Pb), Lithium(Li), Magnesium(Mg), Manganese(Mn), Tungsten(W), Nickel(Ni), Potassium(K), Sodium(Na), Strontium(Sr), Thorium(Th), Tin(Sn), Titanium(Ti), Uranium(U), Vanadium(V) and Zinc(Zn).
• the product may be filtered to reach specifications that are typical of products used in the semiconductor industry.
• compositions comprising any of the products from Families (1 ) through (4) may be used for the chemical vapor phase deposition (CVD) of silicon containing thin films for applications in the semiconductor, flat panel display, photovoltaic, and more generally for silicon based coatings. It is understood that the term "CVD" encompasses all embodiments in which a precursor is brought in a vapor phase in contact with a substrate on which the silicon thin film is to be deposited.
• CVD may mean low pressure chemical vapor deposition (LPCVD), sub-atmospheric chemical vapor phase deposition (SA-CVD), atmospheric chemical vapor deposition (AP-CVD), Flowable chemical vapor deposition (F-CVD), Atomic Layer Deposition (ALD), Molecular Layer Deposition (MLD), Pulsed chemical vapor deposition (P-CVD), flow-modulated chemical vapor deposition (FM-CVD).
• LPCVD low pressure chemical vapor deposition
• SA-CVD sub-atmospheric chemical vapor phase deposition
• AP-CVD atmospheric chemical vapor deposition
• F-CVD Flowable chemical vapor deposition
• ALD Atomic Layer Deposition
• MLD Molecular Layer Deposition
• P-CVD Pulsed chemical vapor deposition
• FM-CVD flow-modulated chemical vapor deposition
• PE in-situ plasma
• PE remote plasma
• HW hot wire
• UV photons
• the precursors of Families (1 ) through (4) may be used in conjunction with a co-reactant that would be typically selected from:
• the precursors of Families (1 ) through (4) may be used in conjunction with another metal or metalloid volatile precursor to deposit silicon containing films.
• examples of such films include but are not limited to SiTiO, SiAIO, SiZrO, SiHfO, SiBO, SiPO, SiAsO, SiBPO, SiGeO, SiBN, SiAIN, SiTiN, CoSiN, NiSiN, TaSiN, WSiN, understanding that the composition does not take into account the potential low level carbon impurities, typically ⁇ 5%, and preferably ⁇ 2%, coming from the precursors and the ligands.
• the compounds of families (1 ), (2) and (4), having a hydrolysable functional group like NR 1 R 2 , N-C ⁇ N, or -Si-NH-Si are particularly suitable for ALD or PE-ALD of silicon oxide or silicon nitride based films, as they provide a reactive site for the precursors to react with the hydroxyl (-OH) or -NH2 groups on the surface substrate and chemically bind to it. They also have a number of silicon atom > 3, and are hence expected to yield a higher growth per cycle versus the existing molecules.
• the compounds of all families are also particularly suitable for LPCVD, PECVD and FCVD owing to their high silicon content and structure that is close to a silicon nitride pre-ceramic.
• These compounds have a rather low vapor pressure and are suitable for deposition by condensation (C-CVD) over a substrate (by maintaining the substrate at a temperature lower than the dew point of the precursor in the deposition equipment).
• the thermally condensed composition may then be further treated by exposure to an oxidizing atmosphere such as O2, O3, steam, or H2O2 vapors, mixtures and plasma thereof, at a temperature preferably between 0°C and 900°C, more preferably between 300° and 800°C, possibly in several steps to avoid the re- evaporation of the composition on the substrate, in order to convert the condensed silazane composition to a silica film.
• Such processes are particularly useful to deposit a dielectric film in fine trenches or holes (gap fill).
• the film may be exposed to a nitriding atmosphere (N2, NH3, hydrazines, and plasma thereof) at a temperature preferably between 100°C and 1 100°C, more preferably between 300° and 900°C for conversion of the short chain polysilazane precursor to large chain polysilazanes and SiN pre-ceramics.
• a nitriding atmosphere N2, NH3, hydrazines, and plasma thereof
• the compounds of families 1 through 4 and preferably the fully C-free compounds of family 1 and 2 may also be useful in formulation for liquid phase deposition such as spin coating, dip coating or spray coating, or as intermediates and ingredients for the synthesis of such formulations.

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