Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—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
• • 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
  • C23C16/06—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 metallic material
  • C23C16/18—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 metallic material from metallo-organic compounds
• • 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
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
• • 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
  • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
  • H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
  • H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
  • H01L21/02192—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
  • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
  • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
  • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Definitions

• lanthanide-containing film forming compositions comprising Lanthanide precursors having the general formulae, L-Ln-C5R4-[(ER2)m-(ER2)n-L'], L-Ln-C4AR3-3-[(ER 2 )m-(ER 2 )n-L']-, L-Ln-C3(m-A2)R2-4-[(ER2)m-(ER 2 )n-L']-, wherein Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an ⁇ 5 bonding mode to the aromatic ring group; A is independently N, Si, B, P or O; each E is independently C, Si, B or P; m and n are independently 0, 1 or 2; m + n >1 ; each R is independently an H or a C1-C4 hydrocarbyl group; adjacent Rs may
• ALD atomic layer deposition
• Lanthanum 2,2-6,6- tetramethylheptanedionate's [La(tmhd)3] melting point is as high as 230 ° C
• Lanthanum tris(bis(trimethylsilyl)amido) [La(tmsa)3] melting point is 150 ° C. Additionally, the delivery efficiency of those precursors is very difficult to control.
• Non-substituted cyclopentadienyl compounds also exhibit low volatility with a high melting point. Molecule design may both help improve volatility and reduce the melting point. However, in process conditions, these classes of materials have been proven to have limited use. For instance, La(iPrCp)3 does not allow an ALD regime above 225 ° C.
• Cp bridged Y and Lu compounds are synthesized and may be used for catalysts or precursors for rare-earth oxide thin films.
• F Edelmann discloses the Cp-one ligand bridged Y compound Me 4 Cp-SiMe2-N(ph)- Y- (F Edelmann, "Lanthanide Aamidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare- earth oxide thin films", Chem. Soc. Rev., 2009, 38, p2253-2268).
• Lanthanide precursors currently available present many drawbacks when used in a deposition process. Consequently, there exists a need for alternate precursors for deposition of Lanthanide-containing films.
• Lanthanide-containing film forming compositions comprising Lanthanide precursors having the general formulae:
• Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an rf bonding mode to the aromatic ring group;
• A is independently N, Si, B, P or O;
• each E is independently C, Si, B or P;
• m and n are independently 0, 1 or 2;
• each R is independently an H or a C1-C4 hydrocarbyl group; adjacent Rs may be joined to form a hydrocarbyl ring;
• L is a -1 anionic ligand selected from the group consisting of NR 2, OR ' , Cp, amidinate, ⁇ -diketonate, or keto-iminate, wherein R ' is an H or a C1-C4 hydrocarbon group; adjacent R s may be joined to form a hydrocarbyl ring; and L' is NR" or
• the aromatic group being a heterocyclic group containing N, Si, B, P or 0;
• the aromal ic group being a methyl substituted pyrrole
• the aromal ic group being an isopropyl substituted pyrrole
• the aromal ic group being a tertbutyl substituted pyrrole
• the aromal ic group being a methyl substituted pyrazole
• the aromal ic group being an isopropyl substituted pyrazole
• the aromal ic group being a tertbutyl substituted pyrazole
• the aromal ic group being a methyl substituted imidazole
• the aromal ic group being an isopropyl substituted imidazole
• the aromal ic group being a tertbutyl substituted imidazole
• the aromal ic group being a methyl substituted silacyclopentadienide; the aromal ic group being an isopropyl substituted silacyclopentadienide the aromal ic group being a tertbutyl substituted silacyclopentadienide; the aromal ic group being a methyl substituted borole;
• the aromal ic group being an isopropyl substituted borole
• the aromal ic group being a tertbutyl substituted borole
• the aromal ic group being a methyl substituted phosphole
• the aromal ic group being an isopropyl substituted phosphole
• the aromal ic group being a tertbutyl substituted phosphole
• the Lanthanide precursor being (Me 2 N)-La-C5H 3 -1 -Me-3-[(CH2)2-NMe]-; the Lanthanide precursor being (Me 2 N)- -Y-C5H3-I -Me-3-[(CH 2 ) 2 -NMe]-; the Lanthanide precursor being (Me 2 N)- -SC-C5H3-I -Me-3-[(CH 2 ) 2 -NMe]-; the Lanthanide precursor being (Me 2 N)- -Ce-CsHs-l -Me-3-[(CH 2 ) 2 -NMe]-; the Lanthanide precursor being (Me 2 N)- -Pr-CsHs-l -Me-3-[(CH 2 ) 2 -NMe]-; the Lanthanide precursor being (Me 2 N)- -Nd-CsHs-l -Me-3-[(CH 2 ) 2 -NMe]-
• the Lanthanide precursor being Cp-La-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-;
• the Lanthanide precursor being Cp-Sc-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-;
• the Lanthanide precursor being Cp-Pr-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-;
• the Lanthanide precursor being Cp-Sm-C5H3-1 -Me-3-[(CH2)2-0]-;
• the Lanthanide precursors disclosed above are introduced into a reactor having a substrate disposed therein. At least part of the Lanthanide precursor is deposited onto the substrate to form the Lanthanide- containing film on the substrate using a vapor deposition process.
• the disclosed method may optionally include one or more of the following aspects:
• the substrate being a Ge02 film
• the substrate being a high k gate dielectric film
• the Lanthanide precursor being a liquid at a temperature below 70°C;
• the Lanthanide precursor being a liquid at a temperature below 40°C
• the Lanthanide-containing film being selected from the group consisting of Ln 2 03, (LnLn')03, L ⁇ Os-Ln ⁇ Os, LnSixOy, LnGe x O y , (Al, Ga, Mn)Ln03, HfLnOx, and ZrLnOx, LnSrCo04, LnSrMn04, wherein Ln' is a different Lanthanide from Ln and x and y are each a number selected from 1 -5 inclusive;
• the reactant species being selected from the group consisting of O2, O3, H2O, H2O2, acetic acid, formalin, para-formaldehyde, and combinations thereof;
• the vapor deposition process being a chemical vapor deposition process
• the vapor deposition process being an atomic layer deposition process
• the vapor deposition process being a spatial ALD process
• the vapor deposition process including a plasma process
• the vapor deposition process being a thermal process.
• Lanthanide-containing film coated substrates comprising the product of the disclosed methods. Notation and Nomenclature
• the indefinite article “a” or “an” means one or more.
• the term "independently" when used in the context of describing R groups should be understood to denote that the subject R group is not only 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.
• 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 “"Pr” refers to a "normal” or linear propyl group
• the abbreviation “'Pr” refers to an isopropyl group
• the abbreviation “Bu” refers to a butyl group
• the abbreviation “"Bu” refers to a "normal” or linear butyl group
• the abbreviation “ f Bu” refers to a fe/f-butyl group, also known as 1 , 1 - dimethylethyl
• the abbreviation “ s Bu” refers to a sec-butyl group, also known as 1 - methylpropyl
• the abbreviation “'Bu” refers to an /so-butyl group, also
• the abbreviation "ortho-” or “o-” refers to an aromatic ring having carbon replacements at 1 ,2 positions; the abbreviation “meta-” or “m-” refers to an aromatic ring having carbon replacements at 1 ,3 positions; the abbreviation “para-” or “p-” refers to an six- memebered aromatic ring having carbon replacements at 1 ,4 positions.
• the compounds shown in following structure formula are represented by (Me2N)-La-C3(m-A2)H2-4-(CH2- -NMe)-
• La is bonded in an if bonding mode to the aromatic ring group;
• A is independently N, Si, B or P.
• ⁇ 5 is the hapticity of the above precursors representing five contiguous atoms of the aromatic ring group bonded to the La atom.
• L-Ln-CsF - [(ER 2 )m-(ER 2 )n-L']-, L-Ln-C4AR3-3-[(ER 2 )m-(ER 2 )n-L']- and L-Ln-C 3 (m-A 2 )R2-4- [(ER2)m-(ER2)n-L']-, refer to the compounds having the following structure formula, respectivel :
• Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an ⁇ 5 bonding mode to the aromatic ring group;
• A is independently N, Si, B, P or 0; each E is independently C, Si, B or P; m and n are independently 0, 1 or 2; m + n >1 ;
• each R is independently an H or a C1 -C4 hydrocarbyl group; and adjacent Rs may be joined to form a hydrocarbyl ring;
• each L is independently a -1 anionic ligand selected from the group consisting of NR2, OR ' , Cp, amidinate, ⁇ -diketonate, or keto-iminate, wherein R ' is an H or a C1-C4 hydrocarbon group; and adjacent R s may be joined to form a hydrocarbyl ring; and each L' is independently
• Ln refers to the Lanthanide group, which includes the following elements: lanthanum (“La”), yttrium (“Y”), scandium (“Sc”), cerium (“Ce”), praseodymium (“Pr”), neodymium (“Nd”), samarium (“Sm”), europium (“Eu”), gadolinium (“Gd”), terbium (“Tb”), dysprosium (“Dy”), holmium (“Ho”), erbium (“Er”), thulium (“Tm”), ytterbium (“Yb”), or lutetium (“Lu”);
• the abbreviation “Cp” refers to cyclopentadienyl;
• A refers to angstroms; prime (“ ' ") is used to indicate a different component than the first, for example (LnLn')O3 refers to a Lanthanide oxide containing two different Lanthan
• 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 may be listed throughout the specification and claims without reference to their proper stoichiometry.
• 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.
• 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.
• Lanthanide-containing film forming compositions are disclosed.
• the Lanthanide-containing film forming compositions comprise Lanthanide precursors having the general formulae,
• Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an ⁇ 5 bonding mode to the aromatic group;
• A-containing aromatic group contains one or two As wherein the two As are at ortho- or meta- positions;
• A is independently N, Si, B, P or O;
• each E is independently C, Si, B or P;
• m and n are independently 0, 1 or 2;
• each R is independently an H or a C1-C4 hydrocarbyl group; adjacent Rs may be joined to form a hydrocarbyl ring;
• each L is independently a -1 anionic ligand selected from the group consisting of NR2, OR ' , Cp, amidinate, ⁇ -diketonate, or keto-iminate, wherein R ' is an H or a C1-C4 hydrocarbon group;
• the Lanthanide-containing film forming compositions further comprise the Lanthanide precursors having the following formulae:
• Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an ⁇ 5 bonding mode to the aromatic group;
• A is independently N, Si, B, P or O;
• each E is independently C, Si, B or P;
• m and n are independently 0, 1 or 2;
• each R is independently an H or a C1-C4 hydrocarbyl group; and adjacent Rs may be joined to form a hydrocarbyl ring;
• each L is independently a -1 anionic ligand selected from the group consisting of NR 2, OR ' , Cp, amidinate, ⁇ -diketonate, or keto-iminate, wherein R ' is an H or a C1-C4 hydrocarbon group; and adjacent R s may be joined to form a hydrocarbyl ring; and each L' is independently
• Preferred Lanthanide precursors include (Me2N)-Ln-C5H3-1 -Me-3-(CH2- CH 2 -NMe)- and (Me 2 N)-Ln-C5H3-1 -Me-3-(CH2-CH 2 -0)-, corresponding to the following structure formula respectively:
• Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr,
• the compounds include Cp-La-C5H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-; Cp- Y-CsHs-1 -Me-3-[(CH 2 ) 2 -NMe]-; Cp-Sc-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-; Cp-Ce-CsHs-1 - Me-3-[(CH 2 ) 2 -NMe]-; Cp-Pr-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-; Cp-Nd-C 5 H 3 -1 -Me-3- [(CH 2 ) 2 -NMe]-; Cp-Sm-C 5 H 3 -1 -Me-3-[(CH 2 ) 2 -NMe]-; Cp-Eu-CsHs-1 -Me-3-[(CH 2 ) 2 -NMe]-;
• the disclosed Lanthanide-containing precursors having the above structures i.e., having one aromatic group with asymmetric structure may be liquid and less or not viscous.
• the disclosed Lanthanide-containing precursors having the above structures may have high vapor pressure and may be used in direct liquid injection (DLI) where the precursor is fed in a liquid state and then vaporized before it is introduced into a reactor.
• DLI direct liquid injection
• bridged aromatic groups for example, cyciopentadienyi (Cp)/amino or bridged Cp/alkoxy, may help to stabilize the compounds.
• Such properties include better control of steric crowding around the metal center, which in turn controls the surface reaction on the substrate and the reaction with a second reactant (such as an oxygen source).
• a second reactant such as an oxygen source.
• Independently fine tuning the substituents on the ligands increases volatility and thermal stability and decreases melting point to yield either liquids or low melting solids.
• Lanthanide precursors with properties suited for the vapor deposition process (i.e., a volatile, yet thermally stable, liquid or low melting solid (having a melting point below about 105 ° C)
• a direct correlation between the properties of the central metal ion (coordination number) and ligands (steric effect, ratio of two heteroleptic ligands) has been observed.
• the metal compound has a 3+ charge and coordination number of 6.
• m is 2 and n is 1 .
• the Lanthanide precursor has a melting point below about 105°C, preferably below about 80 ° C, more preferably below about 70°C, and even more preferably below about 40°C.
• the synthesis of the lanthanide precursors may be carried out by following methods:
• Lanthanide precursor may be deposited to form Lanthanide-containing films using any vapor deposition methods known to those of skill in the art.
• suitable vapor deposition methods include without limitation, conventional chemical vapor deposition (CVD), atomic layer deposition (ALD), or other types of vapor depositions that are variations thereof, such as plasma enhanced ALD (PEALD), plasma enhanced CVD (PECVD), low pressure CVD (LPCVD), pulsed chemical vapor deposition (P-CVD), low pressure CVD (LPCVD), sub- atmospheric CVD (SACVD), atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), thermal ALD, thermal CVD, spatial ALD, hot-wire ALD (HWALD), radicals incorporated deposition, and super critical fluid deposition, or combinations thereof.
• the deposition method is preferably ALD, PE-ALD, or spatial ALD in order to provide suitable step coverage and film
• the substrate upon which the Lanthanide-containing film will be deposited will vary depending on the final use intended.
• the substrate may be chosen from oxides which are used as dielectric materials in MIM, DRAM, FeRam technologies or gate dielectrics in CMOS technologies (for example, HfO2 based materials, T1O2 based materials, GeO2 based materials, ZrO2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based films (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer.
• oxides which are used as dielectric materials in MIM, DRAM, FeRam technologies or gate dielectrics in CMOS technologies (for example, HfO2 based materials, T1O2 based materials, GeO2 based materials, ZrO2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based films (for example, TaN) that are used as
• substrates include, but are not limited to, solid substrates such as metal substrates (for example, Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt and metal silicides, such as TiSi2, C0S12, and NiSi2); metal nitride containing substrates (for example, TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); semiconductor materials (for example, Si, SiGe, GaAs, InP, diamond, GaN, and SiC); insulators (for example, S1O2, SisN 4 , SiON, Hf02, Ta 2 05, Zr02, T1O2, AI2O3, and barium strontium titanate); or other substrates that include any number of combinations of these materials.
• metal substrates for example, Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt and metal silicides, such as TiSi2, C0S12, and NiSi2
• Plastic substrates such as poly(3,4- ethylenedioxythiophene)poly (styrenesulfonte) [PEDOTPSS], may also be used.
• the actual substrate utilized may also depend upon the specific precursor embodiment utilized. In many instances though, the preferred substrate utilized will be selected from TiN, Ru, and Si type substrates.
• the vapor of the Lanthanide precursor is introduced into a reactor containing at least one substrate.
• the temperature and the pressure within the reactor and the temperature of the substrate are held at conditions suitable for vapor deposition of at least part of the Lanthanide precursor onto the substrate.
• conditions within the chamber are such that at least part of the vaporized precursor is deposited onto the substrate to form the Lanthanide-containing film.
• the reactor may be any enclosure or chamber of a device in which deposition methods take place, such as, without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, or other such types of deposition systems.
• the reactor may be maintained at a pressure ranging from about 0.5 mTorr to about 20 Torr.
• the temperature within the reactor may range from about 250°C to about 600°C.
• the temperature may be optimized through mere experimentation to achieve the desired result.
• the substrate may be heated to a sufficient temperature to obtain the desired Lanthanide-containing film at a sufficient growth rate and with desired physical state and composition.
• a non-limiting exemplary temperature range to which the substrate may be heated includes from 150°C to 600°C.
• the temperature of the substrate remains less than or equal to 450°C.
• the Lanthanide precursor may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor. Prior to its vaporization, the Lanthanide precursor may optionally be mixed with one or more solvents, one or more metal sources, and a mixture of one or more solvents and one or more metal sources.
• the solvents may be selected from the group consisting of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, or others.
• the resulting concentration may range from approximately 0.05 M to approximately 2 M.
• the metal source may include any metal precursors now known or later developed.
• the Lanthanide precursor may be vaporized by passing a carrier gas into a container containing the Lanthanide precursor or by bubbling the carrier gas into the Lanthanide precursor.
• the carrier gas may include, but is not limited to, Ar, He, N2, and mixtures thereof.
• the carrier gas and Lanthanide precursor are then introduced into the reactor.
• the container may be heated to a temperature that permits the Lanthanide precursor to be in its liquid phase and to have a sufficient vapor pressure.
• the carrier gas may include, but is not limited to, Ar, He, N2,and mixtures thereof.
• the Lanthanide precursor may optionally be mixed in the container with a solvent, another precursor, or a mixture thereof.
• the container may be maintained at temperatures in the range of, for example, 0-100°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of Lanthanide precursor vaporized.
• the Lanthanide precursor may be mixed with reactant species inside the reactor.
• exemplary reactant species include, without limitation, H2, metal precursors such as TMA or other aluminum-containing precursors, other Lanthanide precursors, TBTDET, TAT-DMAE, PET, TBTDEN, PEN, and any combination thereof.
• the reactant species may include an oxygen source which is selected from, but not limited to, O2, O3, H2O, H2O2, acetic acid, formalin, para-formaldehyde, and combinations thereof.
• the reactant species may include a nitrogen source which is selected from, but not limited to, nitrogen (N2), ammonia and alkyl derivatives thereof, hydrazine and alkyl derivatives thereof, N-containing radicals (for instance N , NH , N H2 ), NO, N2O, NO2, amines, and any combination thereof.
• N2 nitrogen
• N-containing radicals for instance N , NH , N H2
• the reactant species may include a carbon source which is selected from, but not limited to, methane, ethane, propane, butane, ethylene, propylene, t-butylene, isobutylene, CCU, and any combination thereof.
• the reactant species may include a silicon source which is selected from, but not limited to, SiH 4 , S 12H6, SisHs, TriDMAS, BDMAS, BDEAS, TDEAS, TDMAS, TEMAS, (SiH 3 ) 3 N, (SiH 3 ) 2 O, trisilylamine, disiloxane, trisilylamine, disilane, trisilane, an alkoxysilane SiHx(OR 1 )4-x, a silanol Si(OH) x (OR 1 )4-x (preferably Si(OH)(OR 1 )3 ; more preferably Si(OH)(OtBu) 3 an aminosilane SiH x (NR 1 R 2 ) 4 -x (
• the reactant species may include a precursor which is selected from, but not limited to, alkyls such as SbR' 3 or SnR' ' 4 (wherein each R' ' is independently H or a linear, branched, or cyclic C1 - C6 carbon chain), alkoxides such as Sb(OR')3 or Sn(OR')4 (where each R' is independently H or a linear, branched, or cyclic C1 -C6 carbon chain), and amines such as Sb(NR 1 R 2 )(NR 3 R 4 )(NR 5 R 6 ) or Ge(NR 1 R 2 )(NR 3 R 4 )(NR 5 R 6 )(NR 7 R 8 ) (where each precursor which is selected from, but not limited to, alkyls such as SbR' 3 or SnR' ' 4 (wherein each R' ' is independently H or a linear, branched, or cyclic C1 - C6 carbon chain), alkoxides such
• the Lanthanide precursor and one or more reactant species may be introduced into the reactor simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations.
• the Lanthanide precursor may be introduced in one pulse and two additional metal sources may be introduced together in a separate pulse [modified atomic layer deposition].
• the reactor may already contain the reactant species prior to introduction of the Lanthanide precursor.
• the reactant species may be passed through a plasma system localized remotely from the reactor, and decomposed to radicals.
• the Lanthanide precursor may be introduced to the reactor continuously while other reactant species are introduced by pulse (pulsed-chemical vapor deposition).
• a pulse may be followed by a purge or evacuation step to remove excess amounts of the component introduced.
• the pulse may last for a time period ranging from about 0.01 s to about 10 s, alternatively from about 0.3 s to about 3 s, alternatively from about 0.5 s to about 2 s.
• the vapor phase of a Lanthanide precursor is introduced into the reactor, where at least part of the Lanthanide precursor reacts with a suitable substrate in a self-limiting manner. Excess Lanthanide precursor may then be removed from the reactor by purging and/or evacuating the reactor. An oxygen source, such as ozone, is introduced into the reactor where it reacts with the absorbed Lanthanide precursor.
• any excess oxygen source is removed from the reactor by purging and/or evacuating the reactor. If the desired film is a Lanthanide oxide film, this two-step process may provide the desired film thickness or may be repeated until a film having the necessary thickness has been obtained.
• LaGeOx wherein x is a number ranging from 1 to 5 inclusive, may spontaneously form when the ALD LaO film is deposited on a Ge or GeO2 substrate.
• the LaGeOx film may serve as a channel material in metal oxide semiconductor (MOS) devices due to high hole mobility and low dopant activation temperatures.
• MOS metal oxide semiconductor
• the LaOx film may be deposited as a capping layer on an HfOx or ZrOx high k gate dielectric film, with x being a number ranging from 1 to 5 inclusive.
• the LaOx capping layer reduces Fermi level pinning effects between the gate dielectric layer and a metal gate.
• the two-step process above may be followed by introduction of the vapor of a precursor into the reactor.
• the precursor will be selected based on the nature of the Lanthanide metal oxide film being deposited and may include a different Lanthanide precursor.
• the precursor is contacted with the substrate. Any excess precursor is removed from the reactor by purging and/or evacuating the reactor.
• an oxygen source may be introduced into the reactor to react with the precursor. Excess oxygen source is removed from the reactor by purging and/or evacuating the reactor.
• a desired film thickness has been achieved, the process may be terminated. However, if a thicker film is desired, the entire four-step process may be repeated. By alternating the provision of the Lanthanide precursor, precursor, and oxygen source, a film of desired composition and thickness can be deposited.
• the Lanthanide-containing films or Lanthanide-containing layers resulting from the processes discussed above may include La2O3, (LaLn)O3, La2O3-Ln2O3, LaSixOy, LaGexOy, (Al, Ga, Mn)LnO3, HfLaOx or ZrLaOx, LaSrCoO4, LaSrMnO4 where Ln is a different Lanthanide and x is 1 to 5 inclusive.
• the Lanthanide-containing film may include HfLaOx or ZrLaOx.
• the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure.
• further processing such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure.
• the lanthanum-containing film may be exposed to a temperature ranging from approximately 200°C and approximately 1000°C for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, an H-containing atmosphere, a N-containing atmosphere, an O-containing atmosphere, or combinations thereof.
• the temperature is 350°C for 1800 seconds under an inert atmosphere of Argon.
• the resulting film may contain fewer impurities and therefore may have an improved density resulting in improved leakage current.
• the annealing step may be performed in the same reactor in which the deposition process is performed. Alternatively, the substrate may be removed from the reactor, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, has been found effective to reduce carbon and nitrogen contamination of the Lanthanide- containing film. This in turn tends to improve the leakage current and the interface trap density (Dit) of the film.

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