Classifications

• • 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
  • C07F17/00—Metallocenes
• • 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
  • C23C16/22—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
  • C23C16/405—Oxides of refractory metals or yttrium
• • 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

Definitions

• zirconium-containing precursors Disclosed are zirconium-containing precursors, methods of synthesizing the same, and methods of using the same to deposit zirconium oxides or oxynitrides or other metal doped oxides containing layers using vapor deposition processes for manufacturing semi-conductors.
• metal-lnsulator-Metal architectures for RAM applications.
• Various metal compositions have been considered to fulfill both the materials requirements (dielectric constant, leakage current, crystallization temperature, charge trapping) and the integration requirements (thermal stability at the interface, dry etching feasibility).
• the Group IV based materials such as HfO 2 , HfSiO 4 , ZrO 2 , ZrSiO 4 , HfZrO 4 , HfLnOx (Ln being selected from the group comprising scandium, yttrium and rare- earth elements) and more generally HfMOx and ZrMOx, M being an element selected from Group II, Group Ilia, Group 1 Mb, a transition metal, or rare earth metal, are among most promising materials.
• Group IV metals composition may also be considered for electrode and/or Cu diffusion barrier applications, such as TiN for mid-gap metal gate and HfN, ZrN, HfSi, ZrSi, HfSiN, ZrSiN, TiSiN for MIM electrodes.
• vapor phase deposition techniques such as Vapor Deposition or ALD (Atomic Layer Deposition).
• INCORPORATED BY REFERENCE (RULE 20.6) deposition processes require metal precursors that must fulfill drastic requirements for a proper industrial use. Metal-organic precursors are desired for those processes. Various hafnium and zirconium metal-organic compounds have been considered as precursors to enable such a deposition.
• Kruck et al. disclose deposition of a Ti-, Zr-, or Hf- containing film on a substrate by decomposition of tris(dialkylamino) pyrrolyl compounds or bis(dialkylamino)dipyrrolyl compounds.
• Katayama et al. disclose a catalyst system comprising a transition metal compound having at least one of a cyclopentadienyl group or a substituted cyclopentadienyl group and at least one of a cyclic ligand containing a hetero atom and having a delocalized ⁇ bond.
• the extensive listing of exemplary transition metal compounds includes molecules having halide bonds.
• Dussarrat et al. disclose Hf, Zr, and Ti compounds having the formula (R 1 yOp) x (R 2 tCp) z MR' 4- x-z, wherein 0 ⁇ x ⁇ 3; 0 ⁇ z ⁇ 3; 1 ⁇ (x+z) ⁇ 4; 0 ⁇ y ⁇ 7; 0 ⁇ t ⁇ 5; R 1 y Op represents a pentad ienyl (Op) ligand; R 2 t Cp represents a cyclopentadienyl (Cp) ligand; R 1 and R 2 independently represent CI, a linear or branched alkyl group, an N-alkyl amino group, an ⁇ , ⁇ -dialkylamino group, a linear or branched alkoxy group, an alkylsilylamide group, an amidinate group, or a carbonyl group; and R' represents H, F, CI, Br, I, a linear or branched alky
• Norman et al. disclose metal complexes utilizing sterically hindered imidazolate ligands, where at least one of carbons of the imidazolate are substituted with a C1-C10 primary, secondary, or tertiary alkyl; Ci- C10 primary, secondary or tertiary alkoxy; C1-C10 primary, secondary, or tertiary alkylamine; C1-C10 primary, second, or tertiary alkyl functionalized with a heteroatom substituted ring structure selected from the group consisting of imidazole, pyrrole, pyridine, furan, pyrimidine, pyrazole C1-C10 alkyl functionalized
• alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl 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 any propyl group (i.e., n-propyl or isopropyl);
• the abbreviation “iPr” refers to an isopropyl group
• the abbreviation “Bu” refers to any butyl group (n-butyl, iso-butyl, t-butyl, sec-butyl);
• the abbreviation “tBu” refers to a tert-butyl group
• the abbreviation “sBu” refers to a sec-butyl group
• the abbreviation “iBu” refers to an iso-butyl group
• the abbreviation “ph” refers to a phenyl group
• the abbreviation “Cp” refers to cyclopentadieny
• Ri , R2, R3, R4, R5, R6, and R 7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
• Cy-amines refer to saturated N-containing ring systems or unsaturated N-containing ring systems, the N-containing ring system comprising at least one nitrogen atom and 4-6 carbon atoms in a chain.
• the disclosed molecules may further include one or more of following aspects:
• N-containing ring system consisting of at least one nitrogen atom and 4-6 carbon atoms
• N-containing ring system being selected from the group consisting of pyrroles, pyrrolidines, and piperidines;
• N-containing ring system being a pyrrole
• N-containing ring system being a pyrrolidine
• N-containing ring system being a piperidine
• N-containing ring system further comprising one or more substituents independently selected from the group consisting of a C1 -C6 alkyl group;
• the disclosed methods may further include one or more of the following aspects:
• an element of the at least one second precursor being selected from the group consisting of group 2, group 13, group 14, transition metal,
• the element of the at least one second precursor being selected from Mg, Ca, Sr, Ba, Hf, Nb, Ta, Al, Si, Ge, Y, or lanthanides;
• the co-reactant being selected from the group consisting of O 2 , O3, H 2 O, H 2 O 2 , NO, NO 2 , a carboxylic acid, and combinations thereof;
• the Zr-containing layer being a zirconium oxide layer
• the vapor deposition process being a chemical vapor deposition process
• FIG 1 is a thermogravimetric analysis (TGA)/differential thermal analysis (DTA) graph demonstrating the percentage of weight loss with temperature change for Zr(NMe 2 )3(NC 4 H 8 );
• FIG 2 is a TGA/DTA graph for Zr(NMe 2 )2(NC 4 H 8 ) 2 ;
• FIG 3 is a TGA/DTA graph for Zr(NEtMe) 3 (NC 4 H 8 );
• FIG 4 is a TGA graph for purifited Zr(Cp)(NMe 2 )2(NC 4 H 8 );
• zirconium-containing precursors Disclosed are zirconium-containing precursors, methods of synthesizing the same, and methods of using the same.
• the disclosed heteroleptic zirconium-containing precursors are derived from different classes of ligand systems, such as cyclopentadienyl, amide, and/or cyclic amide ligands (saturated ring systems or un-saturated ring systems).
• Precursor design may help improve volatility, reduce the melting point (liquids or very low melting solids), increase reactivity with water, and increase thermal stability for wider process window applications.
• the disclosed zirconium-containing precursors have the following formula:
• Ri , R2, R3, R4, R5, R6, and R 7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
• Cy-amines refer to saturated N-containing ring systems or unsaturated N-containing ring systems, the N-containing ring system
• the C1 -C6 alkyl group includes any linear, branched, or cyclic alkyl groups having from 1 to 6 carbon atoms, including but not limited to Me, tBu, or cyclohexyl groups.
• the configuration of the disclosed precursors was selected in order to optimize the reactivity (in one embodiment, with H 2 O) and, at the same time, the stability.
• the Zr-N bond is weak and will react rapidly on the surface of the substrate. By tuning this molecule, a precursor is obtained that reacts well on the substrate thanks to a weaker site.
• the disclose precursors are surprisingly volatile and stabile. Further stability can be controlled via tuning the cyclic amides ring sizes, ring substitutions and saturation and un-saturation of the rings systems.
• the (Ri-R 5 Cp) ligand has the following chemical structure:
• the cyclopentadienyl ligand may include one or more substitutents (R R 5 ) independently selected from the group consisting of a C1 -C6 alkyl group.
• exemplary (Ri-R 5 Cp) ligands include 1 -(1 ,1 -dimethylethyl)-1 ,3-Cyclopentadienyl; 1 -butyl-1 ,3-cyclopentadienyl; 1 -propyl-1 ,3-cyclopentadienyl; 1 -(1 -methylpropyl)-1 ,3- cyclopentadienyl; 1 -(1 -methylethyl)-1 ,3-cyclopentadienyl; 1 -ethyl-1 ,3- cyclopentadienyl; 1 ,3-cyclopentadienyl; 1 -methyl-1 ,3-cyclopentadienyl; 1 ,2,4
• the (Cy-amines) ligand refers to saturated N-containing ring systems or unsaturated N-containing ring systems, the N-containing ring system comprising at least one nitrogen atom and 4-6 carbon atoms in a chain. Alternatively, the N- containing ring system may consist of at least one nitrogen atom and 4 or 5 carbon atoms.
• Structural formulae for the Cy-amines include:
• the (Cy-amines) ligand may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group.
• the (Cy-amines) ligands include pyrrole ligands (also referred to
• the pyrrole ligands may include one or more substitutents (R') independently selected from the group consisting a C1 -C4 alkyl group.
• exemplary pyrrole ligands include 1 H-Pyrrole; 2-butyl-3-methyl-1 H- Pyrrole; 2-metyl-4-(1 -methylpropyl)-1 H-Pyrrole; 3-(1 ,1 -dimethylethyl)-4-methyl-1 H- Pyrrole; 3-methyl-4-(1 -methylethyl)-1 H-Pyrrole; 2,3,4-triethyl-l H-Pyrrole; 2,4- diethyl-3-propyl-1 H-Pyrrole; 2-ethyl-4-methyl-3-propyl-1 H-Pyrrole; 5-ethyl-2,3- dimethyl-1 H-Pyrrole; 3-methyl-4-propyl-1 H-Pyrrole;
• Exemplary (Cy-amines) ligands include pyrrolidine ligands (also referred to generically herein as NC 4 H 8 ).
• the pyrrolidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group.
• Exemplary pyrrolidine ligands include pyrrolidine, 3-methyl- pyrrolidine; 2-methyl-pyrrolidine; 3,3-dimethyl-pyrrolidine; 3,4-dimethyl-pyrrolidine; 3-ethyl-pyrrolidine; 2,2-dimethyl-pyrrolidine; 2-ethyl-pyrrolidine; 3-(1 -methylethyl)- pyrrolidine; 2,3-dimethyl-pyrrolidine; 3-propyl-pyrrolidine; 2-(1 -methylethyl)- pyrrolidine; 3-ethyl-3-methyl-pyrrolidine; 3,3,4-trimethyl-pyrrolidine; 3-ethyl-3- methyl-pyrrolidine; 2-propyl-pyrrolidine; 2,5-dimethyl-pyrrolidine; 2,4-dimethyl- pyrrolidine; 2-propyl-pyrrolidine; 3-(2-methylpropyl)-pyrrolidine; 3-(1 ,1 - dimethylethyl)-pyrrolidine; 2-ethyl
• Exemplary (Cy-amines) ligands include piperidine ligands (also referred to generically herein as NC 4 H 8 ).
• the piperidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group.
• Exemplary piperidine ligands include piperidine; 2,3,5,6-tetramethyl- piperidine; 2-(1 ,1 -dimethylethyl)-piperidine; 2-(2-methylpropyl)-piperidine; 2-butyl-
• the (ER6R 7 ) ligand has the following chemical structure:
• Exemplary (ER 6 R 7 ) ligands include dialkylamino and dialkylphosphide ligands, such as dimethylamino, ethylmethylamino, diethylamino, methylisopropylamino dimethylphoshpide, ethylmethylphoshpide, diethylphosphide, or
• exemplary precursors have one of the following generic formula: Zr(NC 4 H 8 ) 4 , Zr(NC 5 Hi 0 ) 4 , or Zr(NC 4 H ) , wherein the pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group as described above.
• exemplary precursors have the following generic formula: Zr(ER 6 R 7 )3(Cy-amines), wherein the Cy-amines ligand may be
• Exemplary precursors include Zr(NMe 2 ) 3 (NC 4 H 8 ), Zr(NEtMe) 3 (NC 4 H 8 ), Zr(NEt 2 ) 3 (NC 4 H 8 ), Zr(NMeiPr) 3 (NC 4 H 8 ), Zr(NMe 2 ) 3 (NC 5 Hio), Zr(NEtMe) 3 (NC 5 Hi 0 ), Zr(NEt 2 ) 3 (NC 5 Hi 0 ), Zr(NMeiPr) 3 (NC 5 Hi 0 ), Zr(PMe 2 ) 3 (NC 4 H 4 ), Zr(PEtMe) 3 (NC 4 H 4 ), Zr(PEt 2 ) 3 (NC 4 H 4 ), Zr(PMeiPr) 3 (NC 4 H 4 ), Zr(PMe 2 ) 3 (NC 4 H 8 ), Zr(PMeiPr) 3 (NC 4 H 8 ), Zr(PMe 2 ) 3 (NC 4 H 8 ), Zr(
• pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group as described above.
• exemplary precursors have the following generic formula: Zr(ER 6 R 7 ) 2 (Cy-amines) 2 , wherein the Cy-amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include Zr(NMe 2 ) 2 (NC 4 H 8 ) 2 , Zr(NEtMe) 2 (NC 4 H 8 ) 2 , Zr(NEt 2 ) 2 (NC 4 H 8 ) 2 ,
• pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group as described above.
• exemplary precursors have the following generic formula: Zr(ER 6 R7)(Cy-amines)3, wherein the Cy-amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include Zr(NMe 2 )(NC 4 H 8 ) 3 , Zr(NEtMe)(NC 4 H 8 ) 3 , Zr(NEt 2 )(NC 4 H 8 ) 3 ,
• Zr(NMeiPr)(NC 4 H 8 ) 3 Zr(NMe 2 )(NC 5 Hio) 3 , Zr(NEtMe)(NC 5 Hio) 3 , Zr(NEt 2 )(NC 5 Hio) 3 , Zr(NMeiPr)(NC 5 Hio) 3 , Zr(NMe 2 )(NC 4 H 4 ) 3 , Zr(NEtMe)(NC 4 H 4 ) 3 , Zr(NEt 2 )(NC 4 H 4 ) 3 , Zr(NMeiPr)(NC 4 H 4 ) 3 , Zr(PMe 2 )(NC 4 H 8 ) 3 , Zr(PEtMe)(NC 4 H 8 ) 3 , Zr(PEt 2 )(NC 4 H 8 ) 3 ,
• pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents (R') independently selected from the group consisting of a C1 -C4 alkyl group as described above.
• exemplary precursors have the following generic formula: ZrCp 2 (ER 6 R7)(Cy-amines), wherein the Cp ligand and Cy-amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include ZrCp 2 (NMe 2 )(NC 4 H 8 ), ZrCp 2 (NEtMe)(NC 4 H 8 ), ZrCp 2 (NEt 2 )(NC 4 H 8 ), ZrCp 2 (NMeiPr)(NC 4 H 8 ), ZrCp 2 (NMe 2 )(NC 5 H 10 ),
• cyclopentadienyl, pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents independently selected from the group consisting of a C1 -C6 alkyl group as described above.
• exemplary precursors have the following generic formula: ZrCp(ER 6 R7) 2 (Cy-amines), wherein the Cp ligand and Cy-amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include ZrCp(NMe 2 ) 2 (NC 4 H 8 ), ZrCp(NEtMe) 2 (NC 4 H 8 ),
• cyclopentadienyl, pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents independently selected from the group consisting of a C1 -C6 alkyl group as described above.
• exemplary precursors have the following generic formula: ZrCp(ER 6 R7)(Cy-amines)2, wherein the Cp ligand and Cy-amines ligand may be substituted or unsubstituted as described above.
• Exemplary precursors include ZrCp(NMe 2 )(NC 4 H 8 )2, ZrCp(NEtMe)(NC 4 H 8 ) 2 , ZrCp(NEt 2 )(NC 4 H 8 ) 2 , ZrCp(NMeiPr)(NC 4 H 8 ) 2 , ZrCp(NMe 2 )(NC5H 10 )2,
• cyclopentadienyl, pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents independently selected from the group consisting of a C1 -C6 alkyl group as described above.
• exemplary precursors have the following generic formula: ZrCp(Cy-amines)3, wherein the Cp ligand and Cy- amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include ZrCp(NC 4 H 8 ) 3 , ZrCp(NC 5 H 10 )3, or ZrCp(NC 4 H 4 ) 3 , wherein the Cp, pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents independently selected from the group consisting of a C1 -C6 alkyl group as described above.
• exemplary precursors have the following generic formula: ZrCp2(Cy-amines)2, wherein the Cp ligand and Cy-
• amines ligand may be unsubstituted or substituted as described above.
• Exemplary precursors include ZrCp2(NC 4 H 8 )2, ZrCp2(NC 5 Hi 0 )2, or ZrCp2(NC 4 H 4 ) 2 , wherein the Cp, pyrrole, pyrrolidine, and piperidine ligands may include one or more substitutents independently selected from the group consisting of a C1 -C6 alkyl group as described above.
• the disclosed precursors may be synthesized by combining a hydrocarbon solution of Zr(NR 6 R7) 4 or Zr(R R 5 Cp)(NR6R 7 )3 with a neat or hydrocarbon solution of ligand compound, such as NC 4 H 8 or NC5H10 or NC 4 H 4 , under atmosphere of nitrogen, the outlet of the mixing flask being connected to an oil bubbler.
• a hydrocarbon solution of Zr(NR 6 R7) 4 or Zr(R R 5 Cp)(NR6R 7 )3 with a neat or hydrocarbon solution of ligand compound, such as NC 4 H 8 or NC5H10 or NC 4 H 4 , under atmosphere of nitrogen, the outlet of the mixing flask being connected to an oil bubbler.
• Zr(NR 6 R7) 4 may be produced by reacting ZrCI 4 with Li(NR 6 R7).
• R 5 Cp)(NR 6 R 7 ) may be produced by reacting Zr(R r R 5 Cp)Cl3 with Li(NR 6 R 7 ).
• Exemplary hydrocarbon solutions include diethyl ether or pentane or toluene. The resulting solution is stirred at room temperature overnight. Solvent and volatiles are removed from the reaction mixture under vacuum. Purification of the resulting liquid or solid is carried out by distillation or sublimation, respectively. Additional synthesis details are provided in the Examples. Applicants believe that similar mechanisms may be used to form the PR 5 R6 molecules, but due to the nature of phosphorous containing molecules, have not yet had the opportunity to verify these synthesis mechanisms.
• the disclosed methods provide for the use of the zirconium-containing precursors for deposition of zirconium-containing layers.
• the disclosed methods may be useful in the manufacture of
• the method includes introducing at least one Zr-containing precursor disclosed above into a reactor having at least one substrate disposed therein and depositing at least part of the zirconium-containing precursor onto the at least one substrate to form a zirconium-containing layer using a vapor deposition process.
• the disclosed methods also may be used to form a two element-containing layer on a substrate using a vapor deposition process and, more particularly, for deposition of ZrMO x layers, wherein M is the second element and is selected from the group consisting of group 2, group 13, group 14, transition metal, lanthanides, and combinations thereof, and more preferably from Mg, Ca, Sr, Ba, Hf, Nb, Ta, Al,
• the method includes: introducing at least one Zr- containing precursor disclosed above into a reactor having at least one substrate disposed therein, introducing a second precursor into the reactor, and depositing at least part of the zirconium-containing precursor and at least part of the second precusor onto the at least one substrate to form the two element-containing layer using a vapor deposition process.
• the disclosed zirconium-containing precursors may be used to deposit zirconium-containing layers using any deposition methods known to those of skill in the art.
• suitable deposition methods include without limitation, conventional chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), atomic layer deposition (ALD), pulsed chemical vapor deposition (P-CVD), plasma enhanced atomic layer deposition (PE-ALD), or combinations thereof.
• CVD chemical vapor deposition
• LPCVD low pressure chemical vapor deposition
• ALD atomic layer deposition
• P-CVD pulsed chemical vapor deposition
• PE-ALD plasma enhanced atomic layer deposition
• the deposition method is ALD or PE-ALD.
• the vapor of the zirconium-containing 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 suitable conditions so that contact between the zirconium-containing precursor and substrate results in formation of a Zr-containing layer on at least one surface of the substrate.
• a co- reactant may also be used to help in formation of the Zr-containing layer.
• 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. All of these exemplary reactors are capable of serving as an ALD reactor.
• the reactor may be maintained at a pressure ranging from about 0.5 mTorr to about 20 Torr. In addition, the temperature within the reactor may range from about room
• the temperature of the reactor may be controlled by either controlling the temperature of the substrate holder or controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art.
• the reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth
• a non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 20°C to approximately 600°C.
• the deposition temperature may range from approximately 20°C to approximately 550°C.
• the deposition temperature may range from approximately 300°C to approximately 600°C.
• the substrate may be heated to a sufficient temperature to obtain the desired zirconium-containing layer 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 500°C.
• the substrate upon which the zirconium-containing layer 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, or FeRam technologies (for example, ZrO2 based materials, HfO2 based materials, ⁇ 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based layers (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, or FeRam technologies (for example, ZrO2 based materials, HfO2 based materials, ⁇ 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based layers (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer.
• Other substrates may be used in the manufacture of semiconductors, photovoltaics,
• substrates include, but are not limited to, solid substrates such as metal nitride containing substrates (for example, TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); insulators (for example, SiO 2 , Si 3 N 4 , SiON, HfO 2 , Ta 2 O 5 , ZrO 2 , TiO 2 , AI 2 O 3 , and barium strontium titanate); or other substrates that include any number of combinations of these materials.
• 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, SRO, Ru, and Si type substrates.
• the zirconium-containing precursor may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor. Prior to its
• the zirconium-containing 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
• the resulting concentration may range from approximately 0.05 M to approximately 2 M.
• the metal source may include any metal-containing precursors now known or later developed.
• the zirconium-containing precursor may be vaporized by passing a carrier gas into a container containing the zirconium-containing precursor or by bubbling the carrier gas into the zirconium-containing precursor.
• the carrier gas and zirconium-containing precursor are then introduced into the reactor as a vapor.
• the carrier gas may include, but is not limited to, Ar, He, N 2 ,and mixtures thereof.
• the zirconium-containing precursor may optionally be mixed in the container with one or more solvents, second precursors, or mixtures thereof.
• the container may be heated to a temperature that permits the zirconium-containing precursor to be in its liquid phase and to have a sufficient vapor pressure.
• the container may be maintained at temperatures in the range of, for example, 0-150°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 zirconium-containing precursor vaporized.
• the zirconium-containing precursor may be mixed with co-reactants inside the reactor.
• co-reactants include, without limitation, second precursors such as transition metal containing precursors (eg. Niobium), rare-earth containing precursors, strontium-containing precursors, barium-containing precursors, aluminum-containing precursors such as TMA, and any combination thereof.
• These or other second precursors may be incorporated into the resultant layer in small quantities, as a dopant, or as a second or third metal in the resulting layer, such as ZrMOx.
• the co-reactants may include an oxygen source which is selected from, but not limited to, O2, O3, H 2 O, H2O2, acetic acid, formalin, para-formaldehyde, and combinations thereof.
• the co-reactant is H 2 O.
• the co-reactant may be treated by plasma in order to decompose the co- reactant into its radical form.
• the plasma may be generated or present within the reaction chamber itself. Alternatively, the plasma may generally be at a location removed from the reaction chamber, for instance, in a remotely located plasma system.
• One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
• the co-reactant may be introduced into a direct plasma reactor, which generates a plasma in the reaction chamber, to produce the plasma-treated co-reactant in the reaction chamber.
• exemplary direct plasma reactors include the TitanTM PECVD System produced by Trion Technologies.
• the co-reactant may be introduced and held in the reaction chamber prior to plasma processing. Alternatively, the plasma processing may occur
• In-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder.
• the substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs.
• Typical applied powers in in-situ plasma generators are from approximately 100 W to approximately 1000 W.
• the disassociation of the co-reactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in co-reactant disassociation as a remote plasma system, which may be beneficial for the deposition of metal-nitride- containing films on substrates easily damaged by plasma.
• the plasma-treated co-reactant may be produced outside of the reaction chamber.
• the MKS Instruments' ASTRON ® i reactive gas generator may be used to treat the co-reactant prior to passage into the reaction chamber. Operated at 2.45 GHz, 7kW plasma power, and a pressure ranging from
• the co-reactant O3 may be decomposed into three O " radicals.
• the remote plasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
• the desired zirconium-containing layer also contains another element, such as, for example and without limitation, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, lanthanides (such as Er), or combinations thereof, the co-
• reactants may include a second precursor which is selected from, but not limited to, metal alkyls, such as Ln(RCp)3 or Co(RCp)2, metal amines, such as
• the zirconium-containing precursor and one or more co-reactants may be introduced into the reactor simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations.
• the zirconium- containing precursor may be introduced in one pulse and two additional precursors may be introduced together in a separate pulse [modified atomic layer deposition].
• the reactor may already contain the co-reactant prior to introduction of the zirconium-containing precursor.
• the co-reactant may be passed through a plasma system localized or remotely from the reactor, and decomposed to radicals.
• the zirconium-containing precursor may be introduced to the reactor continuously while other co-reactants 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 zirconium-containing precursor is introduced into the reactor, where it is contacted with a suitable substrate. Excess zirconium-containing precursor may then be removed from the reactor by purging and/or evacuating the reactor.
• An oxygen source is introduced into the reactor where it reacts with the absorbed zirconium-containing precursor in a self-limiting manner. Any excess oxygen source is removed from the reactor by purging and/or evacuating the reactor. If the desired layer is a zirconium oxide layer, this two-step process may provide the desired layer thickness or may be repeated until a layer having the necessary thickness has been obtained.
• the two-step process above may be followed by introduction of the vapor of a second precursor into the reactor.
• the second precursor will be selected based on the nature of the ZrMO x layer being deposited. After introduction into the reactor, the second precursor is contacted with the substrate. Any excess second
• INCORPORATED BY REFERENCE (RULE 20.6) 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 second precursor. Excess oxygen source is removed from the reactor by purging and/or evacuating the reactor. If a desired layer thickness has been achieved, the process may be terminated. However, if a thicker layer is desired, the entire four- step process may be repeated.
• a ZrMO x layer of desired composition and thickness may be deposited.
• layers having a desired stoichiometric M:Zr ratio may be obtained.
• a ZrMO 2 layer may be obtained by having one pulse of the zirconium-containing precursor and one pulse of the second precursor, with each pulse being followed by pulses of the oxygen source.
• the number of pulses required to obtain the desired layer may not be identical to the stoichiometric ratio of the resulting layer.
• Zr(NMe 2 )3(NC 4 H 8 ) A Schlenk flask containing Zr(NMe 2 ) (15.00g, 56.07 mmol) in 100 ml_ diethyl ether was cooled to -40 °C. To this cooled solution was added slowly via cannula a mixture of Pyrrolidine (NC 4 H 8 , 3.99g, 56.07 mmol) in 20 of diethyl ether. The initial clear solution turned slightly turbid, then to pale yellow solution. The reaction mixture was stirred at room temperature for 17h. Solvent and volatiles were removed, resulting in pale yellow viscous liquid 13.2g (80%)
• FIG 1 is a ThermoGravimetric Analysis/Differential Thermal Analysis (TGA/DTA) graph demonstrating the percentage of weight loss with temperature change for this precursor.
• FIG 4 is a TGA graph demonstrating the percentage of weight loss with temperature change for this purified precursor.
• Zr(NMe 2 )(NC 4 H 8 )3 A Schlenk flask containing Zr(NMe 2 ) 4 (30.90 mmol) in 100 ml_ diethyl ether will be cooled to -40 °C. To this cooled solution will be added slowly via cannula a mixture of Pyrrolidine (NC 4 H 8 , 92.70 mmol) in 20 of diethyl ether. The reaction mixture will be stirred at room temperature. Solvent and volatiles were removed.
• Zr(NC 4 H 8 ) 4 A Schlenk flask containing Zr(NMe 2 ) (30.90 mmol) in 100 ml_ diethyl ether will be cooled to -40 °C. To this cooled solution will be added slowly via cannula a mixture of Pyrrolidine (NC H 8 , 123.60 mmol) in 20 of diethyl ether. The resulting reaction mixture will be stirred at room temperature. Solvent and volatiles will be removed.
• Zr(NMe 2 )(NC 4 H 4 )3 A Schlenk flask containing Zr(NMe 2 ) 4 (30.90 mmol) in 100 ml_ diethyl ether will be cooled to -40 °C. To this cooled solution will be added slowly via cannula a mixture of Pyrrole (NC 4 H , 92.70 mmol) in 20 of diethyl ether. The resulting reaction mixture will be stirred at room temperature. Solvent and volatiles will be removed.

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