WO2006012294A2 - Chemical vapor deposition with nucleophilic stable carbene-containing precursors - Google Patents
Chemical vapor deposition with nucleophilic stable carbene-containing precursors Download PDFInfo
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- WO2006012294A2 WO2006012294A2 PCT/US2005/022472 US2005022472W WO2006012294A2 WO 2006012294 A2 WO2006012294 A2 WO 2006012294A2 US 2005022472 W US2005022472 W US 2005022472W WO 2006012294 A2 WO2006012294 A2 WO 2006012294A2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—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
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
Definitions
- the present invention is directed to novel precursors for use in chemical vapor deposition. More particularly, the present invention is directed to chemical vapor deposition precursors which incorporate nucleophilic stable carbene ligands.
- CVD chemical vapor deposition
- metal-, metal-oxide-, metal-nitride, and metal-oxynitride films including flat panel displays, organic light-emitting diodes, low emissivity and solar control coatings, photovoltaic cells, and a variety of transparent-, opto-, and high temperature electronic applications.
- Many precursors for these applications, while of suitable volatility, are either highly pyrophoric (e.g. Et 2 Zn, Mc 3 AI) or highly toxic (e.g. Ni (CO) 4 , W(CO) 6 ).
- the reactivity of potential precursors may be tempered through coordination of simple ⁇ -donors (such as amines and phosphines) to group 13 and 14 species, or through the use of chelating (and partially- or fully-fluorinated) ligands, such as in (hexafluoiOacetylacetonate)Cu(vinyltrimethylsilane) for Cu- deposition.
- simple ⁇ -donors such as amines and phosphines
- chelating (and partially- or fully-fluorinated) ligands such as in (hexafluoiOacetylacetonate)Cu(vinyltrimethylsilane) for Cu- deposition.
- the present invention is directed toward novel precursors, incorporating nucleophilic stable carbene (NSC) ligands, for chemical vapor deposition of metal-, metal-oxide, metal-nitride and metal-oxynitride films.
- NSC nucleophilic stable carbene
- Any of a variety of two- electron donating NSC ligands may be coordinated to main-group and transition- metal fragments, resulting in (for example) (NSC)M-alkyl, -aryl, -hydride, -alkoxide, -amidinate.-diketonate. and -diketiminate species.
- the ability to combine easily functional ized NSCs with metal fragments containing ancillary ligands with a range of steric and electronic environments allows control over the molecular architecture of the precursor, and the resultant ability to modify and control precursor physical characteristics (e.g. volatility, stability).
- the present invention is directed to novel main-group and transition-metal chemical vapor deposition precursors which incorporate nucleophilic stable carbene (NSC) ligands formed from NSCs of Formula 1 :
- NSC nucleophilic stable carbene
- X 1 and X 2 are the same or different and may be -NR 1 R 2 , -OR 1 , -SR 1 , -PR 1 R 2 , -BR 1 R 2 , -SiR 1 R 2 R 3 , -aryl. or -hctcroaryl, and where R 1 , R 2 , and R 3 are each individually a C 1 -C20 group selected from alkyl, aryl, aralkyl, alkaryl, and any of these substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, and phosphorus.
- X 1 and X 2 may be connected by a direct bond or a C I -C20 spacer group which may contain one or more heteroatoms.
- Either or both X 1 and X 2 may have one or more substituents (Y) that coordinate to the metal center. Either or both X 1 and X 2 may contain chiral substituents. Either or both X 1 and X 2 may contain linear, branched, or cyclic substituents.
- L n is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl, halide, silyl. carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide. amide, phosphide, nitride or other groups.
- the precursors of the present invention may also be employed as precursors for dopants used in metal oxide films.
- NSC ligands can coordinate with a metal (M) center as shown below:
- L n is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryi. halide, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide, amide, phosphide, nitride or other groups, and where X 1 and X 2 are the same or different and are selected from -NR 1 R 2 , -OR 1 , -SR 1 , -PR 1 R 2 , - BR 1 R 2 , -SiR 1 R 2 R 3 , -aryl, or -heteroaryi, and where R 1 , R 2 , and R 3 are each individually a C 1 -C20 group selected from alkyl, aryl, aralkyl, alkaryl, and any of R 1
- NSCs ( I ) aie robust, neutral, two-electron donating ligands that are ideally suited lor coordination to transition- and main-group metal centers.
- Precursors incorporating these NSCs are of the general formula (X')(X 2 )C-M-L n .
- X 1 and X 2 arc defined accoi ding to Formula 1
- M is a transition-metal or a main-group metal
- L n is one or more non-NSC ligands bound to the metal center, and where L n may or may not contain one or more additional metal centers.
- One or more such carbcne ligands ( 1 ) can be coordinated to a metal M to form bis(carbene)metal or higher (carbcne) molecules
- Stable NSCs such as imidazol-2-ylidenes (2), diaminocarbenes (3 and 5), l ,2,4-triazol-3-yhdenes (4), perimidinecarbencs (6), bipyridiniumcarbenes (7), (amino)(phosph ⁇ no)carbenes (8), (amino)(alkoxy)carbenes (9), (amino)(aryl) carbenes (10), and (amino)(thio)ca ⁇ benes (1 1) may be coordinated to metal centers such as (for example) aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, silver, and titanium, zinc, tungsten, and tantalum, generating compositions suitable lor use as chemical vapor deposition precursors.
- metal centers such as (for example) aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, silver, and titanium, zinc,
- Ar is a substituted or unsubstitutcd aryl or hctroaryl.
- NSC-mctal complexes may be synthesized by addition of NSCs to metal alkyl, -aryl, -hydride, or - ⁇ lkoxide species, or by the combination of the addition ol ' NSCs to metal halides followed by reaction with lithium-, sodium-, potassium-, or magnesium alkyl, -aryl, -hydride, or -alkoxide reagents.
- NSC NSCM(amidinate) complexes (13) such as formed by the following reactions:
- R s , R y , and R H may be the same or different and are each individually a C l - C20 group selected from alky!, aryl, aralkyl, alkaryl or a silyl group and any of R s , R 9 .
- R l () may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, sil icon, and phosphorus, where L n and L n - may be the same or different and are ancil lary ligand arrays which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl, halide, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne. alkoxide, amide, phosphide, nitride or other groups, and where a is an integer greater or equal to 2, and where the precursor is either neutral or cationic.
- stable NSCs in accordance with the present invention can include (NSC)M[R S C(X ⁇ )CHC(X 4 )R 9 J where X 3 and X 4 may be the same or different and are selected from O or N R " , where R" may be a C I -C20 group selected from alky I, aryl, aralkyl, alkaryl and may be substituted with one or more of fluorine, oxygen, nitrogen, sul fur, silicon, or phosphorus, and which may be formed by addition of NSCs to prclormed M[R 8 C(X 3 )CHC(X 4 )R 9 ], by addition of [R 8 C(X 3 )CHC(X 4 )R 9 ] " anions to (NSC)M-halides.
- transition-metal and main-group elements Ni, Cu, Zn, Ag, Ti, Mo, W, Ta, Al, Ga, Sn. and Mg may be successfully ligated by NSCs for the purpose of generating novel chemical vapor deposition precursors.
- NSC novel chemical vapor deposition precursors.
- These (NSC)-metal- containing species may be used to deposit doped or undoped films of metals, metal- oxides, metal-nitrides, or mctal-oxynitrides.
- NSC nitrogen-containing chemical vapor deposition
- metals metal- oxides
- mctal-nilridcs metal- oxides
- mctal-oxynitrides by atmospheric pressure chemical vapor deposition via conventional chemical vapor deposition techniques including, but not limited to. pyrolyl ic atmospheric pressure CVD, low-pressure CVD, plasma assisted CVD, solution spray CVD, and powder spray CVD.
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Abstract
Novel main-group and transition-metal chemical vapor deposition precursors which incorporate nucleophilic stable carbene ligands for forming doped or undoped metal, metal oxide, and metal-nitride films are described. The coordination of nucleophilic stable carbene ligands to main-group and transition-metal fragments allows control over the molecular architecture of the precursor and the resultant ability to modify and control precursor physical characteristics.
Description
CHEMICAL VAPOR DEPOSITION WITH N UCLEOPH I LIC STABLE CARBENE-CONTAINING PRECURSORS
[0001 ] This application claims priority under 35 U. S. C. § l I 9(e) of prior U. S. Provisional Patent Application No. 60/582,872 filed June 25, 2004, which is incorporated in its entirety by reference herein.
Field of The Invention
[0002] The present invention is directed to novel precursors for use in chemical vapor deposition. More particularly, the present invention is directed to chemical vapor deposition precursors which incorporate nucleophilic stable carbene ligands.
Background
[0003] Chemical vapor deposition (CVD) precursors that are both volatile and easily handled are needed for numerous applications. The development of new materials by CVD is limited by a lack of suitable precursors for applications based on metal-, metal-oxide-, metal-nitride, and metal-oxynitride films (including flat panel displays, organic light-emitting diodes, low emissivity and solar control coatings, photovoltaic cells, and a variety of transparent-, opto-, and high temperature electronic applications). Many precursors for these applications, while of suitable volatility, are either highly pyrophoric (e.g. Et2Zn, Mc3AI) or highly toxic (e.g. Ni (CO)4, W(CO)6).
[0004] The reactivity of potential precursors may be tempered through coordination of simple σ-donors (such as amines and phosphines) to group 13 and 14 species, or through the use of chelating (and partially- or fully-fluorinated) ligands, such as in (hexafluoiOacetylacetonate)Cu(vinyltrimethylsilane) for Cu- deposition. These approaches, however, often also result in significant reductions in precursor volatility. The present invention is directed to novel, easily handled, yet volatile main-group and transition-metal chemical vapor deposition precursors.
Summary of the Invention
[0005] The present invention is directed toward novel precursors, incorporating nucleophilic stable carbene (NSC) ligands, for chemical vapor deposition of metal-, metal-oxide, metal-nitride and metal-oxynitride films. Any of a variety of two- electron donating NSC ligands may be coordinated to main-group and transition- metal fragments, resulting in (for example) (NSC)M-alkyl, -aryl, -hydride, -alkoxide, -amidinate.-diketonate. and -diketiminate species. The ability to combine easily functional ized NSCs with metal fragments containing ancillary ligands with a range of steric and electronic environments allows control over the molecular architecture of the precursor, and the resultant ability to modify and control precursor physical characteristics (e.g. volatility, stability).
Detailed Description of the Invention
[0006] The present invention is directed to novel main-group and transition-metal chemical vapor deposition precursors which incorporate nucleophilic stable carbene (NSC) ligands formed from NSCs of Formula 1 :
K ,C J Formula I
X2
wherein X1 and X2 are the same or different and may be -NR1 R2, -OR1, -SR1, -PR1 R2, -BR1 R2, -SiR1 R2R3, -aryl. or -hctcroaryl, and where R1 , R2, and R3 are each individually a C 1 -C20 group selected from alkyl, aryl, aralkyl, alkaryl, and any of these substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, and phosphorus. X 1 and X2 may be connected by a direct bond or a C I -C20 spacer group which may contain one or more heteroatoms. Either or both X 1 and X2 may have one or more substituents (Y) that coordinate to the metal center. Either or both X 1 and X2 may contain chiral substituents. Either or both X 1 and X2 may contain linear, branched, or cyclic substituents. Ln is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl, halide, silyl. carbonyl, ester, acetate, amine, phosphine, ether, alkene,
alkyne, alkoxide. amide, phosphide, nitride or other groups. The precursors of the present invention may also be employed as precursors for dopants used in metal oxide films.
[0007] The NSC ligands can coordinate with a metal (M) center as shown below:
Wherein M is a transition- or main-group metal, Ln is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryi. halide, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide, amide, phosphide, nitride or other groups, and where X1 and X2 are the same or different and are selected from -NR1 R2, -OR1, -SR1, -PR1 R2, - BR1 R2, -SiR1 R2R3, -aryl, or -heteroaryi, and where R1, R2, and R3 are each individually a C 1 -C20 group selected from alkyl, aryl, aralkyl, alkaryl, and any of R 1 , R", and RJ may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, and phosphorus, where X 1 and X2 may be connected by a direct bond or a C l - C20 spacer group which may contain one or more heteroatoms, where either or both X1 and X2 may have one or more substituents, Y 1 and Y2, that coordinate to M, Y1 and Y2 may be independently OR5, NR5R6, PR5R6, O, NR5, PR5, CR5=CR6R7, CR5R6, SiR3R6, where R\ R6, and R7 are each individually a C 1 -C20 group selected from hydrogen, alkyl, aryl, aralkyl, alkaryl, and any of R\ R6, and R7 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, or phosphorus, where either or both X1 and X2 may contain chiral substituents, and where either or both X1 and X2 may contain linear, branched, or cyclic substituents, where R4 is hydrogen, - alkyl, -aryl, -aralkyl, -alkaryl, or -alkoxide, and z is an integer greater than or equal to 0, and when z is greater than I each R4 may be the same or different, and where a is an integer equal to or greater than 2, , and where a is greater than or equal to 2 the CX 1X2 fragments may be either the same or different, and where the precursor may be either neutral or cation ic.
[0008] NSCs ( I ) aie robust, neutral, two-electron donating ligands that are ideally suited lor coordination to transition- and main-group metal centers. Precursors incorporating these NSCs are of the general formula (X')(X2)C-M-Ln. where X 1 and X2 arc defined accoi ding to Formula 1 , where M is a transition-metal or a main-group metal, and where Ln is one or more non-NSC ligands bound to the metal center, and where Ln may or may not contain one or more additional metal centers. One or more such carbcne ligands ( 1 ) can be coordinated to a metal M to form bis(carbene)metal or higher (carbcne) molecules
[0009] Stable NSCs, such as imidazol-2-ylidenes (2), diaminocarbenes (3 and 5), l ,2,4-triazol-3-yhdenes (4), perimidinecarbencs (6), bipyridiniumcarbenes (7), (amino)(phosphιno)carbenes (8), (amino)(alkoxy)carbenes (9), (amino)(aryl) carbenes (10), and (amino)(thio)caι benes (1 1) may be coordinated to metal centers such as (for example) aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, silver, and titanium, zinc, tungsten, and tantalum, generating compositions suitable lor use as chemical vapor deposition precursors. Such stable NSCs are exempli fied by the structures:
r
where Ar is a substituted or unsubstitutcd aryl or hctroaryl.
[0010] In addition, stable NSCs include (NSC)-[M1-R where R = -alkyl, -aryl, - hydride, and -alkoxidc complexes (12), where [M] represents a metal center with or without additional ancillary ligands, resulting from the reaction:
X1 X1
,C : + [M]R ^C-[M]R (12)
X2 X2
\ \ M1R
,C : + [M]X ,C-[M]X - (12) χ2 χ2 - M1X
These NSC-mctal complexes may be synthesized by addition of NSCs to metal alkyl, -aryl, -hydride, or -πlkoxide species, or by the combination of the addition ol' NSCs to metal halides followed by reaction with lithium-, sodium-, potassium-, or magnesium alkyl, -aryl, -hydride, or -alkoxide reagents.
[001 1 ] Additional stable NSCs in accordance with the present invention include (NSC)M(amidinate) complexes (13) such as formed by the following reactions:
[RaNC(Ra)NR1u][MgX] or
X1 Ln [R8NC(R9)NR10][Li]
,C: + [M]X ,C-[M]X •»- (13) or (14) or (15) or (16)
Xz -MgX2 or LiX
X ' X ' I R -N=C=N-R 10
,c: [M]Rε ,C-[M]R9 (13) or (14) or (15) or (16)
X1 + Ln-[M]X + M'OR'
,C-H (13) or (14) or (15) or (16)
+ [R8NC(R9)NR10][MgX] - M1CI or [R8NC(R9)NR10][Li] - R1OH
- MgX2 or LiX
Wherein, Rs, Ry, and R H) may be the same or different and are each individually a C l - C20 group selected from alky!, aryl, aralkyl, alkaryl or a silyl group and any of Rs, R9. and Rl () may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, sil icon, and phosphorus, where Ln and Ln- may be the same or different and are ancil lary ligand arrays which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl, halide, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne. alkoxide, amide, phosphide, nitride or other groups, and where a is an integer greater or equal to 2, and where the precursor is either neutral or cationic. These NSCs may be formed by addition of NSCs to preformed metalloamidinates, by addition of amidinato- alkali metal or alkaline earth metal reagents to (NSC)M-halide complexes, by addition of carbodiimides
(R8N=C=NR 10) or amidincs (R8NHC(R9)=NR10) to (NSC)M-(alkyl) complexes, or by treatment of melal-halides with azolium salts [X1X2CH][Cl], metal-alkoxides, and amidinato | R8NC(R9)NR l (lp -magnesium or -lithium reagents.
[0012] Similarly, stable NSCs in accordance with the present invention can include (NSC)M[RSC(X^)CHC(X4)R9J where X3 and X4 may be the same or different and are selected from O or N R " , where R" may be a C I -C20 group selected from alky I, aryl, aralkyl, alkaryl and may be substituted with one or more of fluorine, oxygen, nitrogen, sul fur, silicon, or phosphorus, and which may be formed by addition of NSCs to prclormed M[R8C(X3)CHC(X4)R9], by addition of [R8C(X3)CHC(X4)R9]" anions to (NSC)M-halides. or by treatment of neutral | R8CH(X3)CHC(X4)R9] with either (NSC)M-alkyls or with a combination of metal-halides, azolium salts [X1 X2CH][Cl I, metal-alkoxidcs, and neutral | R8CH(X3)CHC(X4)R9J via reactions:
[R τ8°/C-»/(X v3J)CHC(X4)RM
,C: + [M]X . ,C-[M Y]X (17) or (18) or (19) or (20)
X - X"
X s I π R8CH(X3)CHC(X4)R9
,C : [M Y]R - ,C-[M]R »~ (17) or (18) or (19) or (20)
2 - RH
+ L,y[M]X + M'OR'
.C-H [Cl] (17) or (18) or (19) or (20) + R8CH(X3)CHC(X4)R9 - M1CI
- R1OH
- MgX2
[0013] The transition-metal and main-group elements Ni, Cu, Zn, Ag, Ti, Mo, W, Ta, Al, Ga, Sn. and Mg may be successfully ligated by NSCs for the purpose of generating novel chemical vapor deposition precursors. These (NSC)-metal- containing species may be used to deposit doped or undoped films of metals, metal- oxides, metal-nitrides, or mctal-oxynitrides.
[0014] These (NSC)-metal species may be used to deposit films of metals, metal- oxides, mctal-nilridcs or mctal-oxynitrides by atmospheric pressure chemical vapor deposition via conventional chemical vapor deposition techniques including, but not limited to. pyrolyl ic atmospheric pressure CVD, low-pressure CVD, plasma assisted CVD, solution spray CVD, and powder spray CVD.
[0015] Modifications to the NSC substituents and to the ancillary ligands coordinated to the metal (facilitating control of molecular weight and incorporation of fluorinated substituents) allows optimization of precursor properties such as volatility and stability.
[0016] While the present invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications, which arc within the true spirit and scope of the present invention.
Claims
I . A nucleophilic stable carbene precursor comprising:
2. The nucleophilic stable carbene precursor of claim I wherein M is selected from the group: aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, tungsten, si lver, tantalum, and titanium.
3. A nucleophilic stable carbene precursor comprising: 
wherein M is a transition- or main-group metal, Ln is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl, halicle, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide, amide, phosphide, nitride or other groups, and z is an integer greater than I , and X ' and X2 are the same or different and are selected from -NR1 R2, -OR1, -SR1, -PR1 R2, -BR1 R2, -SiR1 R2R3, -aryl, or -heteroaryl where R1, R2, R3, and R4may be the same or different and are each individually hydrogen or a C 1 -C20 group selected from alkyl, aryl, aralkyl, alkaryl, and any of R1, R2, RJ, and R4 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, and phosphorus,X: and X2 may be connected by a direct bond or a C I -C20 spacer group which may contain one or more heteroatoms, either or both X1 and X2 may have one or more substituents, Y1 and Y2, that coordinate to M, Y1 and Y2 may be independently OR3, NR5R6, PR5R6, O, NR5, PR5, CR5=CR6R7, CR5R6, SiR5R6 where R5, R6, and R7 may be the same or different and are each individually hydrogen or a C I -C20 group selected from alkyl. aryl, aralkyl, alkaryl and any of R3, R6, and R7 may be substituted with one or more of fluorine, oxygen, nitrogen, sul fur, silicon, or phosphorus, either or both X 1 and X2 may contain chiral substituents, either or both X1 and X2 may contain linear,, branched, or cyclic substituents, R is -hydride, -alkyl, -aryl, -aralkyl, - alkaryl, or -alkoxide, z is an integer greater than I , each R4 may be the same or different, where a is equal to or greater than 2 the CX1 X2 fragments may be either the same or different, and where the precursor may be either neutral or cationic.
4. The nucleophilic stable carbene precursor of claim 3 wherein M is selected from the group: aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, tungsten, silver, tantalum, and titanium.
5. A nucleophilic stable carbene precursor comprising:
K) 
wherein M is a transition- or main-group metal, Ln is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, heteroaryl. halide, silyl, carbonyl, ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide, amide, phosphide, nitride or other groups, X1 and X2 are the same or different and arc selected from -NR1 R2, -OR1, -SR1, -PR1 R2, -BR1 R2, - SiR1 R2R3, -aryl, or -heteroaryl, where R1, R2, R3, Rs, R9, and R10 may be the same or different and are each individually hydrogen or a C I -C20 group selected from alkyl, aryl, aralkyl, alkaryl, any of R1, R2, R3, R8, R9, and R10 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, and phosphorus, X 1 and X2 may be connected by a direct bond or a C I -C20 spacer group which may contain one or more heteroatoms, either or both X1 and X2 may have one or more substituents, Y1 and Y2, that coordinate to M, Y1 and Y2 may be independently OR5, NR5R6, PR5R6, O, NR5, PR5, CR5=CR6R7, CR5R6, SiR5R6 where R5, R6, and R7 may be the same or different nnd arc each individually hydrogen or a C I -C20 group selected from, alkyl, aryl, aralkyl, alkaryl and any of R"\ R6 , and R7 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, or phosphorus, either or both X 1 and X2 may contain chiral substituents, either or both X1 and X2 may contain linear, branched, or cyclic substituents, where a is greater than or ecμial to 2 the CX1X2 fragments may be either the same or different, and where the precursor is either neutral or cationic.
6. The nucleophilic stable carbene precursor of claim 5 wherein M is selected from the group: aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, tungsten, silver, tantalum, and titanium.
7. A nucleophilic stable carbene precursor comprising: 
wherein M is a transition- or main-group metal, Ln is an ancillary ligand array which may contain one or more metals, and which may include one or more hydrogen, alkyl, aryl, silyl, hcteroaryl. halide. silyl, carbonyl. ester, acetate, amine, phosphine, ether, alkene, alkyne, alkoxide, amide, phosphide, nitride or other groups, X1 and X2 are the same or different and are selected from -IMR1 R2, -OR1, -SR1, -PR1 R2, -BR1 R2, - SiR1 R2R3, -aryl, or -heteroaryl, where R1, R2, R3, R8, and R9 may be the same or different and are each individually hydrogen or a C I -C20 group selected from alkyl, aryl, aralkyl, alkaryl any of R1 , R2, RJ, R8, and R9 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, or phosphorus, X 1 and X2 may be connected by a direct bond or a C 1 -C20 spacer group which may contain one or more heteroatoms, either or both X' and X2 may have one or more substituents, Y1 or Y2, that coordinate to M, Y1 and Y2 may be independently OR5, NR5R6, PR5R6, O, NR5, PR5, CR5=CR6R7. CR5R6, SiR5R6 where R5, R6, and R7 arc each individually a C l - C20 group selected from hydrogen, alkyl, aryl, aralkyl, alkaryl and any of R5, R6 , and R7 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, or phosphorus, either or both X 1 and X2 may contain chiral substituents, either or both X 1 and X2 may contain linear, branched, or cyclic substituents, and XJ and X4 may be the same or different and are selected from -O, -NR1 ', and R1 1 may be a C I -C20 group selected from -alkyl, -aryl, -aralkyl, -alkaryl, where R1 1 may be substituted with one or more of fluorine, oxygen, nitrogen, sulfur, silicon, and phosphorus, where a is greater than or equal to 2 the CX1X2 fragments may be either the same or different, and where the precursor is cither neutral or cationic.
8. The niiclcophilic stable carbene precursor of claim 7 wherein M is selected from the group: aluminum, gallium, indium, tin, magnesium, zinc, iron, copper, nickel, molybdenum, tungsten, silver, tantalum, and titanium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155264A1 (en) * | 2011-05-13 | 2012-11-22 | Greencentre Canada | Group 11 mono-metallic precursor compounds and use thereof in metal deposition |
| WO2019066179A1 (en) * | 2017-09-26 | 2019-04-04 | 주식회사 한솔케미칼 | Vapor deposition precursor having excellent thermal stability and reactivity and preparing method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119660A1 (en) * | 2001-10-02 | 2003-06-26 | Herrmann Wolfgang A. | Novel transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals |
| US20040132934A1 (en) * | 2002-08-01 | 2004-07-08 | Robert Grubbs | Synthesis of macrocyclic polymers by ring insertion polymerization of cyclic olefin monomers |
-
2005
- 2005-06-23 WO PCT/US2005/022472 patent/WO2006012294A2/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119660A1 (en) * | 2001-10-02 | 2003-06-26 | Herrmann Wolfgang A. | Novel transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals |
| US20040132934A1 (en) * | 2002-08-01 | 2004-07-08 | Robert Grubbs | Synthesis of macrocyclic polymers by ring insertion polymerization of cyclic olefin monomers |
Non-Patent Citations (2)
| Title |
|---|
| CETINKAYA B. ET AL.: 'Carbene Complexes. Part VIII. Chromium(0)mIron(0),Rhodium(I),Iridium(I),n ickel(II),Palladium(II),Platinum(II), and Gold(I) Mono- and Oligo-carbene Species from Electron-rich Olefins' JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS: INORGANIC CHEMISTRY vol. 16, 1974, pages 1827 - 1833 * |
| MCGUINNESS D.S. ET AL.: 'Zerovalent Palladium and Nickel Complexes ofheteroc<clic Carbenes: Oxidative Addition of Organic Halides, Carbon-Carbon Coupling Processes, and the Heck Reaction' ORGANOMETALLICS vol. 18, no. 9, 03 April 1999, pages 1596 - 1605 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155264A1 (en) * | 2011-05-13 | 2012-11-22 | Greencentre Canada | Group 11 mono-metallic precursor compounds and use thereof in metal deposition |
| JP2014518944A (en) * | 2011-05-13 | 2014-08-07 | グリーンセンター カナダ | Group 11 monometallic precursor compounds and their use in metal deposition |
| US9453036B2 (en) | 2011-05-13 | 2016-09-27 | Greencentre Canada | Group 11 mono-metallic precursor compounds and use thereof in metal deposition |
| WO2019066179A1 (en) * | 2017-09-26 | 2019-04-04 | 주식회사 한솔케미칼 | Vapor deposition precursor having excellent thermal stability and reactivity and preparing method therefor |
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