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  • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/06—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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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/65—Metal complexes of amines
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  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/02—Guanidine; Salts, complexes or addition compounds thereof
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
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  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/14—Nitrogen atoms not forming part of a nitro radical
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  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/36—Carbonitrides
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  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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  • 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
  • C23C16/50—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 using electric discharges

Definitions

• the disclosed and claimed subject matter relates to organometallic amidinate and guanidinate paddlewheel compounds, compositions containing the compounds and methods of using the compounds as precursors for deposition of metal-containing films.
• Transition metal-containing films are used in semiconductor and electronics applications.
• Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) have been applied as the main deposition techniques for producing thin films for semiconductor devices. These methods enable the achievement of conformal films (metal, metal oxide, metal nitride, metal silicide, and the like) through chemical reactions of metal-containing compounds (precursors). The chemical reactions occur on surfaces which may include metals, metal oxides, metal nitrides, metal silicides, and other surfaces.
• CVD and ALD the precursor molecule plays a critical role in achieving high quality films with high conformality and low impurities.
• the temperature of the substrate in CVD and ALD processes is an important consideration in selecting a precursor molecule.
• the preferred precursor molecules must be stable in this temperature range.
• the preferred precursor is capable of being delivered to the reaction vessel in a liquid phase. Liquid phase delivery of precursors generally provides a more uniform delivery of the precursor to the reaction vessel than solid phase precursors.
• CVD and ALD processes are increasingly used as they have the advantages of enhanced compositional control, high film uniformity, and effective control of doping. Moreover, CVD and ALD processes provide excellent conformal step coverage on highly non-planar geometries associated with modern microelectronic devices.
• CVD is a chemical process whereby precursors are used to form a thin film on a substrate surface.
• the precursors are passed over the surface of a substrate (e.g a wafer) in a low pressure or ambient pressure reaction chamber.
• the precursors react and/or decompose on the substrate surface creating a thin film of deposited material.
• Plasma can be used to assist in reaction of a precursor or for improvement of material properties.
• Volatile by-products are removed by gas flow through the reaction chamber.
• the deposited film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects, and time.
• ALD is a chemical method for the deposition of thin films. It is a self-limiting, sequential, unique film growth technique based on surface reactions that can provide precise thickness control and deposit conformal thin films of materials provided by precursors onto surfaces substrates of varying compositions.
• the precursors are separated during the reaction. The first precursor is passed over the substrate surface producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor or co-reactant is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film over the first-formed monolayer of film on the substrate surface. Plasma may be used to assist with reaction of a precursor or co-reactant or for improvement in materials quality.
• Thin films and in particular thin metal-containing films, have a variety of important applications, such as in nanotechnology and the fabrication of semiconductor devices. Examples of such applications include capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits.
• molybdenum nitride films For forming molybdenum nitride films, the compound Mo(VI)(NMe2)2(NtBu)2: has been used to prepare nitride films. See Chem. Mater., 19, 263-269 (2007).
• the precursor is commonly referred to as MoBure.
• MoBure is evaporated below 100 °C and deposits molybdenum nitride films via thermal atomic layer deposition with ammonia. The growth rate was 0.5 A/cycle within the reactor temperature range of 260-300 °C.
• the film composition contains a Mo:N ratio of 1:1 and was predominately amorphous. Resistivity values of the thin film were not reported. Internal experiments have measured resistivities of >2000 mW-cm for MoBure.
• Molybdenum paddlewheel compounds are generally known in the literature.
• the disclosed and claimed subject matter therefore, provides Group 6 (i.e ., chromium, molybdenum and tungsten) paddlewheel compounds synthesized without acetate ligands.
• These new paddlewheel precursors are thermally stable and are suitable as CVD and ALD precursors that can be preferably delivered in liquid phase, have low impurities and can produce a high-quality film with high conformality and low resistivity.
• amidinate and guanidinate paddlewheel compounds of chromium, molybdenum and tungsten for use as ALD and CVD precursors.
• the precursors are amidinate (“Ad”) paddlewheel compounds have the general Formula I shown below
• M is one of chromium, molybdenum and tungsten
• R 1 , R 2 and R 3 are each independently selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstit
• all four amidinate ligands have the same chemical structure. In another aspect of this embodiment, two or more of the amidinate ligands have the same chemical structure. In another aspect of this embodiment, all four amidinate ligands have a different chemical structure.
• the compounds of Formula I include heterocyclic Ad ligands (Formula II-A and Formula II-B) and/or heterocyclic bicyclic Ad ligands (Formula II-C) as shown below where one or both of (a) R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula II-A:
• M is one of chromium, molybdenum and tungsten
• R 2 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a C 3
• R 1 and R 3 constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula II-B: where: M is one of chromium, molybdenum and tungsten;
• R 1 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH3)3, a C3-C8 unsubstituted cyclic alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C3-C8 unsubstituted aromatic group, a C3-C8 aromatic group substituted with
• R 2 and R 3 constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula II-B: where: M is one of chromium, molybdenum and tungsten; and each of (a) R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6- member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the backbone of the alkylenes and heteroalkylenes in each 5- or 6- membered ring described in Formula II-A and Formula II-B and/or Formula II-C above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• the precursors are guanidinate (“Gd”) paddlewheel compounds have the general Formula III shown below III where: M is one of chromium, molybdenum and tungsten; and
• R 1 , R 2 , R 3A and R 3B are each independently selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 - C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -
• all four guanidinate ligands have the same chemical structure. In another aspect of this embodiment, two or more of the guanidinate ligands have the same chemical structure. In another aspect of this embodiment, all four guanidinate ligands have a different chemical structure.
• the compounds of Formula III include heterocyclic Gd ligands (Formula IV-A and Formula IV-B) and/or heterocyclic bicyclic Gd ligands (Formula IV-C) as shown below where one or both of (a) R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula IV-A: IV- A where: M is one of chromium, molybdenum and tungsten;
• R 2 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a C 3
• R 1 and R x constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one of R 3A and R 3B and R x is the other of R 3A and R 3B that is not connected by a linking group to R 1 .
• the precursor has Formula IV-B: where: M is one of chromium, molybdenum and tungsten;
• R 1 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH3)3, a C3-C8 unsubstituted cyclic alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C3-C8 unsubstituted aromatic group, a C3-C8 aromatic group substituted with
• R 2 and R z constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one of R 3A and R 3B and R x is the other of R 3A and R 3B that is not connected by a linking group to R 2 .
• the precursor has Formula IV-C: where: M is one of chromium, molybdenum and tungsten; and each of (a) R 1 and R x and (b) R 2 and R z independently constitute parts of a 5- or 6- member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one ofR 3A and R 3B and R x is the other of R 3A and R 3B .
• the backbone of the alkylenes and heteroalkylenes in each 5- or 6- membered ring described in Formula IV-A and Formula IV-B and/or Formula IV-C above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• the above precursors, and the more specifically described embodiments below, of compound provide halide-free and oxygen-free precursors for applications where such contaminates are detrimental.
• the disclosed and claimed subject further includes (i) compositions and formulations that include the disclosed and claimed precursors, (ii) methods of using the disclosed and claimed precursors in deposition processes and (iii) metal -containing films derived from the disclosed and claimed precursors produced in deposition processes.
• the method produces thin films with improved properties compared to known methods which could be attributed to the low oxidation state of the paddlewheel precursors.
• Such metal and metal-containing thin films can be produced by thermal or plasma ALD and CVD using the disclosed and claimed precursors.
• the precursor can be used to produce metal -containing (e.g ., molybdenum) thin films under mild conditions.
• molybdenum carbonitride thin films with low electrical resistivity have been deposited in the absence of a plasma in a thermal ALD process from molybdenum (II) amidinate precursor of the disclosed and claimed subject matter.
• molybdenum carbonitride thin films produced from MoBure required a plasma-enhanced process. Without intending or being bound by theory, it appears that the “rigid structure” of the paddlewheel compounds very effectively stabilizes the low valent metal atom to afford a compound with thermal stability and volatility.
• MoBure has an (VI) oxidation state which requires a strongly reducing hydrogen plasma in order to deposit thin films with low resistivity.
• FIG. 2 illustrates the proton ( 1 FT) NMR of tetrakis(N,N’-dimethylformamidinate) dimolybdenum of Example 1;
• FIG. 3 illustrates the proton ( 1 FT) NMR of tetrakis(N,N’-diethylformamidinate) dimolybdenum of Example 2;
• FIG. 4 illustrates the proton ( 1 FT) NMR of tetrakis(N-sec-butyliminopyrrolydinate) dimolybdenum of Example 3;
• FIG. 5 illustrates top down and cross-section SEM of Mo-containing film deposited at 350 °C wafer temperature by NH3 CCVD process of Example 5: 10 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge;
• FIG. 6 illustrates top down and cross-section SEM of Mo-containing film deposited at 350 °C wafer temperature by NEE CCVD process of Example 5: 20 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge; and
• FIG. 7 illustrates Auger depth profile of Mo-containing film deposited at 350 °C wafer temperature by NEE CCVD process of Example 5: 10 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge.
• FIG. 8 illustrates the crystal structure of Mo2(Me-FMD)4
• FIG. 9 illustrates the crystal structure of Mo2(Et-FMD)4
• FIG. 10 illustrates a cross-section TEM of Mo-containing film deposited at 360°C and 375 °C wafer temperature on high aspect ratio patterned wafer by NEE ALD process of the Example 11 : 20 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge;
• FIG. 11 illustrates a cross-section TEM of thin continuous film deposited at 400°C wafer temperature on silicon oxide substrate by NEE CCVD process of Example 12: 10 sec of Mo2(Me-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge;
• FIG. 12 illustrates a photo of the silicon oxide wafers after deposition of Mo metal film by M0O2CI2/EE thermal ALD on the wafers with and without a seed layer deposited by Mo2(Me-FMD)4 , as described in the example 15;
• FIG. 13 illustrates a cross-section TEM of the low resistivity Mo metal film deposited by M0O2Q2/EE thermal ALD on a seed layer deposited by NH3 CCVD process of Example 16: 10 sec of Mo2(Me-FMD)4 / 30 sec Ar purge / 5 sec of NEE/ 30 sec of Ar purge;
• FIG. 14 illustrates simulated powder X-ray Diffraction (PXRD) spectrum using experimental unit cell parameters of Mo2(Me-FMD)4;
• FIG. 15 illustrates simulated powder X-ray Diffraction (PXRD) spectrum using experimental unit cell parameters of Mo2(Et-FMD)4.
• silicon as deposited as a material on a microelectronic device will include polysilicon.
• microelectronic device or “semiconductor device” corresponds to semiconductor wafers having integrated circuits, memory, and other electronic structures fabricated thereon, and flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, or computer chip applications.
• Solar substrates include, but are not limited to, silicon, amorphous silicon, poly crystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium.
• the solar substrates may be doped or undoped. It is to be understood that the term “microelectronic device” or “semiconductor device” is not meant to be limiting in any way and includes any substrate that will eventually become a microelectronic device or microelectronic assembly.
• barrier material corresponds to any material used in the art to seal the metal lines, e.g. , copper interconnects, to minimize the diffusion of said metal, e.g, copper, into the dielectric material.
• Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.
• substantially free is defined herein as less than 0.001 wt. %. “Substantially free” also includes 0.000 wt. %. The term “free of’ means 0.000 wt. %. As used herein, "about” or “approximately” are intended to correspond to within ⁇ 5% of the stated value.
• Ad ligand means amidinate ligand.
• Gd ligand means guanidinate ligand.
• Alkylene means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms unless otherwise stated (e.g, methylene, ethylene, propylene, 1-methylpropylene, 2- methylpropylene, butylene, pentylene, and the like).
• Heteroalkylene means an -(alkylene)- radical as defined above where one, two or three carbons in the alkylene chain is replaced by -0-, N(H, alkyl, or substituted alkyl), S, SO, S02, or CO. In some preferred embodiments, the carbons are replaced by O or N.
• compositions wherein specific components of the composition are discussed in reference to weight percentage (or “weight %”) ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed. Note all percentages of the components are weight percentages and are based on the total weight of the composition, that is, 100%. Any reference to “one or more” or “at least one” includes “two or more” and “three or more” and so on.
• weight percents unless otherwise indicated are “neat” meaning that they do not include the aqueous solution in which they are present when added to the composition.
• “neat” refers to the weight % amount of an undiluted acid or other material (i.e., the inclusion 100 g of 85% phosphoric acid constitutes 85 g of the acid and 15 grams of diluent).
• compositions described herein in terms of weight %, it is understood that in no event shall the weight % of all components, including non-essential components, such as impurities, add to more than 100 weight %.
• such components may add up to 100 weight % of the composition or may add up to less than 100 weight %.
• such composition may include some small amounts of a non-essential contaminants or impurities.
• the formulation can contain 2% by weight or less of impurities. In another embodiment, the formulation can contain 1% by weight or less than of impurities.
• the formulation can contain 0.05% by weight or less than of impurities.
• the constituents can form at least 90 wt%, more preferably at least 95 wt% , more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and can include other ingredients that do not material affect the performance of the wet etchant. Otherwise, if no significant non-essential impurity component is present, it is understood that the composition of all essential constituent components will essentially add up to 100 weight %.
• amidinate and guanidinate paddlewheel compounds of chromium, molybdenum and tungsten for use as ALD and CVD precursors.
• amidinate paddlewheel compounds of Formula I where: M is one of chromium, molybdenum and tungsten; and
• R 1 , R 2 and R 3 are each independently selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH3)3, a C3-C8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a
• R 1 , R 2 and R 3 are each independently selected from H, unsubstituted linear Ci to C 3 alkyl group and an unsubstituted branched C 3 or C 4 alkyl group. In one aspect, one or more of R 1 , R 2 and R 3 is a methyl group. In one aspect, one or more of R 1 , R 2 and R 3 is an ethyl group.
• one or more of R 1 , R 2 and R 3 is a propyl group. In one aspect, one or more of R 1 , R 2 and R 3 is an isopropyl group. In one aspect, one or more of R 1 , R 2 and R 3 is a sec-butyl group. In one aspect, one or more of R 1 , R 2 and R 3 is a n-butyl group. In one aspect, one or more of R 1 , R 2 and R 3 is an iso-butyl group.
• M is chromium. In another aspect of this embodiment, M is molybdenum. In another aspect of this embodiment, M is tungsten.
• the amidinate ligand (“Ad Ligand”) has a structure as
• R 1 a C 1 -C 5 substituted or unsubstituted alkyl group
• R 2 a C 1 -C 5 substituted or unsubstituted alkyl group.
• M Mo and each of R 1 and R 2 is a methyl group (-CH 3 ):
• M Mo and each of R 1 and R 2 is an ethyl group (-CH 2 CH 3 ):
• the compounds of Formula I include heterocyclic Ad ligands (Formula II-A and Formula II-B) and/or heterocyclic bicyclic Ad ligands (Formula II-C) as shown below where one or both of (a) R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula II-A:
• M is one of chromium, molybdenum and tungsten
• R 2 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH3)3, a C3-C8 unsubstituted cyclic alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C3-C8 unsubstituted aromatic group, a C3-C8 aromatic group substituted with a
• R 1 and R 3 constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• R 1 and R 3 constitute part of a 5-member heterocyclic ring.
• R 1 and R 3 are an unsubstituted alkylene linking group containing three carbons.
• R 1 and R 3 are a substituted alkylene linking group containing three carbons.
• R 1 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one halogen atom.
• R 1 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• R 1 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R 3 are an unsubstituted heteroalkylene linking group containing two carbons and an oxygen.
• R 1 and R 3 are an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen.
• R 1 and R 3 are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 1 and R 3 are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R 3 constitute part of a 6-member heterocyclic ring.
• R 1 and R 3 are an unsubstituted alkylene linking group containing four carbons.
• R 1 and R 3 are a substituted alkylene linking group containing four carbons.
• R 1 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one halogen atom.
• R 1 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• R 1 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R 3 are an unsubstituted heteroalkyl ene linking group containing three carbons and an oxygen.
• R 1 and R 3 are an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen.
• R 1 and R 3 are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 1 and R 3 are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• the precursor has Formula II-B: where: M is one of chromium, molybdenum and tungsten;
• R 1 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a C 3
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• R 2 and R 3 constitute part of a 5-member heterocyclic ring.
• R 2 and R 3 are an unsubstituted alkylene linking group containing three carbons.
• R 2 and R 3 are a substituted alkylene linking group containing three carbons.
• R 2 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one halogen atom.
• R 2 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• R 2 and R 3 are a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R 3 are an unsubstituted heteroalkylene linking group containing two carbons and an oxygen.
• R 2 and R 3 are an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen.
• R 2 and R 3 are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R 3 are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R 3 constitute part of a 6-member heterocyclic ring.
• R 2 and R 3 are an unsubstituted alkylene linking group containing four carbons.
• R 2 and R 3 are a substituted alkylene linking group containing four carbons.
• R 2 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one halogen atom.
• R 2 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• R 2 and R 3 are a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R 3 are an unsubstituted heteroalkylene linking group containing three carbons and an oxygen.
• R 2 and R 3 are an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen.
• R 2 and R 3 are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R 3 are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• the precursor has Formula II-C: II-C where: M is one of chromium, molybdenum and tungsten; and each of (a) R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6- member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• M is one of chromium, molybdenum and tungsten
• R 1 and R 3 and (b) R 2 and R 3 independently constitute parts of a 5- or 6- member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsub
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 each independently constitute part of a 5-member heterocyclic ring.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted alkylene linking group containing three carbons.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing three carbons.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing three carbons substituted by at least one halogen atom.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted heteroalkylene linking group containing two carbons and an oxygen. In a further aspect, each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen. In a further aspect, each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen. In a preferred embodiment of this aspect, the halogen is a fluorine.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are the same.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are different.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 each independently constitute part of a 6-member heterocyclic ring.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted alkylene linking group containing four carbons.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing four carbons.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing four carbons substituted by at least one halogen atom.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted heteroalkylene linking group containing three carbons and an oxygen. In a further aspect, each of (a) R 1 and R 3 and (b) R 2 and R 3 are each independently an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen. In a further aspect, each of
• R 1 and R 3 and R 2 and R 3 are each independently a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R 3 are each independently a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are the same.
• each of (a) R 1 and R 3 and (b) R 2 and R 3 are different.
• the tethered heterocyclic Ad ligands (Formula II- A and
• Formula II-B) and/or heterocyclic bicyclic Ad ligands have a structure as illustrated in Table 2:
• R* whichever of R 1 and R 2 does not form a ring with R 3 and is a C 1 -C 5 substituted or unsubstituted alky group.
• the compounds of Formula II-A and/or II-B have the following structure where the Ad ligand is an iminopiperidinate ligand:
• R* whichever of R 1 and R 2 does not form a ring with R 3 and is a C 1 -C 5 substituted or unsubstituted alkyl group.
• M Mo and R* is sec-butyl group (-
• the precursor has Formula II-D: II-D where: M is one of chromium, molybdenum and tungsten; and each of (a) R 1 and R 2 independently constitute parts of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• M is one of chromium, molybdenum and tungsten
• R 1 and R 2 independently constitute parts of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either two or three atoms exclusive of any substituents or pendent chains thereon.
• the tethered heterocyclic Ad ligands (Formula II-D) have a structure as illustrated in Table 3, and are based on 2-imidazoline ligand:
• the tethered heterocyclic Ad ligands (Formula II-D) have a structure as illustrated in Table 4, and are based on 1,4, 5, 6 tetrahydropyrimidine ligand:
• the compounds of Formula II-D have the following structure where the Ad ligand is 2-methyl-2-imidazoline ligand:
• M Cr, Mo, W.
• Gad paddlewheel compounds of chromium, molybdenum and tungsten of Formula III: III where: M is one of chromium, molybdenum and tungsten; and
• R 1 , R 2 , R 3A and R 3B are each independently selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 - C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C3-C8 un
• all four guanidinate ligands have the same chemical structure. In another aspect of this embodiment, two or more of the guanidinate ligands have the same chemical structure. In another aspect of this embodiment, all four guanidinate ligands have a different chemical structure.
• R 1 , R 2 and R 3 are each independently selected from H, unsubstituted linear Ci to C3 alkyl group and an unsubstituted branched C3 or C4 alkyl group.
• one or more of R 1 , R 2 and R 3 is a methyl group.
• one or more of R 1 , R 2 and R 3 is a ethyl group.
• one or more of R 1 , R 2 and R 3 is a propyl group.
• one or more of R 1 , R 2 and R 3 is an isopropyl group.
• one or more of R 1 , R 2 and R 3 is a sec-butyl group.
• one or more of R 1 , R 2 and R 3 is a n-butyl group.
• one or more of R 1 , R 2 and R 3 is an iso-butyl group.
• M is chromium. In another aspect of this embodiment, M is molybdenum. In another aspect of this embodiment, M is tungsten.
• the tethered guanidinate ligand (“Gd Ligand”) has a
• the compounds of Formula III include heterocyclic Gd ligands (Formula IV- A and Formula IV-B) and/or heterocyclic bicyclic Ad ligands (Formula IV-C) as shown below where one or both of (a) R 1 and R 3A or 3B and (b) R 2 and R 3A or 3B independently constitute parts of a 5 - or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen.
• the precursor has Formula IV-A:
• M is one of chromium, molybdenum and tungsten
• R 2 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a C 3
• R 1 and R x constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one of R 3A and R 3B and R x is the other of R 3A and R 3B that is not connected by a linking group to R 1 .
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• R 1 and R x constitute part of a 5-member heterocyclic ring.
• R 1 and R x are an unsubstituted alkylene linking group containing three carbons.
• R 1 and R x are a substituted alkylene linking group containing three carbons.
• R 1 and R x are a substituted alkylene linking group containing three carbons substituted by at least one halogen atom.
• R 1 and R x are a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• R 1 and R x are a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R x are an unsubstituted heteroalkyl ene linking group containing two carbons and an oxygen.
• R 1 and R x are an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen.
• R 1 and R x are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 1 and R x are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R x constitute part of a 6-member heterocyclic ring.
• R 1 and R x are an unsubstituted alkylene linking group containing four carbons.
• R 1 and R x are a substituted alkylene linking group containing four carbons.
• R 1 and R x are a substituted alkylene linking group containing four carbons substituted by at least one halogen atom.
• R 1 and R x are a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• R 1 and R x are a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 1 and R x are an unsubstituted heteroalkylene linking group containing three carbons and an oxygen.
• R 1 and R x are an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen.
• R 1 and R x are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 1 and R x are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or mor more methyl groups.
• the precursor has Formula IV-B:
• M is one of chromium, molybdenum and tungsten
• R 1 is selected from H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, an unsubstituted amine, an substituted amine, -Si(CH 3 ) 3 , a C 3 -C 8 unsubstituted cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, a C 3 -C 8 unsubstituted aromatic group, a C 3
• R 2 and R z constitute part of a 5- or 6-member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one of R 3A and R 3B and R x is the other of R 3A and R 3B that is not connected by a linking group to R 2 .
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• R 2 and R z constitute part of a 5-member heterocyclic ring.
• R 2 and R z are an unsubstituted alkylene linking group containing three carbons.
• R 2 and R z are a substituted alkylene linking group containing three carbons.
• R 2 and R z are a substituted alkylene linking group containing three carbons substituted by at least one halogen atom.
• R 2 and R z are a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• R 2 and R z are a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R 3 are an unsubstituted heteroalkyl ene linking group containing two carbons and an oxygen.
• R 2 and R z are an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen.
• R 2 and R z are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R z are a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R z constitute part of a 6-member heterocyclic ring.
• R 2 and R z are an unsubstituted alkylene linking group containing four carbons.
• R 2 and R z are a substituted alkylene linking group containing four carbons.
• R 2 and R z are a substituted alkylene linking group containing four carbons substituted by at least one halogen atom.
• R 2 and R z are a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• R 2 and R z are a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n- butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• R 2 and R z are an unsubstituted heteroalkylene linking group containing three carbons and an oxygen.
• R 2 and R z are an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen.
• R 2 and R z are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R z are a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• the precursor has Formula IV-C:
• M is one of chromium, molybdenum and tungsten; and each of (a) R 1 and R x and (b) R 2 and R z independently constitute parts of a 5- or 6- member heterocyclic ring and are one of (i) an unsubstituted alkylene linking group, (ii) a substituted alkylene linking group, (iii) an unsubstituted heteroalkylene linking group where containing a hetero atom is selected from oxygen and nitrogen and (iv) a substituted heteroalkylene linking group containing a hetero atom selected from oxygen and nitrogen, where R z is one ofR 3A and R 3B and R x is the other of R 3A and R 3B .
• the backbone of the alkylenes and heteroalkylenes described in the embodiment above will contain either three or four atoms exclusive of any substituents or pendent chains thereon.
• each of (a) R 1 and R x and (b) R 2 and R z each independently constitute part of a 5-member heterocyclic ring.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted alkylene linking group containing three carbons.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing three carbons.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing three carbons substituted by at least one halogen atom. In a further aspect, each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing three carbons substituted by at least one fluorine atom.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing three carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted heteroalkylene linking group containing two carbons and an oxygen.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted heteroalkylene linking group containing two carbons and a nitrogen.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted heteroalkylene linking group containing two carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R x and (b) R 2 and R z are the same.
• each of (a) R 1 and R x and (b) R 2 and R z are different.
• each of (a) R 1 and R x and (b) R 2 and R z each independently constitute part of a 6-member heterocyclic ring.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted alkylene linking group containing four carbons.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing four carbons.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing four carbons substituted by at least one halogen atom. In a further aspect, each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing four carbons substituted by at least one fluorine atom.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently a substituted alkylene linking group containing four carbons substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted heteroalkylene linking group containing three carbons and an oxygen.
• each of (a) R 1 and R x and (b) R 2 and R z are each independently an unsubstituted heteroalkylene linking group containing three carbons and a nitrogen.
• R 1 and R x and (b) R 2 and R z are each independently a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted with a halogen.
• the halogen is a fluorine.
• R 2 and R z are each independently a substituted heteroalkylene linking group containing three carbons, an oxygen or a nitrogen atom and substituted by at least one of a methyl group, ethyl group, n-propyl group, isopropyl, s-butyl, n-butyl, isobutyl or t-butyl group.
• the substituent is one or more methyl groups.
• each of (a) R 1 and R x and (b) R 2 and R z are the same.
• each of (a) R 1 and R x and (b) R 2 and R z are different.
• the tethered heterocyclic Gd ligands (Formula IV-A and
• Formula IV-B and/or heterocyclic bicyclic Gd ligands.
• (Formula IV-C) have a structure as illustrated in Table 6:
• Table 7 identifies specific embodiments of paddlewheel precursors of general formulae (i) M2-(Ad Ligand) 4 and (ii) M2-(Gd Ligand) 4 that include the ligands set forth in Tables 1-6.
• the precursor is M 2 -(3A) 4 set forth in Table 7 where
• the precursor is M 2 -(3A) 4 set forth in Table 7 where
• the precursor is M 2 -(3B) 4 set forth in Table 7 where M Mo:
• the precursor is M 2 -(3B) 4 set forth in Table 7 where M Cr:
• the precursor is M 2 -(3B) 4 set forth in Table 7 where M W:
• the precursor is M 2 -(3D) 4 set forth in Table 7 where
• the precursor is M 2 -(3XX) 4 set forth in Table 7 where
• the precursor is M 2 -(3XX) 4 set forth in Table 7 where
• the precursor is M 2 -(3XX) 4 set forth in Table 7 where
• the precursor is M 2 -(3UU) 4 set forth in Table 7 where
• the precursor is M 2 -(3UU) 4 set forth in Table 7 where
• the precursor is M 2 -(3UU) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3Z) 4 set forth in Table 7 where
• the precursor is M 2 -(3KK) 4 set forth in Table 7 where
• the precursor is M 2 -(3KK) 4 set forth in Table 7 where
• the precursor is M 2 -(3KK) 4 set forth in Table 7 where
• the precursor is M 2 -(3QQ) 4 set forth in Table 7 where
• the precursor is M 2 -(3QQ) 4 set forth in Table 7 where
• the precursor is M 2 -(3QQ) 4 set forth in Table 7 where
• the precursor is M 2 -(3TT) 4 set forth in Table 7 where
• the precursor is M 2 -(3TT) 4 set forth in Table 7 where
• the precursor is M 2 -(3TT) 4 set forth in Table 7 where
• Ad ligands and Gd ligands are not limited to those exemplified in Tables 1-7.
• the disclosed and claimed paddlewheel precursors are generally made according to the following formula (which is exemplified here using molybdenum to form a molybdenum
• molybdenum (P) acetate is suspended in a suitable solvent (e.g,
• Potassium amidinate can be prepared by reaction of the amidinium sulphates with potassium hexamethyldisilazide.
• the reaction mixture is stirred for a period of time (ca. 4-48 h) after which the solvent is removed by vacuum distillation.
• the crude reaction material is extracted with a suitable solvent (e.g, hexane, toluene, THF) and separated from any insoluble solid by filtration.
• the solvent of the filtrate solution is removed by vacuum distillation to afford the product as a solid.
• the solid is purified by vacuum sublimation.
• molybdenum (II) acetate is suspended in a suitable solvent (e.g,
• Sodium amidinate can be prepared by reaction of “amidine” (protonated amidinate ligand) with sodium hydride.
• the reaction mixture is stirred for a period of time (ca. 4-48 h) after which the solvent is removed by vacuum distillation.
• the crude reaction material is extracted with a suitable solvent (e.g , hexane, toluene, THF) and separated from any insoluble solid by filtration.
• the solvent of the filtrate solution is removed by vacuum distillation to afford the product as a solid.
• the solid is purified by re-crystallization.
• the disclosed and claimed subject matter includes synthesizing precursors of formula M2-(Ad Ligand) 4 and/or M2-(Ad Ligand) 4 according to the following reaction where M is one of chromium, molybdenum and tungsten and the Ad Ligand and Gd ligand are as described above (including in Tables 1-6).
• M is chromium.
• M is molybdenum.
• M is tungsten.
• the precursors of formula M2-(Ad Ligand) 4 and/or M2-( Ad Ligand) 4 synthesized by this process include those set forth in Table 7.
• the disclosed precursors may be deposited to form chromium, molybdenum and tungsten containing films using any chemical vapor deposition process known to those of skill in the art.
• chemical vapor deposition process refers to any process wherein a substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposition.
• atomic layer deposition process refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry that deposits films of materials onto substrates of varying compositions.
• the precursors, reagents and sources used herein may be sometimes described as “gaseous,” it is understood that the precursors can be either liquid or solid which are transported with or without an inert gas into the reactor via direct vaporization, bubbling or sublimation. In some case, the vaporized precursors can pass through a plasma generator.
• Chemical vapor deposition processes in which the disclosed and claimed precursors can be utilized include, but are not limited to, those used for the manufacture of semiconductor type microelectronic devices such as ALD, CVD, pulsed CVD, plasma enhanced ALD (PEALD) and/or plasma enhanced CVD (PECVD).
• Suitable deposition processes for the method disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (Metal Organic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (“PECVD”), high density PECVD, photon assisted CVD, plasma-photon assisted (“PPECVD”), cryogenic chemical vapor deposition, chemical assisted vapor deposition, hot-filament chemical vapor deposition, CVD of a liquid polymer precursor, deposition from supercritical fluids, and low energy CVD (LECVD).
• the metal containing films are deposited via atomic layer deposition (ALD), plasma enhanced ALD (PEALD) or plasma enhanced cyclic CVD (PECCVD) process.
• ALD atomic layer deposition
• PEALD plasma enhanced ALD
• PECCVD plasma enhanced cyclic CVD
• the metal-containing film is deposited using an ALD process.
• the metal-containing film is deposited using a CCVD process.
• the metal-containing film is deposited using a thermal CVD process.
• Suitable substrates on which the disclosed and claimed precursors can be deposited are not particularly limited and vary depending on the final use intended.
• the substrate may be chosen from oxides such as HfO 2 based materials, TiO 2 based materials, ZrO 2 based materials, rare earth oxide-based materials, ternary oxide-based materials, etc. or from nitride-based films.
• substrates may include solid substrates such as metal substrates (for example, Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt and metal silicides (e.g., TiSi 2 , CoSi 2 , and NiSi 2 ); metal nitride containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC); insulators (e.g., SiO 2 , Si 3 N 4 , SiON, HfO 2 , Ta 2 O 5 , ZrO 2 , TiO 2 , Al 2 O 3 , and barium strontium titanate); combinations thereof.
• Preferred substrates include silicon oxide, aluminum oxide, TiN, Ru, Co, Cu and
• Si type substrates One advantage of these precursors is the ability to deposit thin continuous films directly on silicon and aluminum oxides.
• an oxidizing agent can be utilized.
• the oxidizing agent is typically introduced in gaseous form.
• suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.
• the deposition methods and processes may also involve one or more purge gases.
• the purge gas which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors.
• Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, and mixtures thereof.
• a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 seem for about 0.1 to 10000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.
• the deposition methods and processes require that energy be applied to the at least one of the precursors, oxidizing agent, other precursors or combination thereof to induce reaction and to form the metal-containing film or coating on the substrate.
• energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof.
• a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface.
• the plasma-generated process may include a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.
• suitable precursors such as those presently disclosed and claimed — may be delivered to the reaction chamber such as a CVD or ALD reactor in a variety of ways.
• a liquid delivery system may be utilized.
• a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor.
• the precursor compositions described herein can be effectively used as source reagents via direct liquid injection (DLI) to provide a vapor stream of these metal precursors into an ALD or CVD reactor.
• DLI direct liquid injection
• the disclosed and claimed precursors include hydrocarbon solvents which are particularly desirable due to their ability to be dried to sub-ppm levels of water.
• hydrocarbon solvents that can be used in the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p- cymene (4-isopropyl toluene), 1,3 -diisopropylbenzene, octane, dodecane, 1,2,4- trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin).
• the disclosed and claimed precursors can also be stored and used in stainless steel containers.
• the hydrocarbon solvent is a high boiling point solvent or has a boiling point of 100 degrees Celsius or greater.
• the disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture used to deliver both metals simultaneously for the growth of a binary metal-containing films.
• a flow of argon and/or other gas may be employed as a carrier gas to help deliver a vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during the precursor pulsing.
• the reaction chamber process pressure is between 1 and 50 torr, preferably between 5 and 20 torr.
• Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures range from about 150 °C to about 550 °C. Higher temperatures can promote higher film growth rates.
• the disclosed and claimed subject matter includes a method for forming a transition metal -containing film on at least one surface of a substrate that includes the steps of: a. providing the at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on the at least one surface by a deposition process chosen from a thermal chemical vapor deposition (CVD) process and a thermal atomic layer deposition (ALD) process using one or more of the disclosed and claimed precursors of as a metal source compound for the deposition process.
• CVD thermal chemical vapor deposition
• ALD thermal atomic layer deposition
• the method includes introducing at least one reactant into the reaction vessel.
• the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group of water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide and combinations thereof.
• the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and combinations thereof.
• the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen/helium plasma, hydrogen/argon plasma, boron-containing compounds, silicon- containing compounds and combinations thereof.
• the disclosed and claimed subject matter includes a method of forming a transition metal-containing film via a thermal atomic layer deposition (ALD) process or thermal ALD-like process that includes the steps of: a. providing a substrate in a reaction vessel; b. introducing into the reaction vessel one or more of the disclosed and claimed precursors; c. purging the reaction vessel with a first purge gas; d. introducing into the reaction vessel a source gas; e. purging the reaction vessel with a second purge gas; f. sequentially repeating steps b through e until a desired thickness of the transition metal-containing film is obtained.
• ALD thermal atomic layer deposition
• the source gas is one or more of an oxygen-containing source gas selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide and combinations thereof.
• the source gas is one or more of a nitrogen-containing source gas selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma and mixture thereof.
• the first and second purge gases are each independently selected one or more of argon, nitrogen, helium, neon, and combinations thereof.
• the method further includes applying energy to the at least one of precursor, the source gas, the substrate, and combinations thereof, wherein the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods and combinations thereof.
• step b of the method further includes introducing into the reaction vessel the precursor using a stream of carrier gas to deliver a vapor of the precursor into the reaction vessel.
• step b of the method further includes use of a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyl toluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene and combinations thereof.
• the disclosed and claimed precursors are utilized to deposit thin liner or seed layer followed by deposition of bulk metal film using another precursor.
• One advantage of the precursors of this invention is the ability to deposit low resistivity thin films directly on metal oxide and silicon oxide substrates.
• thin films deposited by the precursors of invention may initiate growth of metal films from halogen-containing precursors, may prevent halogen diffusion into the substrate, may reduce stress caused by bulk metal film, and may improve step coverage of metal films.
• bulk metal film is deposited using halogen-containing precursor.
• Halogen-containing precursors include but are not limited to molybdenum pentachloride (MoCl 5 ), molybdenum dioxide dichloride (MoO 2 Cl 2 ), molybdenum hexafluoride (MoF 6 ), tungsten pentachloride (WCl 5 ), tungsten hexachloride (WCl 6 ), tungsten dioxide dichloride (WO 2 Cl 2 ), tungsten hexafluoride (WF 6 ), vanadium tetrachloride (VCl 4 ), vanadium oxytrichloride (VOCl 3 ), etc.
• the disclosed and claimed subject matter includes a method of forming low resistivity transition metal-containing film via an atomic layer deposition (ALD) process or ALD-like process that includes the steps of: a. forming a transition metal-containing film on the at least one surface by a deposition process chosen from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using one or more of the disclosed and claimed precursors of as a metal source compound for the deposition process. b.
• ALD atomic layer deposition
• the films deposited by the above methods and using the disclosed and claimed precursors have a resistivity below approximately 500 ⁇ Ohm cm. In another embodiment, the films deposited by the above methods and using the disclosed and claimed precursors have a resistivity below approximately 400 ⁇ Ohm cm. In another embodiment, the films deposited by the above methods and using the disclosed and claimed precursors have a resistivity below approximately 300 ⁇ Ohm cm.
• the films deposited by the above methods and using the disclosed and claimed precursors have a resistivity below approximately 200 ⁇ Ohm cm. In another embodiment, the films deposited by the above methods and using the disclosed and claimed precursors have a resistivity below approximately 100 ⁇ Ohm cm.
• Molybdenum acetate (0.50 g, 1.17 mmol) was suspended in 15 mL of THF.
• N,N’-dimethylformamidine (7.2 g, 100 mmol) was dissolved in 150 mL of THF.
• Example 3 Crystal structure of Tetrakis(N,N’-dimethylformamidinate)
• N,N’-diethylformamidinium sulfate (16.67 g, ⁇ 3. ⁇ mmol) was dissolved in 250 mL of THF.
• a solution of potassium hexamethyldisilazide (29.40 g, 147.4 mmol) in 125 mL of THF was added dropwise under vigorous stirring. The light-yellow slurry was stirred overnight.
• M02OAC4 (7.50 g, 17.5 mmol) was added as a solid and stirring continued over 4 days. All volatile components were removed under reduced pressure to yield a solid.
• the solid was extracted with hexane (3 x 50 mL). Each extraction was filtered to remove insoluble solids. The combined filtrates were reduced to dryness under reduced pressure to afford 7.50 g of a yellow solid.
• N,N’-diethylformamidine (10 g, 100 mmol) was dissolved in 150 mL of THF.
• Sodium hydride (5 g, 210 mmol) was slowly added with vigorous stirring. The resulting suspension was stirred for 3 days at room temperature. The suspension was filtered, and the filtrate evaporated to dryness under vacuum. The resulting off-white solid Sodium N,N’-diethylformamidinate was used without additional purification. Sodium N,N’-diethylformamidinate (12.2 g, 100 mmol) and M02OAC4 (10.7 g, 25 mmol) were combined in 400 mL of THF and stirred for 3 days at room temperature to form an orange solution with suspended solids. The THF was removed under vacuum and the resulting solid extracted with hexanes (3 x 150 mL) and filtered. The resulting hexanes solutions were combined and slowly evaporated to yield orange crystals.
• Example 8 Thermal Chemical Vapor Deposition of Mo-Containing Films
• Thickness of molybdenum-containing films was measured by X-ray fluorescence (XRF). Almost no deposition was observed at 250 °C suggesting that the precursor is thermally stable up to at least this temperature and can be used for atomic layer deposition.
• XRF X-ray fluorescence
• Film sheet resistance was measured by four-point probe electrode method. Film thickness and film resistance are summarized in Table 8. The experiment suggests that above 250 °C the disclosed and claimed precursors can be used for CVD or CCVD of molybdenum-containing films.
• Mo-containing film with low resistivity ⁇ 200 ⁇ Ohm cm
• Ammonia cyclic CVD was demonstrated by 100 cycles of pulsed process using pulses of molybdenum precursor and ammonia co-reagent with argon purge between precursor and co-reagent pulses: 10 or 20 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of NH 3 / 30 sec of Ar purge.
• the films were deposited on Si substrates at 300 °C and 350 °C. Thickness of molybdenum-containing films was measured by X-ray fluorescence (XRF). Film sheet resistance was measured by four-point probe electrode method. Film thickness and film resistance are summarized in Table 9. The experiment shows that the addition of NH 3 pulse increases deposition rate of Mo-containing film.
• FIGs. 5 and 6 show SEM of Mo-containing films deposited by ammonia cyclic
• FIG. 7 shows Auger depth profile of Mo-containing films deposited by ammonia cyclic CVD process and demonstrates incorporation of nitrogen into the film by ammonia cyclic CVD.
• Hydrogen plasma cyclic CVD was demonstrated by 100 cycles of pulsed process using pulses of molybdenum precursor and hydrogen plasma co-reagent with argon purge between precursor and co-reagent pulses: 10 sec of Mo2(Et-FMD)4 / 30 sec Ar purge / 5 sec of Hydrogen plasma with a 175-watt RF power/ 30 sec of Ar purge.
• the films were deposited on Si and TiN substrates at 350 °C. Thickness of molybdenum-containing films was measured by X-ray fluorescence (XRF). Film sheet resistance was measured by four-point probe electrode method. Film thickness and film resistance are summarized in Table 10. The experiment shows that addition of hydrogen-plasma step further reduces film resistivity to as low as 137 ⁇ Ohm cm.
• ALD of Mo-containing films was demonstrated by 100 cycles of pulsed process using pulses of molybdenum precursor and ammonia co-reagent with argon purge between precursor and co-reagent pulses: 10 sec ofMo2(Et-FMD)4/ 30 sec Ar purge/ 5 sec ofNH 3 / 30 sec of Ar purge. Chamber pressure was 20 torr. Film thickness on top, middle and bottom of patterned substrate were measured by TEM. Aspect ratio of the structure (A/R) was calculated by dividing the total structure depth (26000 A) by structure width in the middle of the structure (1818 A), as shown in FIG. 10. Middle A/R was calculated by dividing the depth at the middle (13000 A) by the width at the middle of the structure (1818 A). Bottom A/R was calculated by dividing the depth at the bottom (24725 A) by the width at the bottom of the structure (1090 A).
• This example shows that the precursors of this invention enable conformal deposition of low resistivity MoCN films on high aspect ratio structures.
• Example 12 Deposition of Thin Continuous MoCN Film on Silicon Oxide
• Continuous 2.6 nm MoCN film was deposited by ammonia cyclic CVD (CCVD) by 30 cycles of pulsed process using pulses of Mo2(Me-FMD)4 and ammonia co-reagent with argon purge between precursor and co-reagent pulses: 10 sec of Mo2(Me-FMD)4 / 30 sec Ar purge / 10 sec of NH 3 / 10 sec of Ar purge.
• the film was deposited on thermal silicon oxide at 400 °C. Thickness of molybdenum-containing films was measured by TEM and is shown on FIG. 11. Sheet resistance of this film was measured by four points electrode method, 7850 Ohm sq, which correspond to thin film resistivity of 2041 ⁇ Ohm cm.
• precursors of this invention enable deposition of thin continuous conductive MoCN films on silicon oxide substrates.
• MoCN films were deposited by ammonia cyclic CVD (CCVD) using pulses of Mo2(Me-FMD)4 and ammonia co-reagent with argon purge between precursor and co-reagent pulses: 10 sec of Mo 2 (Me-FMD) 4 / 30 sec Ar purge / 10 sec of NH 3 / 10 sec of Ar purge.
• the films were deposited on thermal silicon oxide at 350 and 400 °C. Thickness of molybdenum-containing films was measured by XRR and film composition was measured by XPS, Table 12.
• the example demonstrates deposition of low resistivity of MoC x N y films on silicon oxide substrate using precursors of the invention, where x is ranging from approximately 0.5 to 1 and N is below 0.5.
• Example 14 Plasma Enhanced Deposition of Mo-Containing Film on Silicon Oxide
• MoCN films were deposited by cyclic CVD (CCVD) using pulses of Mo2(Me- FMD)4 and hydrogen, nitrogen or ammonia co-reagent with argon purge between precursor and co- reagent pulses: 10 sec of Mo2(Et-FMD)4/ 30 sec Arpurge / 10 sec of NFF/ 10 sec of Ar purge. During co-reagent pulse RF plasma was applied. The films were deposited on thermal silicon oxide at 250 °C and 350 °C. Thickness of molybdenum-containing films was measured by XRF and film sheet resistance was measured by four-point probe method Table 13. The example demonstrates deposition of low resistivity MoCN films on silicon oxide substrate using precursors of the invention, where the thickness of MoCN film is ⁇ 30A and resistivity is as low as approximately 300 ⁇ Ohm cm.
• Example 15 Deposition of Mo metal film by M0O2CI2/H2 process on silicon oxide substrate with and without seed layer deposited by Mo2(Me-FMD)4
• Mo metal film was attempted to deposit directly on silicon oxide substrate at 500 °C wafer temperature by 150 cycles of the following process: 2 sec of M0O2CI2/ 6 sec of Ar purge/10 sec of FF/ 5 sec of Ar purge (chamber pressure was 30 torr).
• M0O2CI2 was purchased from Sigma Aldrich and delivered from a 316SS container heated to 60 °C. No Mo deposition was observed on silicon oxide wafer as shown in FIG.
• Mo metal film was deposited using 150 cycles of the same M0O2CI2/H2 process but on a seed layer deposited by 30 cycles of the following process: 10 sec of Mo2(Me-FMD)4 / 30 sec Arpurge / 10 sec of NFF/ 10 sec of Ar purge (chamber pressure was 1 torr, wafer temperature was 400 °C). Continuous Mo film was deposited when Mo2(Me-FMD)4 is used as shown in FIG. 12.
• Example 16 Deposition of Mo-metal film by M0O2Q2/H2 Process on a Patterned
• Mo metal film was deposited on a patterned silicon oxide substrate.
• the seed layer was deposited at 400 °C wafer temperature by 30 cycles of the following sequence: 10 sec of Mo2(Me-FMD)4 / 30 sec Ar purge / 10 sec of NH 3 / 10 sec of Ar purge (chamber pressure was 1 torr).
• bulk Mo metal film was deposited at 500 °C by 1100 cycles of the following sequence: 2 sec of M0O2CI2/ 6 sec of Ar purge/10 sec of Fh/ 5 sec of Ar purge (chamber pressure was 30 torr).
• M0O2CI2 was purchased from Sigma Aldrich and delivered from a 316SS container heated to 60 °C.
• FIG. 13 shows conformal fill of patterned silicon oxide substrate by the process of the invention.
• This class of compound provides halide-free and oxygen-free precursors for applications where such contaminates are detrimental.
• Precursor properties such as thermal stability, volatility, and composition, are optimal when the amidinate ligand is a formamidinate.
• the nitrogen alkyl substituents are small (C1-C5) and the exocyclic substituent of the cyclic carbon of the amidine ligand is a hydrogen atom.
• Another suitable amidine ligand is the iminopyrrolidinate. This amidine is monocyclic and asymmetric.
• Metal and metal-containing thin films can be produced by thermal or plasma Atomic Layer Deposition and Chemical Vapor Deposition. The method produces thin films with improved properties compared to known methods which could be attributed to the low oxidation state of the paddlewheel precursor.
• a homoleptic molybdenum (II) amidinate or guanidinate paddlewheel compound is obtained by appropriate selection of the ligand.
• Small amidines such as formamidines
• small guanidines or sterically unencumbered mono-cyclic and bi-cyclic amidines and guanidines (e.g, iminopyrrolidines) form homoleptic molybdenum (II) paddlewheel compounds.
• the larger amidine, N,N-di-isopropyl-acetamidine forms a heteroleptic molybdenum (II) amidinate paddlewheel compound. Avoiding oxygen in the ligand composition and in the metal coordination sphere eliminates the possibility of oxygen contamination during the thin film deposition process.
• the described method provides molybdenum films by low temperature, thermal
• Atomic Layer Deposition A low temperature, thermal process provides better integration into existing semiconductor manufacturing methods, better materials compatibility than higher temperature processes, and enables lower thermal budget.
• the ability to produce molybdenum films using ALD provides the advantages inherent to that film growth method, including high uniformity of thickness, ability to coat high aspect ratio features, and precise control of film thickness for very thin layers. Additionally, due to the design of the precursor, thin film contaminates such as oxygen and halides are avoided.
• the rigid paddlewheel structure improves the shelf-life of the precursor at the required container temperature.
• the low oxidation state of the molybdenum atoms deposits electron-rich thin films with desirable electrical properties. In addition, the deposition rate is more than double compared to MoBure.

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