DEFECT ENGINEERED HIGH QUALITY MULTILAYER EPITAXIAL GRAPHENE GROWTH WITH THICKNESS CONTROLLABILITY

Tangali S. Sudarshan; Tawhid Rana; MVS Chandrashekhar

Patent

Atlas literature

Patent

US 11,680,333 B2

DEFECT ENGINEERED HIGH QUALITY MULTILAYER EPITAXIAL GRAPHENE GROWTH WITH THICKNESS CONTROLLABILITY

Tangali S. Sudarshan, Tawhid Rana, MVS Chandrashekhar

University of South Carolina, Columbia, SC (US)·Jun. 20, 2023·US

Drawings

Patent drawings and their descriptions. Click a drawing to enlarge it.

FIG. 1

FIGS. 1A-1C show an atomic model of epitaxial graphene 20 growth, through chemically accelerated silicon removal using an exemplary halogen gas (SiF₄), where

FIG. 2

FIGS. 2A and 2B show a comparison of Raman analysis of surface treatment, with

FIG. 3

FIGS. 3A and 3B show AFM images of surfaces after 35 epitaxial graphene growths using SiF4, where

FIG. 4

FIG. 4 shows a general cross-section of a SiC material 40 having a plurality of graphene layers thereon to form a multilayer graphene ﬁlm.

FIG. 5

FIGS. 5A-5E show an exemplary method for sequentially forming a patterned graphite coating on a SiC material. Repeat use of reference characters in the present …

Claims

Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.

1 independent · 11 dependent

1
Independentmultilayer graphene filmSiF₄SiC
A method for forming a graphene ﬁlm on a silicon carbide material, the method comprising: heating the silicon carbide material to a growth tempera-ture, wherein the growth temperature is about 1,000° C. to about 2,200° C.; and exposing the silicon carbide material to a growth atmo-sphere comprising a halogen species, wherein the halo-gen species comprises silicon tetraﬂuoride, wherein the halogen species reacts with the silicon carbide material to remove silicon therefrom, and wherein the growth atmosphere has a partial pressure of the halogen species that is about 10-4 Torr to about 100 Torr, wherein the graphene ﬁlm comprises a plurality of graphene layers with defects on the surface of the silicon carbide material as determined by the presence of a graphene G-peak and a defect induced D-peak when the gra-phene layers are characterized via Raman spectroscopy, wherein a ratio of the intensity of the D-peak to the G-peak is less than about 0.2, wherein the graphene ﬁlm is a multilayer graphene ﬁlm.
1. 2
  Dependent← claim 1
  The method as in claim 1, wherein the growth tem-perature is about 1,300° C. to about 1,600° C.
2. 3
  Dependent← claim 1
  The method as in claim 1, wherein the growth atmo-sphere is substantially free from any hydrogen species.
3. 4
  Dependent← claim 1
  The method as in claim 1, wherein the growth atmo-sphere is substantially free from any hydrogen species and any oxygen species.
4. 5
  Dependent← claim 1
  The method as in claim 1, wherein the silicon carbide material is heated in an inert gas atmosphere without any halogen species present.
5. 6
  Dependent← claim 1SiF₄
  The method as in claim 1, wherein the halogen species reacts with the silicon carbide material to remove silicon therefrom according to the equation: SiF₄+Siﬁ2SiF2.
6. 7
  Dependent← claim 1
  The method as in claim 1, wherein the growth atmo-sphere consists essentially of the halogen species and at least one inert gas.
7. 8
  Dependent← claim 1
  The method as in claim 1, wherein the growth atmo-sphere consists essentially of the halogen species and an inert gas selected from the group consisting of Ar, He, Xe, N2, and mixtures thereof.
8. 9
  Dependent← claim 1
  The method as in claim 1, further comprising: forming a pattern in the multilayer graphene ﬁlm utilizing lithography.
9. 10
  Dependent← claim 1multilayer graphene film
  The method as in claim 1, wherein the multilayer graphene ﬁlm has a thickness of two graphene ﬁlms to about 1 mm.
10. 11
  Dependent← claim 1multilayer graphene film
  The method as in claim 1, wherein the multilayer graphene ﬁlm has a thickness of two graphene ﬁlms to about 1 µm.
11. 12
  Dependent← claim 1SiC
  The method as in claim 1, wherein the silicon carbide material a substrate, powder, granule, whisker, wire, coating, or a combination thereof.

Materials

Materials described outside the worked examples.

multilayer graphene film

Grown Film Product

silicon tetrafluoride

SiF₄

Halogen Species Precursor

Process steps

Additional fabrication and treatment steps described in the patent.

Epitaxial Graphene Growth

Step 1

Temperature

1000, 2200°C

Ambient

halogen species (SiF4) with optional inert gas (Ar, He, Xe, N2)

Characterization

Measurements and analyses referenced in the patent, with their drawing references.

raman spectroscopy

Raman Spectroscopy

FIGS. 2A and 2B show a comparison of Raman analysis of surface treatment, with

Figure references

FIG. 2

afm

Reported properties

Performance values and ranges asserted in the specification or claims.

Property	Value	Material
Raman D-peak to G-peak intensity ratio	≤ 0.2 dimensionless	multilayer graphene film
Thickness	≤ 40 cm

Cited prior art

Patents and literature cited by this patent (applicant and examiner references).

Cited patents · 10

US 6,579,833 B16,579,833 B1 6/2003 McNallan et al.
US 7,061,021 B27,061,021 B2 6/2006 Sudarshan et al.
US 7,220,978 B27,220,978 B2 5/2007 Ma et al.
US 9,644,288 B29,644,288 B2 5/2017 Sudarshan et al.
US 9,782,846 B29,782,846 B2 10/2017 Sudarshan et al.
US 9,842,898 B29,842,898 B2 12/2017 Sudarshan et al.
US 9,966,491 B29,966,491 B2 5/2018 Chandrashekhar et al.

Why these are connected

Related documents with shared materials, methods, properties, or citations.

DEFECT ENGINEERED HIGH QUALITY MULTILAYER EPITAXIAL GRAPHENE GROWTH WITH THICKNESS CONTROLLABILITY | Matter42 Literature

Cited non-patent literature · 2

Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene. Presser et al., “Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene,” Advanced Functional Materials, vol. 21, No. 5, Mar. 8, 2011, pp. 810-833.
Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure. Peng, “Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure,” Scientiﬁc Reports, Jan. 28, 2013, pp. 1-7. Chowdhury, et al., “High growth rate 4H-SiC epitaxial growth using dichlorosilane in a hot-wall CVD reactor,” Cornell University Materials Science, (2010), pp. 1-30, doi: 10.1016/j.jcrysgro.2010. 11.128. Cicala, et al. Plasma deposition of amorphous SiC:H,F alloys from SiF4CH4H2 mixtures under modulated conditions, J. Appl. Phys. 79, (1996), pp. 8856-8858. doi: 10.1063/1.362473. Daas, et al., “Comparison of epitaxial graphene growth on polar and non-polar 6H-SiC faces: On the growth of multilayer ﬁlms” Crystal Growth and Design, 12, (202), pp. 3379-3387. Daas, et al., “Molecular Gas Adsorption Induced Carrier Transport Studies of Epitaxial Grapheneusing IR Reﬂection Spectroscopy,” Mat. Sci. For., (2012); 717-720, pp. 665-668. Daniels, et al., “Evidence of Electrochemical Graphene Functionaliza- tion by Raman Spectroscopy”, Mat. Sci. For. 7, (2012); 17-720, pp. 661-664. Drowart, et al. “Thermodynamic Study of SiC Utilizing a Mass Spectrometer,” Journal of Chemical Physics, 29, (1958), pp. 1015- 1021. Dubois, et al, “A carbonaceous chemical ﬁlter for the selective detection of NO2 in the environment” Carbon, 52, (2013), pp. 17-29. Emtsev, et al. “Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide,” Nat. Mater. 8, (2009), pp. 203-207. Ganguly, et al. “Polycrystalline silicon carbide ﬁlms deposited by low power radiofrequency plasma decomposition of SiF4CF4H2 gas mixtures,” J. Appl. Phys. 69, (1991), pp. 3915-3923. Gutmann, V. “Halogen Chemistry,” Academic press, 1967. Itoh, et al. “High quality 4HSiC homoepitaxial layers grown by step controlled epitaxy,” Appl. Phys, Lett. 65, (1994), pp. 1400-1402. doi: 10.1063/1.112064. Janaf thermo-chemical data book (http://kinetics.nist.gov/janaf/) (Web). Kawashima, et al., “Fundamentals, overtones, and combinations in the Raman spectrum of graphite” Phys. Rev. B, 52, (1995), pp. 10053-10059. Kida, et al. “Growth and Characterization of SiC Films by Hot-Wire Chemical Vapor Deposition at Low substrate Temperature Using SiF4/CH4/H2 Mixture,” Japanese Journal of Applied Physics, 47(1), (2008), pp. 566-568. Kumagawa, et al. “Hydrogen etching of silicon carbide,” Japanese Journal of Applied Physics 8 (1969), pp. 421-428. Lavia, et al. “4H-SiC epitaxial layer growth by trichlorosilane (TCS),” Journal of Crystal Growth 311 (2008), pp. 107-113. Li, et al. “Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils” Science, 324, (2009), pp. 1312- 1314. Lin, et al., “JOO-GHz Transistors from Wafer-Scale Epitaxial Graphene” Science, 327, (2010), p. 662. Oshima, et al., “Ultra-thin epitaxial ﬁlms of graphite and hexagonal boron nitride on solide surfaces” J. Phys.: Condens. Matt., 9, (1997), pp. 1-20. Pedersen, et al., “Growth characteristics of chloride-based SiC epitaxial growth” PSS Rap. Rev. Lett., 2, (2008), 278. Pedersen, et al. “Very high growth rate of 4H-SiC epilayers using the chlorinated precursor methyltrichlorosilane (MTS),” Journal of Crystal Growth, 307(2), (2007), pp. 334-340. ISSN 0022-0248, 10.1016/j.jcrysgro.2007.07.002. Rana, et al., “Elimination of silicon gas phase nucleation using silicon tetraﬂuoride (SiF4) chemistry for high quality thick SiC homoepitaxy” Phys. Stat. Solid A, 209(12), pp. 2455-2462. DOI: 10.1002/pssa.201228319. Rana, et al., “Behavior of Particles in Growth Raactor and Their Effect on Silicon Carbide Epitaxial Growth” Material Science Forum, 717-720, (2012), pp. 153-156. Robinson, et al. “Correlating Raman Spectral Signatures with Carrier Mobility in Epitaxial Graphene: A Guide to Achieving High Mobility on the Wafer Scale,” Nano Letters9(8), (2009), pp. 2873- 2885. Talukdar, et al., “Aerosol dynamics modeling of silicon nanoparticle formation during silane pyrolysis: a comparison of three solution methods,” Aerosol Science 35, (2004), pp. 889-908. Timms, et al., “Silicon-Fluorine Chemistry. I. Silicon Diﬂuoride and the Perﬂuorosilanes,” J. of the American Chem. Society 87(13), (1965), pp. 2824-2828.10.1016/j.jcrysgro.2010

Cited non-patent literature · 2

Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene. Presser et al., “Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene,” Advanced Functional Materials, vol. 21, No. 5, Mar. 8, 2011, pp. 810-833.
Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure. Peng, “Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure,” Scientiﬁc Reports, Jan. 28, 2013, pp. 1-7. Chowdhury, et al., “High growth rate 4H-SiC epitaxial growth using dichlorosilane in a hot-wall CVD reactor,” Cornell University Materials Science, (2010), pp. 1-30, doi: 10.1016/j.jcrysgro.2010. 11.128. Cicala, et al. Plasma deposition of amorphous SiC:H,F alloys from SiF4CH4H2 mixtures under modulated conditions, J. Appl. Phys. 79, (1996), pp. 8856-8858. doi: 10.1063/1.362473. Daas, et al., “Comparison of epitaxial graphene growth on polar and non-polar 6H-SiC faces: On the growth of multilayer ﬁlms” Crystal Growth and Design, 12, (202), pp. 3379-3387. Daas, et al., “Molecular Gas Adsorption Induced Carrier Transport Studies of Epitaxial Grapheneusing IR Reﬂection Spectroscopy,” Mat. Sci. For., (2012); 717-720, pp. 665-668. Daniels, et al., “Evidence of Electrochemical Graphene Functionaliza- tion by Raman Spectroscopy”, Mat. Sci. For. 7, (2012); 17-720, pp. 661-664. Drowart, et al. “Thermodynamic Study of SiC Utilizing a Mass Spectrometer,” Journal of Chemical Physics, 29, (1958), pp. 1015- 1021. Dubois, et al, “A carbonaceous chemical ﬁlter for the selective detection of NO2 in the environment” Carbon, 52, (2013), pp. 17-29. Emtsev, et al. “Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide,” Nat. Mater. 8, (2009), pp. 203-207. Ganguly, et al. “Polycrystalline silicon carbide ﬁlms deposited by low power radiofrequency plasma decomposition of SiF4CF4H2 gas mixtures,” J. Appl. Phys. 69, (1991), pp. 3915-3923. Gutmann, V. “Halogen Chemistry,” Academic press, 1967. Itoh, et al. “High quality 4HSiC homoepitaxial layers grown by step controlled epitaxy,” Appl. Phys, Lett. 65, (1994), pp. 1400-1402. doi: 10.1063/1.112064. Janaf thermo-chemical data book (http://kinetics.nist.gov/janaf/) (Web). Kawashima, et al., “Fundamentals, overtones, and combinations in the Raman spectrum of graphite” Phys. Rev. B, 52, (1995), pp. 10053-10059. Kida, et al. “Growth and Characterization of SiC Films by Hot-Wire Chemical Vapor Deposition at Low substrate Temperature Using SiF4/CH4/H2 Mixture,” Japanese Journal of Applied Physics, 47(1), (2008), pp. 566-568. Kumagawa, et al. “Hydrogen etching of silicon carbide,” Japanese Journal of Applied Physics 8 (1969), pp. 421-428. Lavia, et al. “4H-SiC epitaxial layer growth by trichlorosilane (TCS),” Journal of Crystal Growth 311 (2008), pp. 107-113. Li, et al. “Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils” Science, 324, (2009), pp. 1312- 1314. Lin, et al., “JOO-GHz Transistors from Wafer-Scale Epitaxial Graphene” Science, 327, (2010), p. 662. Oshima, et al., “Ultra-thin epitaxial ﬁlms of graphite and hexagonal boron nitride on solide surfaces” J. Phys.: Condens. Matt., 9, (1997), pp. 1-20. Pedersen, et al., “Growth characteristics of chloride-based SiC epitaxial growth” PSS Rap. Rev. Lett., 2, (2008), 278. Pedersen, et al. “Very high growth rate of 4H-SiC epilayers using the chlorinated precursor methyltrichlorosilane (MTS),” Journal of Crystal Growth, 307(2), (2007), pp. 334-340. ISSN 0022-0248, 10.1016/j.jcrysgro.2007.07.002. Rana, et al., “Elimination of silicon gas phase nucleation using silicon tetraﬂuoride (SiF4) chemistry for high quality thick SiC homoepitaxy” Phys. Stat. Solid A, 209(12), pp. 2455-2462. DOI: 10.1002/pssa.201228319. Rana, et al., “Behavior of Particles in Growth Raactor and Their Effect on Silicon Carbide Epitaxial Growth” Material Science Forum, 717-720, (2012), pp. 153-156. Robinson, et al. “Correlating Raman Spectral Signatures with Carrier Mobility in Epitaxial Graphene: A Guide to Achieving High Mobility on the Wafer Scale,” Nano Letters9(8), (2009), pp. 2873- 2885. Talukdar, et al., “Aerosol dynamics modeling of silicon nanoparticle formation during silane pyrolysis: a comparison of three solution methods,” Aerosol Science 35, (2004), pp. 889-908. Timms, et al., “Silicon-Fluorine Chemistry. I. Silicon Diﬂuoride and the Perﬂuorosilanes,” J. of the American Chem. Society 87(13), (1965), pp. 2824-2828.10.1016/j.jcrysgro.2010

Cited non-patent literature · 2

Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene. Presser et al., “Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene,” Advanced Functional Materials, vol. 21, No. 5, Mar. 8, 2011, pp. 810-833.
Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure. Peng, “Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure,” Scientiﬁc Reports, Jan. 28, 2013, pp. 1-7. Chowdhury, et al., “High growth rate 4H-SiC epitaxial growth using dichlorosilane in a hot-wall CVD reactor,” Cornell University Materials Science, (2010), pp. 1-30, doi: 10.1016/j.jcrysgro.2010. 11.128. Cicala, et al. Plasma deposition of amorphous SiC:H,F alloys from SiF4CH4H2 mixtures under modulated conditions, J. Appl. Phys. 79, (1996), pp. 8856-8858. doi: 10.1063/1.362473. Daas, et al., “Comparison of epitaxial graphene growth on polar and non-polar 6H-SiC faces: On the growth of multilayer ﬁlms” Crystal Growth and Design, 12, (202), pp. 3379-3387. Daas, et al., “Molecular Gas Adsorption Induced Carrier Transport Studies of Epitaxial Grapheneusing IR Reﬂection Spectroscopy,” Mat. Sci. For., (2012); 717-720, pp. 665-668. Daniels, et al., “Evidence of Electrochemical Graphene Functionaliza- tion by Raman Spectroscopy”, Mat. Sci. For. 7, (2012); 17-720, pp. 661-664. Drowart, et al. “Thermodynamic Study of SiC Utilizing a Mass Spectrometer,” Journal of Chemical Physics, 29, (1958), pp. 1015- 1021. Dubois, et al, “A carbonaceous chemical ﬁlter for the selective detection of NO2 in the environment” Carbon, 52, (2013), pp. 17-29. Emtsev, et al. “Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide,” Nat. Mater. 8, (2009), pp. 203-207. Ganguly, et al. “Polycrystalline silicon carbide ﬁlms deposited by low power radiofrequency plasma decomposition of SiF4CF4H2 gas mixtures,” J. Appl. Phys. 69, (1991), pp. 3915-3923. Gutmann, V. “Halogen Chemistry,” Academic press, 1967. Itoh, et al. “High quality 4HSiC homoepitaxial layers grown by step controlled epitaxy,” Appl. Phys, Lett. 65, (1994), pp. 1400-1402. doi: 10.1063/1.112064. Janaf thermo-chemical data book (http://kinetics.nist.gov/janaf/) (Web). Kawashima, et al., “Fundamentals, overtones, and combinations in the Raman spectrum of graphite” Phys. Rev. B, 52, (1995), pp. 10053-10059. Kida, et al. “Growth and Characterization of SiC Films by Hot-Wire Chemical Vapor Deposition at Low substrate Temperature Using SiF4/CH4/H2 Mixture,” Japanese Journal of Applied Physics, 47(1), (2008), pp. 566-568. Kumagawa, et al. “Hydrogen etching of silicon carbide,” Japanese Journal of Applied Physics 8 (1969), pp. 421-428. Lavia, et al. “4H-SiC epitaxial layer growth by trichlorosilane (TCS),” Journal of Crystal Growth 311 (2008), pp. 107-113. Li, et al. “Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils” Science, 324, (2009), pp. 1312- 1314. Lin, et al., “JOO-GHz Transistors from Wafer-Scale Epitaxial Graphene” Science, 327, (2010), p. 662. Oshima, et al., “Ultra-thin epitaxial ﬁlms of graphite and hexagonal boron nitride on solide surfaces” J. Phys.: Condens. Matt., 9, (1997), pp. 1-20. Pedersen, et al., “Growth characteristics of chloride-based SiC epitaxial growth” PSS Rap. Rev. Lett., 2, (2008), 278. Pedersen, et al. “Very high growth rate of 4H-SiC epilayers using the chlorinated precursor methyltrichlorosilane (MTS),” Journal of Crystal Growth, 307(2), (2007), pp. 334-340. ISSN 0022-0248, 10.1016/j.jcrysgro.2007.07.002. Rana, et al., “Elimination of silicon gas phase nucleation using silicon tetraﬂuoride (SiF4) chemistry for high quality thick SiC homoepitaxy” Phys. Stat. Solid A, 209(12), pp. 2455-2462. DOI: 10.1002/pssa.201228319. Rana, et al., “Behavior of Particles in Growth Raactor and Their Effect on Silicon Carbide Epitaxial Growth” Material Science Forum, 717-720, (2012), pp. 153-156. Robinson, et al. “Correlating Raman Spectral Signatures with Carrier Mobility in Epitaxial Graphene: A Guide to Achieving High Mobility on the Wafer Scale,” Nano Letters9(8), (2009), pp. 2873- 2885. Talukdar, et al., “Aerosol dynamics modeling of silicon nanoparticle formation during silane pyrolysis: a comparison of three solution methods,” Aerosol Science 35, (2004), pp. 889-908. Timms, et al., “Silicon-Fluorine Chemistry. I. Silicon Diﬂuoride and the Perﬂuorosilanes,” J. of the American Chem. Society 87(13), (1965), pp. 2824-2828.10.1016/j.jcrysgro.2010

Cited non-patent literature · 2

Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene. Presser et al., “Carbide-Derived Carbons—From Porous Networks to Nanotubes and Graphene,” Advanced Functional Materials, vol. 21, No. 5, Mar. 8, 2011, pp. 810-833.
Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure. Peng, “Direct Transformation of Amorphpous Silicon Carbide into Graphene Low Temperature and Ambient Pressure,” Scientiﬁc Reports, Jan. 28, 2013, pp. 1-7. Chowdhury, et al., “High growth rate 4H-SiC epitaxial growth using dichlorosilane in a hot-wall CVD reactor,” Cornell University Materials Science, (2010), pp. 1-30, doi: 10.1016/j.jcrysgro.2010. 11.128. Cicala, et al. Plasma deposition of amorphous SiC:H,F alloys from SiF4CH4H2 mixtures under modulated conditions, J. Appl. Phys. 79, (1996), pp. 8856-8858. doi: 10.1063/1.362473. Daas, et al., “Comparison of epitaxial graphene growth on polar and non-polar 6H-SiC faces: On the growth of multilayer ﬁlms” Crystal Growth and Design, 12, (202), pp. 3379-3387. Daas, et al., “Molecular Gas Adsorption Induced Carrier Transport Studies of Epitaxial Grapheneusing IR Reﬂection Spectroscopy,” Mat. Sci. For., (2012); 717-720, pp. 665-668. Daniels, et al., “Evidence of Electrochemical Graphene Functionaliza- tion by Raman Spectroscopy”, Mat. Sci. For. 7, (2012); 17-720, pp. 661-664. Drowart, et al. “Thermodynamic Study of SiC Utilizing a Mass Spectrometer,” Journal of Chemical Physics, 29, (1958), pp. 1015- 1021. Dubois, et al, “A carbonaceous chemical ﬁlter for the selective detection of NO2 in the environment” Carbon, 52, (2013), pp. 17-29. Emtsev, et al. “Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide,” Nat. Mater. 8, (2009), pp. 203-207. Ganguly, et al. “Polycrystalline silicon carbide ﬁlms deposited by low power radiofrequency plasma decomposition of SiF4CF4H2 gas mixtures,” J. Appl. Phys. 69, (1991), pp. 3915-3923. Gutmann, V. “Halogen Chemistry,” Academic press, 1967. Itoh, et al. “High quality 4HSiC homoepitaxial layers grown by step controlled epitaxy,” Appl. Phys, Lett. 65, (1994), pp. 1400-1402. doi: 10.1063/1.112064. Janaf thermo-chemical data book (http://kinetics.nist.gov/janaf/) (Web). Kawashima, et al., “Fundamentals, overtones, and combinations in the Raman spectrum of graphite” Phys. Rev. B, 52, (1995), pp. 10053-10059. Kida, et al. “Growth and Characterization of SiC Films by Hot-Wire Chemical Vapor Deposition at Low substrate Temperature Using SiF4/CH4/H2 Mixture,” Japanese Journal of Applied Physics, 47(1), (2008), pp. 566-568. Kumagawa, et al. “Hydrogen etching of silicon carbide,” Japanese Journal of Applied Physics 8 (1969), pp. 421-428. Lavia, et al. “4H-SiC epitaxial layer growth by trichlorosilane (TCS),” Journal of Crystal Growth 311 (2008), pp. 107-113. Li, et al. “Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils” Science, 324, (2009), pp. 1312- 1314. Lin, et al., “JOO-GHz Transistors from Wafer-Scale Epitaxial Graphene” Science, 327, (2010), p. 662. Oshima, et al., “Ultra-thin epitaxial ﬁlms of graphite and hexagonal boron nitride on solide surfaces” J. Phys.: Condens. Matt., 9, (1997), pp. 1-20. Pedersen, et al., “Growth characteristics of chloride-based SiC epitaxial growth” PSS Rap. Rev. Lett., 2, (2008), 278. Pedersen, et al. “Very high growth rate of 4H-SiC epilayers using the chlorinated precursor methyltrichlorosilane (MTS),” Journal of Crystal Growth, 307(2), (2007), pp. 334-340. ISSN 0022-0248, 10.1016/j.jcrysgro.2007.07.002. Rana, et al., “Elimination of silicon gas phase nucleation using silicon tetraﬂuoride (SiF4) chemistry for high quality thick SiC homoepitaxy” Phys. Stat. Solid A, 209(12), pp. 2455-2462. DOI: 10.1002/pssa.201228319. Rana, et al., “Behavior of Particles in Growth Raactor and Their Effect on Silicon Carbide Epitaxial Growth” Material Science Forum, 717-720, (2012), pp. 153-156. Robinson, et al. “Correlating Raman Spectral Signatures with Carrier Mobility in Epitaxial Graphene: A Guide to Achieving High Mobility on the Wafer Scale,” Nano Letters9(8), (2009), pp. 2873- 2885. Talukdar, et al., “Aerosol dynamics modeling of silicon nanoparticle formation during silane pyrolysis: a comparison of three solution methods,” Aerosol Science 35, (2004), pp. 889-908. Timms, et al., “Silicon-Fluorine Chemistry. I. Silicon Diﬂuoride and the Perﬂuorosilanes,” J. of the American Chem. Society 87(13), (1965), pp. 2824-2828.10.1016/j.jcrysgro.2010