+

WO1994026953A1 - Procede de fabrication de films de diamant orientes - Google Patents

Procede de fabrication de films de diamant orientes Download PDF

Info

Publication number
WO1994026953A1
WO1994026953A1 PCT/US1994/005237 US9405237W WO9426953A1 WO 1994026953 A1 WO1994026953 A1 WO 1994026953A1 US 9405237 W US9405237 W US 9405237W WO 9426953 A1 WO9426953 A1 WO 9426953A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
carbon
transition metal
diamond
hydrogen
Prior art date
Application number
PCT/US1994/005237
Other languages
English (en)
Inventor
Wei Zhu
Peichun Yang
Jeffrey T. Glass
Original Assignee
North Carolina State University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North Carolina State University filed Critical North Carolina State University
Priority to AU68313/94A priority Critical patent/AU6831394A/en
Publication of WO1994026953A1 publication Critical patent/WO1994026953A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

Definitions

  • This invention relates to the field of materials, and, more particularly, to a method for fabricating diamond films on nondiamond substrates, such as for microelectronic applications, and the structures produced according to the method.
  • Background of the Invention Diamond is a preferred material for semiconductor devices because it has semiconductor properties that are superior to conventional semiconductor materials, such as silicon, germanium or gallium arsenide. Diamond provides a higher energy bandgap, a higher breakdown voltage, and a higher saturation velocity than these traditional semiconductor materials.
  • diamond yields a substantial increase in projected cutoff frequency and maximum operating voltage compared to devices fabricated using more conventional semiconductor materials.
  • silicon is typically not used at temperatures higher than about 200°C and gallium arsenide is not typically used above 300°C. These temperature limitations are caused, in part, because of the relatively small energy band gaps for silicon (1.12 eV at ambient temperature) and gallium arsenide (1.42 eV at ambient temperature) .
  • Diamond in contrast, has a large band gap of 5.47 eV at ambient temperature, and is thermally stable up to about 1400°C.
  • Diamond has the highest thermal conductivity of any solid at room temperature and exhibits good thermal conductivity over a wide temperature range.
  • the high thermal conductivity of diamond may be advantageously used to remove waste heat from an integrated circuit, particularly as integration densities increase.
  • diamond has a smaller neutron cross-section which reduces its degradation in radioactive environments, that is, diamond is a "radiation-hard" material.
  • heteroepitaxial growth of single crystal diamond thin films on nondiamond substrates by chemical vapor deposition (CVD) has long been sought due to its enormous potential impact on the microelectronics industry.
  • Promising candidate substrate materials for the heteroepitaxial growth of diamond include cBN, ⁇ - SiC, BeO, Ni, Cu, Si, and a few refractory metals such as Ta, and Mo.
  • nickel is an effective catalyst metal for diamond crystallization under high pressure and high temperature (HPHT) conditions. See, for example, Preparation of Diamond by Bovenkerk et al. , Nature, pp. 1094-1098, October 10, 1959. Although a detailed mechanism of the catalytic effect has not been completely developed, it is believed that its strong reactivity with carbon is essential in the catalytic HPHT diamond growth process. However, nickel's high solubility for carbon and its strong catalytic effect on hydrocarbon decomposition and subsequent graphite formation at low pressures have prevented CVD diamond nucleation on its surface without the deposition of an intermediate graphite layer.
  • a graphite interlayer generally forms immediately when nickel substrates are placed in a methane-hydrogen CVD environment. This has precluded the possible development of an oriented relationship between the diamond film and the nickel substrate, even though diamond might eventually nucleate and grow on the graphite interlayer.
  • the graphite interlayer also prevents good mechanical adhesion to the underlying substrate.
  • an object of the present invention to provide a method for forming an oriented diamond film on a nondiamond substrate, particularly to enable the growth of a single crystal diamond film on the nondiamond substrate. It is another object of the present invention to provide a method for forming a diamond film on a nondiamond substrate using CVD techniques while avoiding the formation of graphite so as to permit formation of an oriented diamond film and/or to produce strong mechanical adhesion between the nondiamond substrate and the thus formed diamond film.
  • a method including the steps of saturating a surface region of a transition metal substrate, capable of dissolving carbon, with carbon and hydrogen; forming oriented diamond nuclei on the saturated surface region of the substrate; and growing diamond on the oriented diamond nuclei to form the oriented diamond film.
  • the substrate transition metal is preferably selected from the group consisting of nickel, cobalt, chromium, magnesium, iron, and alloys thereof, and more preferably, is selected from the group consisting of nickel, cobalt, and alloys thereof which have a relatively close lattice match to diamond.
  • oriented diamond film is meant that the individual diamond nuclei are substantially in alignment with the lattice of corresponding portions of the nondiamond substrate. If the nondiamond substrate is a polycrystalline substrate, the oriented diamond film will also be polycrystalline. Moreover, if the nondiamond substrate is single crystal, and especially if the nondiamond substrate material has a relatively close lattice match with diamond, the oriented diamond film may be further grown into a single crystal diamond film. As would be readily understood by those skilled in the art, with proper growing conditions, individual oriented diamond nuclei can be grown together so that grain boundaries effectively disappear.
  • the saturation of the transition metal surface region may be performed directly from gaseous specie including carbon and hydrogen.
  • the step of saturating the surface region of the substrate with carbon and hydrogen preferably includes heating the substrate at a predetermined temperature of about 900° to 1300°C, and more preferably about 1100°C and for a predetermined time of about 0.5 minutes to 10 hours, and, more preferably, about 0.5 hours to 4 hours in a hydrogen and carbon-containing gas atmosphere.
  • the hydrogen and carbon-containing gas preferably includes methane and hydrogen.
  • the methane is preferably in the range of about 1% to 100% by mass of the gas, and, more preferably about 5% to 20% by mass.
  • the saturated surface region of the substrate is preferably provided by forming a carbon-containing layer on the substrate, and heating the substrate and carbon- containing layer at a predetermined temperature in the range of about 900° to 1300°C, and more preferably, about 1100°C in a hydrogen gas atmosphere.
  • the carbon containing layer may be provided by depositing a layer of diamond powder onto the substrate as disclosed in the parent application, serial number 07/973,633, filed on November 9, 1992, the entire disclosure of which is incorporated herein by reference.
  • the carbon-containing layer may be provided by depositing a nondiamond carbon-containing powder onto the substrate.
  • the nondiamond carbon-containing powder may include one or more of graphite; fullerenes, such as C 60 or C 70 ; soot; carbon black; sugar charcoal; and the like, onto the substrate.
  • the carbon-containing layer may also be provided by an in-situ formed layer on the surface of the substrate.
  • the in-situ deposited layer may include graphite, glassy carbon, soot and diamond-like carbon (DLC) .
  • DLC diamond-like carbon
  • the substrate may be exposed to a 0.5% methane in hydrogen gas at a temperature of about 500°C.
  • the substrate may be exposed to a 5% methane in hydrogen gas at a temperature of about 900°C.
  • the substrate and carbon-containing layer are preferably heated to a predetermined temperature in the range of about 900° to 1200°C.
  • An aspect of the present invention is that observing the appearance of the carbon-containing layer during heating serves to indicate when the surface is saturated and, thus, when the temperature can be reduced for nucleation and diamond growth.
  • the heating time may be about 0.5 hour for a diamond powder, about 5 minutes for a graphite powder, and about 15 minutes for fullerenes, each heating time period also depending upon the thickness of the layer.
  • the transition metal substrate may be either single crystal or polycrystalline.
  • the diamond is preferably formed on a low index plane oriented face selected from the group consisting of ⁇ 100 ⁇ , ⁇ ll ⁇ , ⁇ ill ⁇ , ⁇ 120 ⁇ , ⁇ 112 ⁇ , ⁇ 114 ⁇ , and ⁇ 221 ⁇ .
  • the method of the present invention is desirably used to produce a microelectronic structure including an oriented diamond film.
  • the oriented diamond film may be used for forming diamond-based semiconductor devices, such as for high temperature or radiation-hardened applications. Alternately, an additional layer of single crystal semiconducting diamond may be readily deposited onto the oriented diamond film for fabricating diamond semiconductor devices thereon.
  • the microelectronic structure includes a transition metal substrate capable of dissolving carbon, a surface region on the transition metal substrate including transition metal-carbon-hydrogen states, and the oriented diamond film on the surface region.
  • the substrate has a surface region saturated with carbon and hydrogen.
  • the transition metal is preferably selected from the group consisting of nickel, cobalt, chromium, magnesium, iron, and alloys thereof, and more preferably is a single crystal material, selected from the group consisting of nickel, cobalt, and alloys thereof which have a relatively close lattice match to diamond.
  • the oriented diamond film is preferably formed on a low index plane oriented face selected from the group consisting of ⁇ 100 ⁇ , ⁇ ll ⁇ , ⁇ ill ⁇ , ⁇ 120 ⁇ , ⁇ 112 ⁇ , ⁇ 114 ⁇ , and ⁇ 221 ⁇ .
  • FIG. 1 is a schematic diagram of a conventional CVD reactor as used for carrying out the method according to the invention.
  • FIG. 2A-2E are schematic cross-sectional views illustrating the method according to the present invention according to a first nucleation model .
  • FIGS. 3A-3D are schematic cross-sectional views illustrating the method according to the present invention according to a second nucleation model.
  • FIGS. 4A-4E are schematic cross-sectional views illustrating the method according to the present invention according to a partial dissolution and reorientation model starting with diamond particles.
  • FIGS. 5A-5F are schematic cross-sectional views illustrating the method according to the present invention according to a partial dissolution and reorientation model starting with nondiamond carbon- containing particles.
  • FIGS. 6A and 6B are SEM micrographs of diamond films grown on a ⁇ 100> oriented single crystal Ni surface and a ⁇ 111> oriented single crystal Ni surface, respectively, as described in Example 1.
  • FIGS. 7A-7C are SEM micrographs of diamond films grown on a single crystal Ni surface using C 60 , graphite, and gaseous carbon, respectively, as described in Example 1.
  • FIGS. 8A and 8B are SEM micrographs of diamond films grown on a ⁇ 100> oriented single crystal Ni surfaces, as described in Example 2.
  • FIGS. 9A and 9B are SEM micrographs of diamond films grown on a ⁇ 111> oriented single crystal Ni surfaces, as described in Example 2.
  • FIG. 10 is a Raman spectrum measured from the surface of a diamond film, as described in Example 2. Description of the Preferred Embodiments
  • the reactor 10 includes an evacuable chamber 11, a substrate holder 12, a substrate 15, one or more gas ports 13, and one or more tungsten filament heaters 14, as would be readily understood by those skilled in the art.
  • the reactor 11 may also include associated substrate temperature sensing means, not shown, such as a thermocouple or optical pyrometer as would be readily understood by those skilled in the art.
  • the method according to the present invention may be readily carried out using other conventional semiconductor tools, such as an ECR or plasma enhanced CVD processing chamber.
  • the nondiamond substrate 15 preferably includes a transition metal selected from the group consisting of nickel, cobalt, chromium, magnesium, iron, and alloys thereof. More preferably, the substrate may be single crystal and include a transition metal may be selected from the group consisting of nickel, cobalt and alloys thereof which have a relatively close lattice match to diamond. These transition metals are capable of dissolving carbon and are highly reactive with carbon.
  • the method includes the steps of saturating a surface region of a transition metal substrate 15 with carbon and hydrogen; forming oriented diamond nuclei on the saturated surface region of the substrate; and growing diamond on the oriented diamond nuclei to form the oriented diamond film.
  • the saturation of the transition metal surface region may be performed directly from gaseous specie including carbon and hydrogen.
  • the step of saturating the surface region of the substrate 15 with carbon and hydrogen preferably includes heating the substrate 15 at a predetermined temperature and for a predetermined time in a hydrogen and carbon-containing gas atmosphere.
  • the hydrogen and carbon-containing gas preferably includes pure methane or methane and hydrogen.
  • the methane concentration may be in the range of about 1% and 100% by mass, and more preferably, about 2% to 5% by mass in hydrogen.
  • other gasses may also be used to saturate the surface region of the transition metal substrate.
  • the saturated surface region of the substrate 15 is preferably provided by forming a carbon-containing layer on the substrate, and heating the substrate and carbon-containing layer at a predetermined temperature and for a predetermined time in a hydrogen gas atmosphere.
  • the carbon containing layer may be provided by depositing a layer of diamond powder onto the substrate as disclosed in the parent application, serial number 07/973,633, filed on November 9, 1992.
  • the carbon-containing layer may be provided by depositing a nondiamond carbon-containing powder onto the substrate.
  • the nondiamond carbon-containing powder may include one or more of graphite, a fullerene such as C 60 or C 70 , soot, carbon black, sugar charcoal, and the like, onto the substrate.
  • a fullerene such as C 60 or C 70
  • soot carbon black
  • sugar charcoal and the like
  • the carbon-containing layer may also be provided by an in-situ formed layer of graphite, glassy carbon, soot or diamond-like carbon (DLC) on the substrate.
  • DLC diamond-like carbon
  • the substrate may be exposed to a 0.5% methane in hydrogen gas at a temperature of about 500°C.
  • the substrate may be exposed to a 5% methane in hydrogen gas at a temperature of about 900°C.
  • the substrate and carbon-containing layer are preferably heated or annealed at a predetermined temperature in the range of about 900° to 1300°C, and more preferably about 1100°C, particularly where Ni is the substrate material.
  • the time for heating the substrate is preferably determined by observing the appearance of the carbon-containing layer during heating. For example, when the layer has been heated for a sufficient time, the layer changes to a shiny or reflective appearance and heating may be stopped or the temperature lowered for diamond nucleation and growth.
  • the transition metal substrate 15 may be either single crystal or polycrystalline.
  • the diamond is preferably formed on a low index plane oriented face selected from the group consisting of ⁇ l00 ⁇ , ⁇ ll ⁇ , ⁇ ill ⁇ , ⁇ 120 ⁇ , ⁇ 112 ⁇ , ⁇ 114 ⁇ , and ⁇ 221 ⁇ .
  • the step of depositing the diamond onto the oriented diamond nuclei preferably includes chemical vapor deposition using a carbon and hydrogen containing gas mixture, such as a methane and hydrogen gas mixture, while the substrate is maintained at a predetermined temperature in the range of about 700° to 1000°C, and more preferably in the range of about 900° to 950°.
  • the methane and hydrogen gas mixture for example, preferably includes a methane concentration in the range of about 0.1 to 1.5% by mass, and more preferably no more than about 0.5% methane by mass.
  • a methane concentration in the range of about 0.1 to 1.5% by mass, and more preferably no more than about 0.5% methane by mass.
  • other gas mixtures for CVD formation of diamond may be readily used.
  • the CVD deposition of diamond may be carried out at conventional CVD pressures, such as in the range of about 10 to 150 Torr.
  • FIGS. 2A-2E a first nucleation model is explained wherein a carbon- containing powder 22 is deposited onto the substrate 15 (FIG. 2A) . As shown in FIG. 2B, upon heating or annealing to about 1100°C, the carbon seeds 22 dissolve into the surface of the substrate 15 forming molten areas or Ni-C-H surface states 23.
  • FIG. 2C shows solidified Ni-C-H intermediate surface states at a relatively lower temperature, for example, about 950°C.
  • diamond 30 nucleates on the solidified intermediate surface states 23 and can be grown out wherein the diamond nuclei grow together thereby eliminating grain boundaries to form the oriented diamond film as shown in FIG. 2E.
  • FIGS. 3A-3E Another similar mechanism or model is illustrated in FIGS. 3A-3E.
  • This mechanism is a second nucleation process in which diamond nucleates on a Ni substrate 15 saturated with both carbon and hydrogen. It is believed that the diamond seeds 20 (FIG. 3A) are completely dissolved into the Ni lattice (FIG. 3B) , but the carbon remains highly concentrated in the regions 23 where the diamond seeds are originally located, and is less highly concentrated in adjacent regions 24. While diamond seeds are illustrated in this second nucleation model, those of skill in the art will readily appreciate that nondiamond carbon-containing material may also be used. As would be readily understood by those skilled in the art, for heavy seeding, the highly concentrated Ni-C-H regions 23 may extend across the entire substrate in a layer rather than in discrete areas as shown in the illustrated embodiment.
  • the nucleation of oriented diamond 30 (FIG. 3C) is believed to occur only in those surface regions 23 where the carbon-to-nickel atomic ratio is above a certain value.
  • This C/Ni ratio may be used to define the chemical composition of the correct surface states upon which diamond will nucleate.
  • the orientations of diamond nuclei 30 are readily coincident with the substrate surface Ni lattice because of the close lattice parameter match of the two.
  • the first and second nucleation models regard the locally supersaturated sites with carbon and hydrogen in the Ni surface as diamond nucleation centers. Both carbon and hydrogen dissolve into the Ni lattice, but they remain highly concentrated in the surface region.
  • the orientation of the diamond nuclei can be coincident with the surface Ni lattice which has a close lattice parameter match with diamond.
  • the Ni-C-H areas 23 are portrayed as bumps or protrusions on the substrate surface indicative of their retention of a partially crystalline structure, while in the second nucleation model the Ni-C-H is completely dissolved into the bulk Ni lattice.
  • FIGS. 4A-4E another proposed mechanism for formation of the oriented diamond is a partial dissolution and reorientation mechanism.
  • the substrate 15 is first seeded with diamond powder (FIG. 4A) .
  • FIG. 4B illustrates partial dissolution of the diamond seeds 20 after annealing in hydrogen at about 1100°C and formation of the intermediate Ni-C-H surface states 23.
  • FIG. 4C rotation of the diamond seeds 20 is believed to occur by lattice potential through the molten media 23.
  • FIG. 4D diamond nucleation and growth causes the seeds 20 to grown through metallic surface layers
  • FIG. 4E illustrates continuing growth of the diamond.
  • the partial dissolution and reorientation model considers that the diamond seeds 20 are only partially dissolved in the Ni lattice of the substrate 15 upon annealing and are surrounded by the molten Ni- C-H media 23.
  • the remaining diamond seeds are believed to possess a regular shape bounded with low index planes such as ⁇ lOO ⁇ and ⁇ ill ⁇ to assume a minimum surface energy.
  • the interface between the molten media and the solid Ni lattice is also likely composed of low index planes.
  • Such a configuration will allow the partially dissolved diamond seeds to reorient themselves into alignment with the Ni lattice through a capillary force similar to the operating mechanism in "graphoepitaxy", as described, for example by V. I. Klykov and N. N.
  • the major supportive evidence for the partial dissolution and reorientation mechanism includes the surprisingly similar growth morphology of the diamond films to those Si films grown by typical graphoepitaxy processes (V. I. Klykov, N. N. Sheftal and E. Hartmann, Acta Physica Academiae Scientiarum Hungaricae, 47 (1979) 167) .
  • FIGS. 5A-5F a partial dissolution and reorientation model is illustrated wherein the seed material is a nondiamond carbon powder rather than the diamond seeds as discussed above. Accordingly, as shown in FIGS. 5A and 5B, it is theorized without applicants wishing to be bound thereto that a transition from the nondiamond carbon powder to diamond first occurs in the presence of Ni and atomic hydrogen. The remaining steps of the proposed mechanism are as described above with respect to the diamond powder seeding.
  • the partial dissolution and reorientation mechanism emphasizes the role of molten eutectic phases in the development of orientation. It considers that the diamond seeds 20 are only partially dissolved. Upon annealing at the high temperature, the diamond seeds 20 react rapidly with the Ni lattice and form nickel-carbon (or nickel-carbide) eutectic phases, nickel hydrides and possibly Ni-C-H ternary phases 23.
  • the M.P. of the Ni-C eutectic is 1318°C at atmospheric pressure (H. M. Strong, Acta
  • Metallurgica 12, 1411 (1964)), and the M.P. of nickel hydride is 1150°C (A. R. Badzian and T. Badzian, in Chemical Vapor Deposi tion of Refractory Metals and Ceramics, edited by T. M. Besmann, B. M. Gallois and J. Warren, Mat. Res. Soc. Symp. Proc. 250, Pittsburgh, PA, 1992, p. 339) .
  • a ternary eutectic compound consisting of Ni, C and H could have an even lower M.P.
  • each model or mechanism recognizes the importance of the Ni-C-H intermediate states formed by high temperature annealing in hydrogen atmosphere.
  • the ternary intermediate states act as a molten media to facilitate the reorientation of the partially dissolved diamond seeds
  • the ternary surface states are direct templates for the nucleation of epitaxial diamond.
  • the precise nature of these surface states that is, their composition and structure, are unknown.
  • each mechanism encounters difficulties in explaining all of the experimental observations.
  • the partial dissolution and reorientation model is weak in that it can not account for the encouraging results associated with the use of nondiamond powders unless transformation of nondiamond powders into diamond structure is believed to occur on the Ni surface in the presence of atomic hydrogen (FIGS. 5A-5F) .
  • the major supportive evidence for the partial dissolution and reorientation mechanism includes the surprisingly similar growth morphology of the diamond films to those Si films grown by typical graphoepitaxy processes.
  • the method of the present invention is desirably used to produce a microelectronic structure including an oriented diamond film.
  • the oriented diamond film may be used for forming diamond-based semiconductor devices, such as for high temperature or radiation-hard applications. Alternately, a layer of single crystal semiconducting diamond may be readily deposited onto the oriented diamond film for fabricating diamond semiconductor devices thereon.
  • the microelectronic structure includes a transition metal substrate capable of dissolving carbon, a surface region on the transition metal substrate including transition metal-carbon-hydrogen states, and the oriented diamond film on the surface region. In other words, the substrate has a surface region saturated with carbon and hydrogen.
  • the transition metal is preferably selected from the group consisting of nickel, cobalt, chromium, magnesium, iron, and alloys thereof, and more preferably, selected from the group consisting of nickel, cobalt, and alloys thereof which have a relatively close lattice match to diamond.
  • the oriented diamond film is preferably formed on a low index plane oriented face selected from the group consisting of ⁇ l00 ⁇ , ⁇ ll ⁇ , ⁇ ill ⁇ , ⁇ 120 ⁇ , ⁇ 112 ⁇ , ⁇ 114 ⁇ , and ⁇ 221 ⁇ .
  • EXAMPLE 1 The deposition experiments were performed in a typical hot filament .CVD reactor 10 as described above. Briefly, the process started with seeding single crystal Ni substrates 15 with diamond powders and then annealing the seeded substrates at a temperature of 1100°C in a hydrogen atmosphere. The annealing time was controlled by the visual appearance of the seeded substrates which would change from dark- gray in the initial annealing stage to reflective or shiny when the desired surface stated was formed. After the annealing, the temperature was lowered to 900°C for normal diamond nucleation and growth. The process conditions at this stage included a pressure of 20 torr, a total gas flow rate of 800 seem, and a methane concentration of 0.5% in H 2 .
  • nondiamond carbon powders such as C 60
  • graphite and soot as seeds have also been conducted recently.
  • in-si tu deposited graphite layers on Ni surfaces at low temperatures have also been utilized. During the annealing, the Ni surface seeded with C 60 would turn from red-brown to gray and subsequently to shiny. The surface seeded with graphite and soot would turn from black to light-gray.
  • Ni substrates have been pretreated in-si tu at 1100°C in a hydrogen atmosphere with a high methane concentration (such as 5.0%) .
  • the purpose of such a treatment was to effectively saturate the Ni surface with gaseous carbon and form desirable Ni-C-H surface states upon which oriented diamond could nucleate.
  • the subsequent deposition resulted in highly oriented diamond nuclei as shown in FIG. 7C.
  • the degree of orientation for diamond nucleated on such in- situ pretreated Ni surfaces saturated with gaseous carbon at high temperatures is comparable with those nucleated on diamond seeded substrates.
  • the duration of the anneal was effectively controlled by the visual appearance of the seeded substrates which would change from dark-gray in the initial annealing stage to reflective or shiny when the desirable Ni-C-H surface states were formed.
  • the temperature was lowered to 900°C for normal diamond nucleation and growth at a pressure of 20 Torr and a total gas flow rate of 800 seem.
  • the methane concentration in hydrogen was varied depending on the preferred orientation of the final film. For the ⁇ 100> orientation, the methane concentration was set at 0.5% in H 2 , and for the ⁇ 111> orientation, the methane concentration was controlled at 0.3% in H 2 .
  • both ⁇ 100> and ⁇ 111> oriented films could be grown on single crystal Ni surfaces under the above experimental conditions. It can be seen that in many areas, individual nuclei were grown together with the grain boundaries being eliminated. This was extremely encouraging because it indicated that there was very little misorientation among the neighboring nuclei. As the percentage of such oriented nuclei is further increased and suitable growth condition are determined to foster the selective growth of the preferred orientations, complete single crystal films can be developed with essentially no grain boundaries present which is highly desirable for electronics devices applications. Currently, consistent orientations of about 85% of the diamond nuclei have been realized in an area of about 5x5mm 2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Le procédé de fabrication de films de diamant orientés consiste à saturer une région superficielle d'un substrat de métal de transition capable de dissoudre le carbone au moyen de carbone et d'hydrogène; à former des noyaux de diamant orientés sur la région superficielle saturée du substrat; et à provoquer la croissance du diamant sur les noyaux de diamant orientés de manière à former ledit film de diamant orienté. En théorie, la saturation forme des états de surface hydrogène-carbone-métal de transition (métalx-Cy-H2, où x+y+z=1) sur le substrat de métal de transition tout en supprimant la formation de graphite. Le diamant peut ensuite être déposé sur les noyaux de diamant orientés par des techniques de dépôt chimique en phase vapeur de manière à former un film de diamant orienté sur le substrat non diamant. Ledit substrat non diamant est, de préférence, un métal de transition monocrystallin capable de dissoudre le carbone. Le métal de transition est, de préférence, choisi dans le groupe dans lequel figurent le nickel, le cobalt, le chrome, le magnésium, le fer et des alliages de ces derniers. Les structures produites selon ce procédé sont également décrites, y compris un film de diamant orienté sur un substrat de métal de transition non diamant.
PCT/US1994/005237 1993-05-17 1994-05-11 Procede de fabrication de films de diamant orientes WO1994026953A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68313/94A AU6831394A (en) 1993-05-17 1994-05-11 Method for fabricating oriented diamond films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US062,473 1987-06-15
US6247393A 1993-05-17 1993-05-17

Publications (1)

Publication Number Publication Date
WO1994026953A1 true WO1994026953A1 (fr) 1994-11-24

Family

ID=22042729

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/005237 WO1994026953A1 (fr) 1993-05-17 1994-05-11 Procede de fabrication de films de diamant orientes

Country Status (2)

Country Link
AU (1) AU6831394A (fr)
WO (1) WO1994026953A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014081654A1 (fr) * 2012-11-21 2014-05-30 National Oilwell DHT, L.P. Éléments coupants fixes de trépan comprenant des tables de coupe dures composées de diamants synthétiques obtenus par dépôt chimique en phase vapeur
CN114751408A (zh) * 2022-03-25 2022-07-15 浙江工业大学 一种低压下基于石墨制备金刚石的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849199A (en) * 1987-03-30 1989-07-18 Crystallume Method for suppressing growth of graphite and other non-diamond carbon species during formation of synthetic diamond
JPH04132687A (ja) * 1990-09-21 1992-05-06 Natl Inst For Res In Inorg Mater ダイヤモンド単結晶膜の合成法
EP0530021A2 (fr) * 1991-08-30 1993-03-03 Sumitomo Electric Industries, Limited Couche de diamant et méthode pour sa production
WO1993005207A1 (fr) * 1991-09-03 1993-03-18 Chang R P H Procede de formation de cristallites de diamant et article produit de cette maniere
US5298286A (en) * 1992-11-09 1994-03-29 North Carolina State University Method for fabricating diamond films on nondiamond substrates and related structures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849199A (en) * 1987-03-30 1989-07-18 Crystallume Method for suppressing growth of graphite and other non-diamond carbon species during formation of synthetic diamond
JPH04132687A (ja) * 1990-09-21 1992-05-06 Natl Inst For Res In Inorg Mater ダイヤモンド単結晶膜の合成法
EP0530021A2 (fr) * 1991-08-30 1993-03-03 Sumitomo Electric Industries, Limited Couche de diamant et méthode pour sa production
WO1993005207A1 (fr) * 1991-09-03 1993-03-18 Chang R P H Procede de formation de cristallites de diamant et article produit de cette maniere
US5298286A (en) * 1992-11-09 1994-03-29 North Carolina State University Method for fabricating diamond films on nondiamond substrates and related structures

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BELTON ET AL: "NUCLEATION OF CHEMICALLY VAPOR DEPOSITED DIAMOND ON PLATINUM AND NICKEL SUBSTRATES", THIN SOLID FILMS, vol. 212, no. 1/2, 15 May 1992 (1992-05-15), LAUSANNE CH, pages 68 - 80 *
NARAYAN ET AL: "enhancement of nucleation and adhesion of diamond films on copper, stainless steel, and silicon substrates", JOURNAL OF APPLIED PHYSICS., vol. 71, no. 2, 15 January 1992 (1992-01-15), NEW YORK US, pages 966 - 971 *
PATENT ABSTRACTS OF JAPAN vol. 164, no. 16400 (C - 977) 21 September 1990 (1990-09-21) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014081654A1 (fr) * 2012-11-21 2014-05-30 National Oilwell DHT, L.P. Éléments coupants fixes de trépan comprenant des tables de coupe dures composées de diamants synthétiques obtenus par dépôt chimique en phase vapeur
GB2526940A (en) * 2012-11-21 2015-12-09 Nat Oilwell Dht Lp Fixed cutter drill bit cutter elements including hard cutting tables made from CVD synthetic diamonds
RU2638220C2 (ru) * 2012-11-21 2017-12-12 Нэшнл Ойлвэл Дхт, Л.П. Режущие элементы бурового долота с закрепленными резцами, содержащие твердые режущие пластины, выполненные из синтетических алмазов, сформированных химическим осаждением из паровой фазы
US9976231B2 (en) 2012-11-21 2018-05-22 National Oilwell DHT, L.P. Fixed cutter drill bit cutter elements including hard cutting tables made from CVD synthetic diamonds
CN114751408A (zh) * 2022-03-25 2022-07-15 浙江工业大学 一种低压下基于石墨制备金刚石的方法
CN114751408B (zh) * 2022-03-25 2023-09-05 浙江工业大学 一种低压下基于石墨制备金刚石的方法

Also Published As

Publication number Publication date
AU6831394A (en) 1994-12-12

Similar Documents

Publication Publication Date Title
US5849413A (en) Oriented diamond film structures on nondiamond substrates
US5298286A (en) Method for fabricating diamond films on nondiamond substrates and related structures
Yang et al. Nucleation of oriented diamond films on nickel substrates
Narayan et al. Laser method for synthesis and processing of continuous diamond films on nondiamond substrates
Zhu et al. Oriented diamond films grown on nickel substrates
US5130111A (en) Synthetic diamond articles and their method of manufacture
EP0378378B1 (fr) Fabrication d'outils de coupe recouverts d'un composite à base de diamant
Kobashi Diamond films: chemical vapor deposition for oriented and heteroepitaxial growth
Haubner et al. Diamond deposition on chromium, cobalt and nickel substrates by microwave plasma chemical vapour deposition
Zhang et al. Recent advances in cubic boron nitride deposition
Saitoh et al. Growth of cubic boron nitride on diamond particles by microwave plasma enhanced chemical vapor deposition
Liu et al. Nucleation of oriented diamond particles on cobalt substrates
US20090286352A1 (en) Diamond Bodies Grown on SIC Substrates and Associated Methods
US7435296B1 (en) Diamond bodies grown on SiC substrates and associated methods
US5540904A (en) Isotopically-pure carbon-12 or carbon-13 polycrystalline diamond possessing enhanced thermal conductivity
Yang et al. Diamond nucleation on nickel substrates seeded with non-diamond carbon
JP3728464B2 (ja) 単結晶ダイヤモンド膜気相合成用基板の製造方法
Liu et al. Enhancement of nucleation of diamond films deposited on copper substrate by nickel modification layer
JPH0948693A (ja) 単結晶ダイヤモンド膜の形成方法
WO1994026953A1 (fr) Procede de fabrication de films de diamant orientes
JP2662608B2 (ja) ダイヤモンド単結晶膜の合成法
US5488232A (en) Oriented diamond film structures on non-diamond substrates
Suzuki et al. Current status of heteroepitaxy of CVD diamond
WO1994016125A1 (fr) Procede de synthese de diamant en phase vapeur
GB2257427A (en) Ivsotopically-pure carbon 12 or carbon 13 polycrystalline diamond

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU BB BG BR BY CA CH CN CZ DE DK ES FI GB GE HU JP KG KP KR KZ LK LU LV MD MG MN MW NL NO NZ PL PT RO RU SD SE SI SK TJ TT UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载