# US 12,217,949 B2 · Magnetically enhanced high density plasma-chemical vapor deposition plasma source for depositing diamond and diamond-like films > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,217,949 B2 - Document ID: US12217949B2 - Status: Granted - Kind: B2 - Application number: 17/495,730 - Filed: 2021-10-06 - Published: 2022-02-10 - Granted: 2025-02-04 - Earliest claimed: 2015-12-21 - Assignees: IonQuest Corp. - Applicants: IonQuest Corp. - Inventors: Bassam Hanna Abraham - Web page: https://patentgrep.com/patent/US12217949B2 ## CPC - H01J 37/3444: {Associated circuits} - C23C 14/0057: {using reactive gases other than O2, H2O, N2, NH3 or CH4} - C23C 14/0605: {Carbon} - C23C 14/14: Metallic material, boron or silicon - C23C 14/345: {using substrate bias} - C23C 14/3485: {using pulsed power to the target} - C23C 14/35: by application of a magnetic field, e.g. magnetron sputtering {(C23C14/3457 takes precedence)} - C23C 14/354: {Introduction of auxiliary energy into the plasma} - H01J 37/321: {the radio frequency energy being inductively coupled to the plasma} - H01J 37/32825: {Working under atmospheric pressure or higher} - H01J 37/3405: {Magnetron sputtering} - H01J 37/3417: {Arrangements} - H01J 37/3426: {Material} - H01J 37/3435: {Target holders (includes backing plates and endblocks)} - H01J 37/345: {Magnet arrangements in particular for cathodic sputtering apparatus (material of magnets or magnets in general H01F1/00, H01F7/00)} - H01J 37/3452: {Magnet distribution} - H01J 37/3455: {Movable magnets} - H01J 37/3464: {Operating strategies} - H01J 37/3467: {Pulsed operation, e.g. HIPIMS} - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) - 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract A method of sputtering a layer on a substrate includes positioning an HEDP magnetron in a vacuum with an anode, cathode target, magnet assembly, substrate, and feed gas; applying a plurality of unipolar negative direct current (DC) voltage pulses from a pulse power supply to a pulse converting network (PCN), wherein the PCN comprises at least one inductor and at least one capacitor; and adjusting an amplitude, pulse duration, and frequency associated with the plurality of unipolar negative DC voltage pulses and adjusting a value of at least one of the at least one inductor and the at least one capacitor, thereby causing a resonance mode associated with the PCN. The substrate is operatively coupled to ground by a first diode, thereby attracting positively charged ions sputtered from the cathode target and plasma to the substrate. A corresponding apparatus and computer-readable medium are also disclosed. ## Claims ### Claim 1 A method of sputtering a layer on a substrate, the method comprising: positioning a HEDP magnetron in a vacuum with an anode, a cathode target, a magnet assembly, the substrate, and a feed gas; applying a plurality of unipolar negative direct current (DC) voltage pulses from a pulse power supply to a pulse converting network (PCN), the PCN comprising at least one inductor, a transformer, a full-wave diode bridge, and at least one capacitor; and adjusting an amplitude, pulse duration, and frequency associated with the plurality of unipolar negative DC voltage pulses and adjusting a value of at least one of the at least one inductor and the at least one capacitor using the PCN configured to cause said adjusting, thereby causing a resonance mode associated with the PCN, the PCN being configured to convert the unipolar negative DC voltage pulses to an asymmetric alternating current (AC) signal that generates a high-density plasma discharge on the HTEDP magnetron with pulse current densities in a range of about 0.1 to 20 A/cm2, the asymmetric AC signal operatively coupled to the cathode target, the PCN being configured to convert the unipolar negative DC voltage pulses to the asymmetric AC signal comprising a first negative voltage and a first positive voltage followed by a second negative voltage generating plasma for use during a subsequent negative voltage, the PCN being configured to cause an increase in amplitude of at least one of the negative voltage pules of the asymmetric AC signal in response to an increase in amplitude or pulse duration of the plurality of unipolar negative DC voltage pulses and the PCN being in the resonance mode, thereby causing sputtering discharge associated with the H-EDP magnetron to form the layer from the cathode target on the substrate, the substrate being connected to ground by a first diode, thereby attracting positively charged ions sputtered from the cathode target and the plasma to the substrate. ### Claim 2 (depends on 1) The method, as defined by claim 1, further comprising applying a negative bias voltage to a second diode operatively coupled to the substrate, thereby attracting positively charged ions sputtered from the cathode target and the plasma to the substrate, a value of the negative bias voltage being in a range of about 10 to 500 V. ### Claim 3 (depends on 1) The method, as defined by claim 1, wherein the cathode target comprises at least one of a hollow shape and flat shape. ### Claim 4 (depends on 1) The method, as defined by claim 1, wherein a value of a magnetic field associated with the HEDP magnetron and disposed parallel to a surface of the cathode target is in a range of about 150 to 1000 G. ### Claim 5 (depends on 1) The method, as defined by claim 1, wherein the feed gas comprises a noble gas, the noble gas comprising at least one of Ar, Ne, Kr, Xe, He. ### Claim 6 (depends on 1) The method, as defined by claim 1, wherein the feed gas comprises a mixture of a noble gas and a reactive gas, the reactive gas being reactive with atoms from the cathode target. ### Claim 7 (depends on 1) The method, as defined by claim 1, wherein the feed gas comprises a mixture of a noble gas and a gas comprising atoms from the cathode target. ### Claim 8 (depends on 1) The method, as defined by claim 1, further comprising rotating the magnet assembly at a speed in a range of about 1 to 400 revolutions per minute. ### Claim 9 (depends on 1) The method, as defined by claim 1, wherein the cathode target comprises at least one of the following elements: B, C, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg, Ca, Sr, Ba. ### Claim 10 (depends on 1) The method, as defined by claim 1, wherein the substrate comprises at least a portion of at least one of an automotive engine, valve, injector head, crank shaft, bushing, bearing, sprocket, cell phone, mobile phone, iPhone, iPod, touch screen, cutting tool, drill bit, insert for cutting tool, semiconductor wafer with a diameter in a range of about 25 to 450 mm, razor blade, film used to manufacture an electronic memory device, RAM, PCRAM, ReRam, solid state battery, and DLC hard mask. ### Claim 11 (depends on 1) The method, as defined by claim 1, wherein the first negative voltage comprises a first amplitude and the second negative voltage comprises a second amplitude, the second amplitude being less than the first amplitude. ### Claim 12 (depends on 1) The method, as defined by claim 1, wherein the magnet assembly comprises at least one of an unbalanced magnetic field and balanced magnetic field. ### Claim 13 (depends on 1) The method, as defined by claim 1, wherein the first diode comprises at least one of a fast switching, fast recovery diode, and fast recovery epitaxial diode (FRED). ### Claim 14 (depends on 1) The method, as defined by claim 1, wherein the asymmetric AC signal comprises a third negative pulse following the second negative pulse, a second positive pulse following the third negative pulse, and a fourth negative pulse following the second positive pulse. ### Claim 15 (depends on 1) The method, as defined by claim 1, wherein the asymmetric AC signal comprises an ignition negative pulse followed by negative voltage glow discharge prior to the first negative pulse. ### Claim 16 An apparatus that sputters a layer on a substrate, the apparatus comprising: a high-energy density plasma (HEDP) magnetron configured to be positioned in a vacuum with an anode, a cathode target, a magnet assembly, the substrate, and a feed gas; a pulse power supply, the pulse power supply providing a plurality of unipolar negative direct current (DC) voltage pulses; and a pulse converting network (PCN) comprising at least one inductor, a transformer, a full-wave diode bridge, and at least one capacitor, the PCN being configured to convert the unipolar negative DC voltage pulses to an asymmetric alternating current (AC) signal that generates a high-density plasma discharge on the HEDP magnetron with pulse current densities in a range of about 0.1 to 20 A/cm2, the PCN being configured to adjust an amplitude, pulse duration, and frequency of the plurality of unipolar negative DC voltage pulses and a value of at least one of the at least one inductor and the at least one capacitor to cause a resonance mode associated with the PCN, the asymmetric AC signal operatively coupled to the cathode target, the PCN being configured to convert the unipolar negative DC voltage pulses to the asymmetric AC signal comprising a first negative voltage and a first positive voltage followed by a second negative voltage-generating plasma for use during a subsequent negative voltage, the PCN being configured to cause an increase in amplitude of at least one of the negative voltage pules of the asymmetric AC signal in response to an increase in amplitude or pulse duration of the plurality of unipolar negative DC voltage pulses and the PCN being in the resonance mode, thereby causing sputtering discharge associated with the HEDP magnetron to form the layer from the cathode target on the substrate, the substrate being connected to ground by a first diode, thereby attracting positively charged ions sputtered from the cathode target and the plasma to the substrate. ### Claim 17 (depends on 16) The apparatus, as defined by claim 16, further comprising a negative bias voltage power supply, the negative bias voltage power supply operatively coupling a negative bias voltage to the substrate using a second diode, thereby attracting positively charged ions sputtered from the cathode target and the plasma to the substrate, a value of the negative bias voltage being in a range of about 10 to 500 V. ### Claim 18 (depends on 16) The apparatus, as defined by claim 16, wherein the cathode target comprises at least one of a hollow shape and a flat shape. ### Claim 19 (depends on 16) The apparatus, as defined by claim 16, wherein a value of a magnetic field associated with the HEDP magnetron and disposed parallel to a surface of the cathode target is in a range of about 150 to 1000 G. ### Claim 20 (depends on 16) The apparatus, as defined by claim 16, wherein the feed gas comprises a noble gas, the noble gas comprising at least one of He, Ar, Kr, Xe, Ne. ### Claim 21 (depends on 16) The apparatus, as defined by claim 16, wherein the feed gas comprises a mixture of a noble gas and a reactive gas, the reactive gas being reactive with atoms from the cathode target. ### Claim 22 (depends on 16) The apparatus, as defined by claim 16, wherein the feed gas comprises a mixture of a noble gas and a gas comprising atoms from the cathode target. ### Claim 23 (depends on 16) The apparatus, as defined by claim 16, wherein the magnet assembly rotates at a speed in a range of about 1 to 400 revolutions per minute. ### Claim 24 (depends on 16) The apparatus, as defined by claim 16, wherein the cathode target comprises at least one of the following elements: B, C, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, I, Tl, Pb, Bi, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg, Ca, Sr, Ba. ### Claim 25 (depends on 16) The apparatus, as defined by claim 16, wherein the substrate comprises at least a portion of at least one of an automotive engine, valve, injector head, crank shaft, bushing, bearing, sprocket, cell phone, mobile phone, iPhone, iPod, touch screen, cutting tool, drill bit, insert for cutting tool, semiconductor wafer with a diameter in a range of about 25 to 450 mm, razor blade, film used to manufacture an electronic memory device, RAM, PCRAM, ReRam, solid state battery, and DLC hard mask. ### Claim 26 (depends on 16) The apparatus, as defined by claim 16, wherein the PCN is configured to convert the unipolar negative DC voltage pulses to the asymmetric alternating current signal that comprises the first negative voltage that comprises a first amplitude and the second negative voltage that comprises a second amplitude, the second amplitude being less than the first amplitude. ### Claim 27 (depends on 16) The apparatus, as defined by claim 16, wherein the magnet assembly comprises at least one of an unbalanced magnetic field and a balanced magnetic field. ### Claim 28 (depends on 16) The apparatus, as defined by claim 16, wherein the first diode comprises at least one of a fast switching, fast recovery diode, and fast recovery epitaxial diode (FRED). ### Claim 29 (depends on 16) The apparatus, as defined by claim 16, wherein the PCN is configured to convert the unipolar negative DC voltage pulses to the asymmetric AC signal that comprises a third negative pulse following the second negative pulse, a second positive pulse following the third negative pulse, and a fourth negative pulse following the second positive pulse. ### Claim 30 (depends on 16) The apparatus, as defined by claim 16, wherein the PCN is configured to convert the unipolar negative DC voltage pulses to the asymmetric AC signal that comprises an ignition negative pulse followed by negative voltage glow discharge prior to the first negative pulse. ### Claim 31 An electrically and magnetically enhanced ionized physical vapor deposition (I-PVD) sputtering apparatus, the apparatus comprising: a magnetron, the magnetron positioned in a vacuum with an anode, a cathode target, a magnetic assembly, the substrate, and a feed gas; a pulse forming network (PFN) receiving a plurality of unipolar negative direct current (DC) voltage pulses from a pulse power supply, the PFN comprising at least one inductor, a transformer, a full-wave diode bridge, and at least one capacitor, the PFN being configured to adjust at least one of an amplitude, pulse duration, and frequency associated with the plurality of unipolar negative DC voltage pulses and a value of at least one of the at least one inductor and the at least one capacitor to cause a resonance mode associated with the PFN, the PFN being configured to convert the unipolar negative DC voltage pulses to an asymmetric alternating current (AC) signal that generates an asymmetric AC discharge on the magnetron with pulse current densities in a range of about 0.1 to 20 A/cm2, the asymmetric AC signal operatively coupled to the cathode target, the PFN being configured to convert the unipolar negative DC voltage pulses to the asymmetric AC signal comprising a first negative voltage and a first positive voltage followed by a second negative voltage generating plasma for use during a subsequent negative voltage associated with the asymmetric AC signal, thereby increasing ionization of sputtered target material on the substrate during sputtering, the substrate being connected to ground by a first diode, thereby attracting positively charged ions sputtered from the cathode target and the plasma to the substrate.