US20140263181A1 - Method and apparatus for generating highly repetitive pulsed plasmas - Google Patents

Method and apparatus for generating highly repetitive pulsed plasmas Download PDF

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US20140263181A1
US20140263181A1 US13/860,393 US201313860393A US2014263181A1 US 20140263181 A1 US20140263181 A1 US 20140263181A1 US 201313860393 A US201313860393 A US 201313860393A US 2014263181 A1 US2014263181 A1 US 2014263181A1
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plasma
radio frequency
pulsed
reactor chamber
pulsed radio
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Jaeyoung Park
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Plasmanano Corp
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Assigned to PLASMANANO CORPORATION reassignment PLASMANANO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PARK, JAEYOUNG
Priority to EP14770343.3A priority patent/EP2971226B1/fr
Priority to PCT/US2014/026628 priority patent/WO2014151895A2/fr
Publication of US20140263181A1 publication Critical patent/US20140263181A1/en
Priority to US15/648,198 priority patent/US11427913B2/en
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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
    • C23C16/44—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
    • C23C16/515—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 using pulsed discharges
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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
    • C23C16/02—Pretreatment of the material to be coated
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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
    • C23C16/44—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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/452—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
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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
    • C23C16/44—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
    • C23C16/453—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 passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
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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
    • C23C16/44—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
    • C23C16/45557—Pulsed pressure or control pressure
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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
    • C23C16/44—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
    • C23C16/505—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 using radio frequency discharges
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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
    • C23C16/505—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 using radio frequency discharges
    • C23C16/509—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 using radio frequency discharges using internal electrodes
    • C—CHEMISTRY; METALLURGY
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    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
    • H01J37/3211—Antennas, e.g. particular shapes of coils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/32137—Radio frequency generated discharge controlling of the discharge by modulation of energy
    • H01J37/32146—Amplitude modulation, includes pulsing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H05H1/4645—Radiofrequency discharges
    • H05H1/4652—Radiofrequency discharges using inductive coupling means, e.g. coils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H2242/00—Auxiliary systems
    • H05H2242/20—Power circuits
    • H05H2242/24—Radiofrequency or microwave generators

Definitions

  • Appendix A (6 pages) is a listing of the numbered elements in the diagrams. Appendix A forms part of the specification and is incorporated herein by reference.
  • the disclosure is related to the highly repetitive radio frequency pulsed inductive plasma generation at high gas pressures.
  • the disclosure is related to the operation of said pulsed plasma system in its applications to the materials processing such as nano scale material manufacturing, toxic chemical processing, plasma assisted material deposition and coating, surface removal, surface activation and surface property modification.
  • the pulsed plasma system may also be used for nanodevice fabrication such as the selected activation, deposition, removal of nanomaterials such as nanowires, nanoparticles, quantum dots, nanophosphors—on different substrates and surfaces.
  • Plasma processing has been used in many industrial applications such as plasma etching, thin film deposition, ion implantation, surface modification, and others due to its ability to convert electrical power into superior chemical/thermal reactivity. While plasma device operates in a wide range of gas pressures, the majority of plasma sources have been operated in a vacuum or at low gas pressure. A plasma device may use radio frequency (RF) power to generate the plasma and there are many different plasma sources such as RF capacitive discharge, RF inductive discharge, transformer coupled plasmas (TCP), and helicon sources that can operate in the low gas pressure condition. While these plasma sources have been successfully utilized in semiconductor chip manufacturing and vacuum thin film coating, the low gas pressure operation has limited the use of plasma tools to situations in which a high throughput is not critical.
  • RF radio frequency
  • One way to overcome the throughput issue is to utilize a plasma source that operates at high gas pressures between 1 torr and 2,000 torr.
  • RF inductive plasma generation at atmospheric pressure has been around since 1960s.
  • DC and AC arc plasmas operate at atmospheric pressure range and are used for thermal plasma spray, arc welding, arc deposition and others type of applications requiring high thermal reactivity.
  • the technical challenge of these high pressure plasma sources are their inherent tendency to operate at a high gas temperature at 2,000 C or higher when the input power level is increased to above 10 W/cc level in order to increase the reactive species generation and to achieve high throughput.
  • RF high pressure discharge well known alpha-to-gamma state transition highlights this tendency.
  • Arc deposition can provide high quality coating such as Titanium nitride on to metal cylinders but not on to the flexible polymer surface.
  • the collisions between plasma particles (i.e. ions and electrons) and the neutral gas particles become very frequent at high gas pressure.
  • electron-argon elastic collision frequency is about 26 GHz.
  • electrons are not magnetized in general at such high gas pressure.
  • electron-argon collisions are too frequent for electrons to complete even one cyclotron motion between collisions unless the magnetic field strength exceeds 1 Tesla, which is hard to generate in a large volume.
  • the magnetic field strength exceeds 1 Tesla, which is hard to generate in a large volume.
  • the only allowable plasma waves are Langmuir wave (or plasma oscillation) for electrons, ion acoustic wave (or sound wave) for ions and electromagnetic light wave as described in “Waves in Plasmas” by Thomas Stix, Springer, 1992. Since none of those waves are easily usable for power coupling from externally applied RF fields to the plasmas, the high gas pressure conditions make the RF inductive plasma generation technically challenging. In comparison, DC/AC arcs utilize physical electrodes to generate the plasma, thus a lack of available plasma waves is not an issue.
  • the second reason is engineering and technology in nature. Specifically, there is a lack of readily available high power RF power supplies and RF tuning systems to deliver very large power to antenna for very short period of time.
  • Typical RF power generator operates at 13.56 MHz and delivers the steady-state power output of 1-10 kW into 50 ohm load. This means that a typical RF power system operates with the maximum current rating of 10-20 A and the maximum voltage 500-1000V. Since the resonance circuits, whether in parallel or in series, can only increase either current or voltage but not both at the same time, it is technically challenging to initiate or to sustain high power coupling to plasma above 10 kW, especially for a short pulse duration of less than 10 ms which complicates adjustment in the tuning circuit.
  • the time lag to initiate the gas breakdown from the RF power onset increases from less than 1 microsecond to 100 microseconds or more with increasing gas pressure for a fixed antenna voltage and current.
  • the necessary EMF voltage is approximately 500 V per centimeter of reactor circumference at 10 torr for a reactor size of 5 centimeter diameter. Since these level of EMF voltage cannot be easily generated by readily available RF power generator and the available tuning circuit, a different approach is necessary to initiate, maintain and control the highly repetitive short pulse RF plasmas at high gas pressures.
  • FIG. 1A illustrates an embodiment of a radio frequency pulsed inductive plasma reactor
  • FIGS. 1 B 1 and 1 B 2 are a top view and a side view, respectively, of the radio frequency pulsed inductive plasma reactor in FIG. 1 ;
  • FIG. 2 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor
  • FIG. 3A illustrates an embodiment of the radio frequency pulsed inductive plasma reactor with a substrate
  • FIG. 3B illustrates an embodiment of the radio frequency pulsed inductive plasma reactor with a substrate and a lock load system
  • FIG. 4 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor having a material collection system
  • FIG. 5 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor
  • FIG. 6A illustrates another embodiment of the radio frequency pulsed inductive plasma reactor that has dual pulsed RF power systems
  • FIGS. 6 B 1 and 6 B 2 are a top view and side view, respectively. of the plasma reactor in FIG. 6A ;
  • FIG. 6C illustrates another embodiment of the radio frequency pulsed inductive plasma reactor that has antennas and a single pulsed RF power system
  • FIGS. 7A-7E illustrate another embodiment of the radio frequency pulsed inductive plasma reactor, termed as “pulsed plasma spray device”, that transports the activated materials from the plasma reactor to the target surfaces located outside the reactor;
  • FIG. 8 shows Paschen curve data for the radio frequency pulsed inductive plasma reactor
  • FIG. 9 shows particle in cell simulation results with breakdown delay time as a function of azimuthal electrical strength of the antenna for gas pressure in argon using 1 MHz RF power;
  • FIG. 10A-10D show experimental results for the pulse plasma reactor
  • FIGS. 11A-11C show examples of a resonance circuit that may be used in the pulsed plasma reactor.
  • FIG. 12 illustrates an hourglass shaped reactor chamber embodiment of the pulsed plasma reactor.
  • the disclosure is particularly applicable to pulsed RF inductive plasma system and method and it is in this context that the disclosure will be described. It will be appreciated, however, that the system and method has greater utility since it may be used for materials processing such as nano scale material and device manufacturing, toxic chemical processing, plasma assisted material deposition and coating, surface removal, surface activation and surface property modification.
  • the pulsed plasma system may also be used for nanodevice fabrication such as the selected activation, deposition, removal of nanomaterials, such as nanowires, nanoparticles, quantum dots, nanophosphors, on different substrates and surfaces.
  • the nanodevice fabrication may be done on surfaces including Silicon, SiC, AN, GaN, Sapphire as well as glass, plastics, polymers, fabric, paper, fiberglass, composite materials, metals and alloys.
  • the nanodevices may be formed on both flexible and rigid substrate and surfaces.
  • porous and absorbent materials may be used as well as solid materials.
  • a pulsed RF plasma source described below may limit the duration of energy transfer between the plasma electrons at 1-10 eV range to the gas molecules by directly controlling the plasma source duration.
  • the range of pulse duration may be 10 ⁇ s-10 ms.
  • the collision frequency between the electrons and the gas molecules is frequent, as much as 26 GHz at 10 torr of Argon gases, the efficiency of energy transfer rate is reduced due to a large mass difference between the electron and the argon atom.
  • the gas molecule heating caused by electron can be limited and controlled by such pulse duration.
  • the heat transfer from the plasmas including the electrons and the heated molecules to the surrounding structure is gradual and requires sufficient time to build up the thermal effects.
  • the pulse duration By keeping the pulse duration less than 10 ms, the thermal effects to the plasma facing components are greatly reduced.
  • the pulsed radio frequency (RF) inductive plasma source operating at high gas pressures has advantages over conventional steady-state RF plasma sources with improved efficiency of generating plasma reactivity and with reduced thermal damages to plasma facing components. Since a high reaction throughput is critical for industrial applications of plasma source for materials processing including nanotechnology applications, it is beneficial to generate pulsed RF plasma at gas pressures from 1 torr to 2,000 torr and preferable from 5 torr to 2,000 torr, resulting in high plasma densities between 10 15 cm ⁇ 3 and 10 17 cm ⁇ 3 during the pulse. At such plasma densities, plasmas can generate copious amounts of reactive radicals from a wide range of precursor materials by rapid thermal, chemical and electrical energy transfer from plasma electrons to the precursor materials.
  • FIG. 1A illustrates a first embodiment of a radio frequency pulsed inductive plasma reactor that generates an radio frequency inductive plasma at gas pressures from 1 torr to 2000 torr (and preferably from 5 torr to 2000 torr) and FIGS. 1 B 1 and 1 B 2 are a top view and a side view, respectively, of the radio frequency pulsed inductive plasma reactor in FIG. 1A .
  • the reactor may have a reactor chamber 102 that may have a particular shape, such as a cylinder in FIG. 1B or an hourglass shape as shown in FIG. 12 , and may also have an inlet region at one end and an outlet at an opposite end of the chamber.
  • the reactor chamber may be of any shape and may be for example, square, rectangular, oval or a hexagon.
  • the reactor chamber may have a diameter of between 0.5 inches to 12 inches.
  • the thickness of the walls of the reactor chamber may be 0.5 mm to 5 mm depending on the properties of the material used for the walls.
  • the reactor chamber walls may also be made of two or more materials as long as a dielectric (non-metal) material is used adjacent the antenna.
  • the reactor may also have a pulsed radio frequency generator that is coupled to the reactor chamber 102 .
  • the pulsed radio frequency generator may further include an antenna 107 and a pulsed radio frequency source 108 (that generates a pulsed signal 109 ) that is coupled to the antenna.
  • the antenna 107 may surround a portion of the reactor chamber 102 .
  • the antenna 107 may be a multi-turn coil that encircles the portion of the reactor chamber 102 as shown in FIGS. 1A , 1 B 1 and 1 B 2 .
  • the reactor may also have an inlet 101 that has an entry point for a carrier gas and one or more reactive precursors materials that are turned into a plasma in the reactor chamber.
  • the reactor may also have a pressurizing system 104 that may be used to maintain the gas pressure in the reactor chamber.
  • the pressuring system may further include a pump 106 and a valve 105 .
  • any precursor material (a gas, a liquid or solid precursors) may be used and the pumping may be continuous or operated using a timed pulse.
  • the precursor material may be a solid precursor material having a linear size of between 10 nm to 0.1 mm and preferably a linear size larger than 10 nm and less than 0.1 mm.
  • the precursor material may be a liquid precursor material having a linear size of between 10 nm to 0.1 mm and preferably a linear size larger than 10 nm and less than 0.1 mm.
  • the one or more reactive precursor materials may be, for example, a reactive gas containing hydrogen, oxygen, nitrogen, fluorine, chlorine, sulfur, phosphor and hydrocarbon.
  • the one or more reactive precursor materials may be acids, bases, polymers, metals, ceramics, and composite materials.
  • the carrier gas and the one or more reactive precursors may be introduced into the reactor chamber at the inlet 101 and the pressurizing system may maintain a pressure in the reactor chamber of 1 torr to 2000 torr. Then, a pulsed radio frequency signal is generated by the pulsed radio frequency source 108 and that signal is coupled to the antenna 107 which initiates a breakdown of the carrier gas and one or more reactive precursors and generates a plasma due to the breakdown of the carrier gas and one or more reactive precursors.
  • the reactor generates a pulsed plasma.
  • the pulse plasma means that the duration of plasma generation is short compared to other relevant time scales for plasma source operation. Two specific time scales are chosen to define the pulse plasma operation. One is a time scale relevant to the thermal damage to the RF source structures without complex active cooling systems.
  • the plasma generation involves significant heat generation in the plasma medium and subsequent heat transfer to surrounding structures, including but not limited to the antenna, an enclosure of the pulsed radio frequency generator, one or more walls of the reactor chamber, a substrate for surface treatment, nozzles in the inlet, a material collection system such as filter and collectors.
  • the plasma reactor can operate to generate reactive plume onto various target surfaces for deposition, coating, surface removal, surface modification and treatment.
  • the amount of thermal energy per each pulse can be limited, so even thermally sensitive targets can be utilized. Examples will be plastics, polymers, fiberglass, fabric, ceramics, glass, and even papers as well as metals, alloys and composite materials.
  • the reactor 100 may implement a plasma pulse operation from 10 ⁇ s to 10 ms, where previous intermittent plasma source operation using RF power cannot adequately address due to the RF power supply and plasma coupling limitation.
  • the second time scale is the time scale relevant to a transit time of the gas flow across/through the plasma reactor.
  • gas flow that carries precursor materials in various phases such as gas, liquid droplets, and solid particles into the plasma reaction volume.
  • the precursor materials receive thermal, chemical, electrical energies from the plasmas and undergo desirable reactions.
  • the control of the precursor materials reactivity is governed by the gas flow speed, which is difficult to control precisely over the entire reaction volume as described in “Nanoparticle formation using a plasma expansion process”, by N. Rao, S. Girshick, J.
  • the gas flow needs to be very large, on the order of 100 liters per minute or more, in order to control the plasma reactivity that is described in U.S. Pat. No. 6,994,837 that is incorporated herein by reference.
  • the pulsed plasma operation allows reliable and accurate control of the precursor material reactivity by controlling the pulse duration, when the pulse duration is comparable or shorter than the gas transit time.
  • the typical transit time is about 1 ms to 10 ms for a 10 cm length plasma reactor.
  • the pulse plasma operation from 10 ⁇ s to 10 ms provides simple and reliable control of the precursor material reactivity by regulating the thermal, chemical and electrical energy transfer from the plasmas.
  • this ionization energy is 15.8 eV for the first electron removal.
  • the loss channels may include electron impact excitation followed radiation loss, electron loss to the surrounding boundary, and electron heating of neutral gas atoms by collisions.
  • an energy budget of 150 eV in order to ionize a 5% of gas in the reactor volume, an energy input from pulsed RF power system to the plasmas needs to be 17 J for the reactor volume of 100 cm 3 and a gas pressure of 5 torr, which results in the plasma density of 7 ⁇ 10 15 cm ⁇ 3 .
  • the amount of energy input needs to be 170 J for the reactor volume of 100 cm 3 , which results in the plasma density of 7 ⁇ 10 16 cm ⁇ 3 .
  • the required pulse powers are 1.7 MW for 5 torr and 17 MW for 50 torr.
  • the required pulse powers are 17 kW for 5 torr and 170 kW for 50 torr.
  • additional input powers may be needed in order to generate thermal and chemical reactivity to the precursor materials, by raising temperatures of precursor materials, by dissociating and decomposing precursor materials and generating reactive radicals from precursor materials.
  • high RF power coupling to the plasma during the pulse is needed for the RF pulsed plasmas to be useful in plasma materials processing.
  • High power RF pulse plasmas can utilize a wide range of precursor materials. As shown above, the pulsed RF plasmas can generate very high plasma densities in the range of 10 15 cm ⁇ 3 and 10 17 cm ⁇ 3 during the pulse, if properly powered and controlled. These high plasma densities are what make the pulsed RF plasma reactor very attractive for a wide range of plasma applications. In comparison, typical plasma densities of vacuum based plasma sources such as RF ICP, RF TCP, and RF capacitive discharges are between 1 ⁇ 10 10 cm ⁇ 3 and 1 ⁇ 10 12 cm ⁇ 3 . Separately, spatially averaged plasma densities are typically less than 1 ⁇ 10 10 cm ⁇ 3 in corona discharges and dielectric barrier discharges operating at atmospheric pressure.
  • Atmospheric pressure glow discharges using RF or AC power typically operate up to 1 ⁇ 10 12 cm ⁇ 3 before collapsing into a localized gamma mode, where the plasma generation is limited into the current channel.
  • the pulsed rf plasmas in this invention have comparable plasma densities to various thermal plasmas such as DC arcs, AC arcs, and thermal induction plasma torches operating with rf power. It is noted that the operating mode of DC arcs, AC arcs and thermal induction plasma torches are either steady state or long pulse operation with the pulse duration much greater than 10 ms.
  • the thermal induction plasma torch is a mature technology producing the steady-state plasmas with densities in the range of 10 14 cm ⁇ 3 and 10 17 cm ⁇ 3 , along with the gas temperatures between 3,000 C and 7,000 C, generating high thermal and chemical reactivity as described in Tekna Plasma Systems Inc., Sherbrooke, Quebec, Canada (www.tekna.com) which is incorporated herein by reference.
  • the induction plasma torch has found niche industrial applications in nano-powder and nanomaterial synthesis using gas and solid precursor materials.
  • the pulsed RF plasma reactor can minimize inefficiencies and challenges related to high rate of heat generation and dissipation of the steady-state thermal discharges by utilizing short pulse plasma generation.
  • the pulsed RF plasma reactor operating with plasma densities, in the range of 10 15 cm ⁇ 3 and 10 17 cm ⁇ 3 and with input powers between 10 kW and 10 MW, can generate high gas temperature and associated high chemical reactivity comparable to those steady-state thermal plasmas during the pulse duration in a controlled manner.
  • the RF pulsed plasmas can utilize a wide range of precursor materials from reactive gases containing oxygen, nitrogen, fluorine, chlorine, sulfur, phosphor to hydrocarbon, acids, base, polymers, metals, ceramics, and composite materials in any phases of gas, liquid droplets and solid particles. Since the solid particle precursors up to 100 ⁇ m have been used in the induction thermal plasmas operating between 50 kW and 1 MW, it is projected that the similar particle size up to 100 ⁇ m can also be utilized in the pulsed rf plasma reactor
  • liquid droplets and solid particles are particularly useful for industrial applications for metal and high temperature ceramic and composite materials since it reduces or eliminates the use of highly toxic and reactive organometallic gas precursors.
  • the use of liquid droplets and solid particles also reduces the processing complexities related to maintaining the proper chemical composition or stochiometry of the materials. For example, one of the challenges of the thin film solar cells using copper indium gallium selenide (CIGS) is the proper ratio among copper, indium, gallium and selenide during the deposition process.
  • the pulsed plasma reactor allows the use of chemically complex precursor materials in its solid or liquid from for surface deposition and coating. The same is true for synthesis and applications of YAG (Yttrium aluminium game) phosphor.
  • the pulsed operation of the pulsed RF plasma reactor provides a means to control the amount of activated precursors materials by controlling the energy transfer between the plasma electrons and the precursor materials using the pulse duration.
  • the high plasma density and subsequent high rate of reactive species generation is important in the area of nanotechnology including nanomaterial manufacturing and nano-device fabrication using plasmas.
  • the key issue is large surface areas of the nano materials in the nanotechnology applications.
  • the nano-device fabrication utilizing selected activation, deposition, removal, and patterning of nanomaterials and the structures cannot proceed at rate required for industrial scale.
  • low pressure plasmas and catalytic reaction path are not well suited for industrial scale nano-device fabrication, which is one of the reasons that nanotechnology adoption is still nascent in the industrial applications.
  • a duty factor of the pulsed operation should be in the range of 1-10% level to maintain reasonable degree of throughput.
  • 1% duty factor corresponds to repetition rate of 1 Hz-1 kHz.
  • IGBT is the most suitable solid state switch at present time though other types of solid state switches such as IGCT or GTO may be used.
  • RF inductive plasma system has advantages over other plasma generation system.
  • One of them is the non-contact nature of plasma power coupling.
  • the plasma is generated by the RF power from the external antenna outside the plasma reactor wall.
  • DC and AC plasma generation requires power electrodes to be in contact with the plasmas. Without the exposed power electrodes, there is no plasma damage to the electrodes, thus providing better reliability and reducing materials contamination.
  • the RF frequency for plasma power coupling in the disclosure is given between 50 kHz to 10 MHz. At a short pulse duration between 10 ⁇ s-200 ⁇ s, high RF frequency is important for reactivity control by pulse duration. At 1 MHz RF frequency, the control of pulse duration by a number of RF cycle is 1 ⁇ s increment.
  • the pulsed plasma can control its reactivity within 10%, assuming linear increase in reactivity with pulse duration. If the frequency of RF power is decreased to 100 kHz, it is not possible to provide proper control of reactivity for the 10 ⁇ s pulse. It is thus desirable to operate the RF power period between 0.5% and 10% of total pulse duration. For longer pulse duration above 200 ⁇ s, the more relevant consideration is the efficiency of RF inductive power coupling between the antenna and the plasmas. For a fixed antenna inductance L, the maximum available instantaneous power on the antenna is given as I*L*dI/dt or 6.28*L*I 2 *f, where I is the current flow in the antenna and f is the frequency of the RF power.
  • the required RF current is 280 A at 1 MHz RF frequency. If the RF frequency is decreased to 100 kHz for the same antenna, the required current to provide the same 500 kW is now 900 A.
  • Higher currents in RF power system usually resulted in higher energy loss due to resistive power dissipation in cables, antenna and switches as well significant electromagnetic interference related to parasite inductances in the system.
  • the electric field value multiplied with the electrode spacing between the parallel pate it is necessary to multiply a factor of 2 ⁇ or 6.28 to the published parallel plate breakdown voltage, in order to estimate the proper breakdown voltage needed for the for the cylindrical RF antenna configuration.
  • the radius of the cylindrical antenna to estimate the “pd” value in the Paschen curve. So, in the case of a cylindrical antenna with a radius of 2.54 cm (or 1 inch), the pd value then becomes 12.7 torr cm at 5 torr argon pressure and the pd value becomes 127 torr cm at 50 torr argon pressure.
  • the required breakdown voltages are 600 Volt for 12.7 torr cm and 4,000 Volt for 127 torr cm. After the required conversion factor of 2 ⁇ or 6.28 to properly account for the cylindrical geometry, it is clear that one needs very high antenna voltages to achieve breakdown, 3,600 V for 12.7 torr cm and 25 kV for 127 torr cm.
  • the Paschen curve represent a minimum breakdown voltage, not the required voltage to breakdown the gas rapidly within 1-100 ⁇ s time scale. Typically, one needs a factor of 1.5 to 3 higher voltages to the antenna above the Paschen breakdown voltage within 1-100 ⁇ s time scale in order to ensure rapid and reliable breakdown.
  • the pulsed plasma reactor may use an RF electrical circuit using solid state switches and a cylindrical coil antenna configuration that can generate an antenna voltage of 20 kV at a RF frequency of 1 MHz.
  • V antenna 6.28f*L antenna *I antenna , where V antenna is the voltage across the antenna, f is the RF frequency, L antenna is the antenna inductance, and I antenna is the antenna current.
  • an inductance is about 1.0 ⁇ H for a 6 turn cylindrical coil made of 6 mm copper tube with 50 mm diameter and with 10 mm pitch, corresponding to the coil length of 60 mm. This coil will encompass about 120 cm 3 of reactor volume.
  • the antenna current needs to be 3.2 kA.
  • a series resonance circuit can be used, as shown in FIG. 11A , with the resonance capacitor to minimize the impedance in order to flow this much current.
  • the series resonance circuit has a finite resistance on the order of 0.1-0.2 ohm from the various electrical components such as wires, connectors and switches, prior to plasma loading.
  • This RF system can be readily built by existing commercial IGBT. Note that in this case, a circulating RF power is ⁇ 1 MW, assuming the voltage and the current values are in rms.
  • IXYS corporation offers a discrete IGBT with a voltage rating of 1200V rating, a current rating of 50-100 A and fast switching time of 43 ns, see part number IXYH50N120C3.
  • IXYH50N120C3 By utilizing multiple IGBTs such as the above IGBTs from IXYS, it is then possible to construct RF pulse power system that can deliver 3.2 kA at 320V.
  • RF resonance circuits Although the choice of RF resonance circuits depends on many things, it is noted that a series resonance circuit is better suited because of the inherent robustness of parallel connection of IGBTs, compared to series connection of IGBTs.
  • the overvoltage failure mode of solid state switch is much more challenging than overcurrent failure mode.
  • the IGBT system can handle larger than rated current, while the overvoltage failure is independent of the pulse duration.
  • hybrid circuit combining the benefits of the series resonance circuit and the parallel resonance circuit can be used in combination as shown in FIG. 11C .
  • the interaction between the plasmas and the RF antenna changes dramatically. This is because the gas medium is dielectric in nature with the appropriate dielectric constant of 1, while the plasma medium is electrical conductor with its conductivity comparable to copper. Since there is no appropriate plasma wave mode at high gas pressures, the RF power coupling to the plasma can be viewed as induction heating after breakdown. From the RF circuit point of view, this means there will be real resistance component in the RF circuit from the power coupling to the plasmas and decreased inductance of antenna from the induced current in the plasmas. There are three ways to handle this change in RF circuit composition. The first way is to do nothing and then the series or parallel resonance circuit will be out of resonance due to the reduced inductance of the antenna.
  • a second way is to change the switching frequency of the IGBTs to compensate the plasma coupling as shown in FIG. 5 and it is very useful to utilize the solid state switching RF powers since the RF frequency can be dynamically adjusted during the pulse by providing proper gate timing.
  • this method of change RF frequency during the pulse operation is very difficult in the case of vacuum tube based RF power system.
  • typically a tuning circuit changes the capacitor value once the gas breakdown is achieved to compensate the change in antenna inductance. This second way, however, has some potential downside risk that needs to be considered.
  • a separate set of RF antenna is deployed in the plasma reactor, preferably at the same axial location of the 1 st antenna, and this 2 nd antenna handles the plasma sustainment and the RF power delivery after the breakdown by the 1 st antenna.
  • the location of the secondary antenna has to be overlapped (see FIG.
  • the RF circuit for the 2 nd antenna it is more advantageous to utilize the parallel resonance circuit, as shown in FIG. 11B . This is because the 2 nd antenna does not need high voltage operation since its operation depends on the existence of plasmas in the reactor by the 1 st antenna.
  • a RF electrical circuit using solid state switches and cylindrical coil antenna configuration that can generate deliver 1 MW of RF power to 0.5 ohm plasma load.
  • An inductance is about 0.2 ⁇ H for a 2 turn cylindrical coil made of 6 mm copper tube with 50 mm diameter and with 15 mm pitch, corresponding to the coil length of 30 mm. This coil will encompass about 60 cm 3 of reactor volume.
  • the resonance frequency of 0.4 MHz in order to improve the RF penetration into the reactor volume.
  • the inductive impedance of the antenna is 0.5 ohm. Assuming the real part of antenna resistance is 0.5 ohm from the plasma loading, the total impedance of the antenna is 0.5 ohm.
  • the RF voltage needs to be 700 V and the RF current needs to be 1.4 kA.
  • a RF switching power system using IGBTs for those parameters.
  • this provides two possible configuration to power this 2 nd antenna.
  • One is the use of 2 nd RF pulsed switching system to operate this 2 nd antenna in order to deliver 1 MW of RF power to the plasma load of 0.5 ohm, as shown in FIG. 6A .
  • the other is to utilize a single RF pulse power system with two antenna in a hybrid resonance circuit, as in FIG. 6C and FIG. 11C .
  • the RF pulse power system operates at high frequency, for example at 1 MHz, and utilizes the series resonance circuit for the 1 st antenna with high inductance to initiate the plasmas.
  • the RF pulse power system can then operate at lower frequency, for example at 0.4 MHz, and utilize the parallel resonance circuit for the 2 nd antenna with low inductance to deliver high power to sustain the plasma. Since the resonance conditions are different for the series resonance circuit and the parallel resonance circuit, only one part of the hybrid circuit is active at each frequency. Either configuration will be acceptable, though the choice of RF resonance circuits depends on many things such as cost, system complexities, controllability, efficiency and others.
  • the plasma electrons can transfer its energy to gas molecules via collisions, resulting in gas heating. While the collision frequency is high, the rate of energy transfer efficiency is low for each collision due to very large discrepancy in mass.
  • the general expression for gas heating by plasma electrons is given as dT gas /dt ⁇ n e ⁇ >T e (m e /m gas ), where T gas the gas temperature, n e is the electron density in the plasma, ⁇ is the electron gas collision cross section, ⁇ is the electron velocity, T e is the electron temperature and m e /m gas is the mass ratio between electron and gas atoms.
  • the plasma electron density is 1.4 ⁇ 10 16 cm ⁇ 3 , assuming a 5% ionization fraction.
  • the plasma density can be controlled by the RF pulse input power, while the average electron temperature is between 5 and 10 eV in a wide range of input powers, based on the experimental and theoretical database of rf thermal plasmas in steady state. It is noted that the plasmas establish its density and temperature equilibrium for a given rf input power in a very short time, typically within a few ⁇ s due to the rapid response of electrons to the applied rf electric fields. We will use 5 eV electron in this example, resulting in electron thermal velocity of 9.4 ⁇ 10 7 cm/s and electron temperature of 57,000 Kelvin.
  • electron-gas collision cross section is approximately 1 ⁇ 10 ⁇ 15 cm 2 for argon gas.
  • dT gas /dt is 1 ⁇ 10 8 Kelvin/s or 100 Kelvin/ ⁇ s.
  • the gas temperature in the pulsed plasma reactor will gradually increase over the pulse duration by electron gas heating.
  • the pulse duration control provides a powerful yet convenient method to adjust the reactor gas temperature, especially for pulse duration between 10 ⁇ s and 10 ms.
  • the gas temperature is one of the critical parameters to determine the thermal and chemical reaction of the precursors, this results provide the basis for the reactivity control of the pulse plasmas. It is noted that we have ignored the energy loss mechanism by gas via conduction, convection and radiation, so the temperature rise will be less than this value and the gas temperature will likely saturate between 5,000 C and 10,000 C. It is also noted that the gas heating rate can be controlled by plasma density or RF pulse power. Finally, we note that in the case of liquid and solid precursor materials, the heating rate of those non-gaseous medium will be less than the one of the gas precursor materials since the only surface layer of the liquid and solid materials can absorb the energy directly from the plasmas.
  • the pulse plasma reactor only generates a small amount heat during the pulse operation. It is noted that the heat capacity of the gas is very small, 12.6 J/(mole ⁇ Kelvin). Since the pulse plasmas heat only a small amount of gas molecules, 2.3 ⁇ 10 ⁇ 5 mole of argon gas for 100 cm 3 reactor volume at 5 torr, the total amount of heat from the high temperature is gas is relatively small. Even at 5,000 C, the argon gas in the pulsed reactor will only contain 1.5 J of energy at the above condition. Even at very high repetition rate of 1 kHz, the total gas heating results in 1.5 kW, equivalent to a household hair dryer. This is because of the short pulse nature of pulsed RF plasma operation.
  • thermally sensitive materials as substrate, filter and reactor wall materials in the RF pulsed plasmas.
  • Example will be plastics, polymers, fiberglass, fabric, ceramics, glass, and even papers. If a flexible materials can be utilized, roll-to-roll plasma surface treatment can greatly increase the materials throughput compared to batch system.
  • a repetitively pulsed RF plasma source present a major paradigm change in how the plasma reactor operates with respect to carrier gas and precursor materials injection, gas pumping and reactor operating pressures.
  • a similar example is the internal combustion engine with the timed ignition, fuel injection, compression and exhaust. Since the plasma activation of precursor materials occurs only during the RF power pulse or during the afterglow phase immediately after the RF power pulse, it can be beneficial to operate the plasma reactor with timed carrier gas and precursor materials injection.
  • the gas pumping may be operated in a pulsed mode in synchronization of pulsed RF power or pulsed gas and precursor injection. Even the reactor pressure can be controlled and modulated in time domain with respect to other pulses in the systems such as RF power, injection and pumping.
  • the disclosure introduces the concept of timed pulsed operation among RF pulse power, gas and precursor materials injection, pumping and dynamic reactor pressure control.
  • the benefits from the pulsed operation of RF power, injection, and pumping reactor pressure are: reduction of materials and electricity usage, increase in reaction throughputs.
  • the timing control among different pulses represents a powerful control tool for plasma reactivity.
  • the timing control in connection with the RF power level and the pulse duration can selectively increase one or multiple chemical reaction paths compared to other reaction paths.
  • the reaction selectivity allows the RF pulsed plasma reactor to better control reaction stoichiometry in material synthesis and film deposition and to provide a mechanism of crystal phase control in polymorphic materials synthesis.
  • the pulsed flow of activated reactive materials onto the target substrate can fundamentally alter the interaction between the reactive radicals from the plasmas and the substrate surface layer.
  • the reactive materials flow onto the target substrate and adsorb on the surface area. Since the reactive materials flow stops after the pulse operation, the affected surface layer can undergo relaxation prior to the next wave of reactive materials flow. By controlling the time lapse between the repetitively pulsed reactive materials flow, it is possible to control the property of the surface deposition. Similar mechanism can work for surface layer removal and surface treatment process.
  • FIG. 2 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor.
  • the inlet area may have two inlets 201 , 210 wherein one inlet is for a carrier gas and the other inlet is for the precursor materials.
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG. 1 that generates a plasma 103 .
  • FIG. 3A illustrates an embodiment of the radio frequency pulsed inductive plasma reactor with a substrate 302 that is inside the reactor chamber for deposition, coating, surface modification and treatment, surface removal and/or nano-device fabrication on the substrate.
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG.
  • FIG. 3B illustrates an embodiment of the radio frequency pulsed inductive plasma reactor with a moveable substrate 320 and a lock load system 318 for deposition, coating, surface modification and treatment, surface removal and/or nano-device fabrication on the substrate.
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG. 1 that generates a plasma 103 .
  • the load lock system transports the substrate in and out of the reactor chamber and may have a set of vacuum locks 319 . This embodiment may be used to move large sized substrates into/out of the reactor chamber.
  • FIG. 4 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor having a material collection system for collecting nano materials 402 produced inside of the reactor from the precursors.
  • the material collection system collects different materials generated during the plasma generator and sustainment process.
  • the material collection system may be one or more filters 404 and/or one or more collectors 406 .
  • the material collection system may capture nanoparticles, nanofibers, nanowires, nanocrystals such as quantum dots and nanophosphors synthesized from the reactor.
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG. 1 that generates a plasma 103 .
  • FIG. 5 illustrates another embodiment of the radio frequency pulsed inductive plasma reactor with dynamic RF frequency tuning 500 to improve RF coupling after breakdown and plasma generation.
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG. 1 that generates a plasma 103 .
  • the loading of the antenna by the plasma will change the value of the antenna inductance, which will cause the resonance frequency to shift to a different value compared to the pre-breakdown.
  • a tuning network typically adjusts the capacitor value in order to compensate the change in resonance frequency, which takes more than 10 ms response time due to its mechanical nature of the adjustment.
  • this invention utilizes the change in rf frequency of the power system, triggered by the onset of plasma formation.
  • One of the benefits of using solid state switching rf system is its ability to change the rf frequency by simply changing the switching pulse timing.
  • the control system timing can be pre-programmed to increase the switching frequency after the breakdown to compensate the change in the antenna inductance by the plasma after breakdown.
  • FIGS. 6A-6C illustrate other embodiments of the radio frequency pulsed inductive plasma reactor that has dual pulsed RF power systems 108 , 602 .
  • the rest of the reactor is the same and has the same reference numbers (which are therefore not described in detail here) as the reactor in FIG. 1 that generates a plasma 103 .
  • the first RF power system may include elements 107 - 109 and the second may include elements 602 , 604 and 606 (pulsed signal, RF source and antenna).
  • FIG. 6C illustrates another embodiment in which the two antennas 107 , 604 may be both driven by a common RF source 108 that generates the pulsed RF signal 109 .
  • each pulsed RF power source is interposed as shown in FIG. 6A , but may also be configured differently.
  • a first pulsed RF power source may be used to initiate the plasma generation and then the second pulsed RF power source may be used to sustain the plasma once it is generated.
  • FIGS. 7A-7E illustrate process for generating pulse plasma using the pulsed plasma reactor.
  • a pulsed plasma spray source is another example of pulse plasma source and timed operation of gas injection and pumping.
  • the plasma source needs to operate at atmospheric pressure or above atmospheric pressure in order to transport plasma activated reactive species onto the target surface located in the ambient environment.
  • a thermal plasma spray is one example of such device that thermally activates precursor materials in the plasma reaction volume and the activated materials such as melted metals and ceramics are sprayed onto a target surface located outside the reactor in an ambient pressure.
  • RF pulsed plasma operation can occur at gas pressures below atmospheric pressure, while thermally and chemically activated materials can be sprayed onto a target surface located in an ambient pressure.
  • Step 1 ( FIG. 7A ): At t 0 , the plasma reactor volume is sealed by a seal 707 that is closed from the ambient environment and the gas pumping is provided to maintain low gas pressure in the reactor volume. No RF power is being applied in this step. During this process, the inlet valve 201 , 210 may be closed (filled pattern) and the pumping valve 105 may be open (unfilled pattern.)
  • Step 2 ( FIG. 7B ): Between t 1 and t 2 , carrier gas and precursor materials are introduced into the plasma reactor with operation of pulsed inlet valves 201 , 210 .
  • the gas pressure in the reactor is maintained between 5 torr and 500 torr by the balance between the gas inflow and the pumping, while being sealed by the seal 707 from the ambient pressure.
  • the pumping valve 105 may be open.
  • Step 3 ( FIG. 7C ): Between t 2 and t 3 , pulsed RF powers are applied and generate plasmas 103 .
  • the plasma can activate precursor materials and generate reactive species. It is noted that rapid plasma heating will increase the pressure in the reactor volume from its initial pressure and the seal 707 is still closed and thus no materials are coming out of an exit nozzle 708 .
  • the inlet valve 201 , 210 may be open and the pumping valve 105 may be open.
  • Step 4 ( FIG. 7D ): Between t 3 and t 4 , the activated materials by the pulsed plasmas leave the reactor and flow toward the outlet. With the use of rotating pneumatic seals 707 , an exit nozzle 708 is open, which allow the activated materials 713 to flow onto a target surface 706 located outside the reactor at ambient pressure. At the same time, the gas pumping path is closed. If the reactor gas pressure during the pulsed plasma operation exceeds the atmospheric pressure, the outflow of the reactive materials can be directed toward the target surface without additional gas injection. If the reactor gas pressure during the pulsed plasma operation is below the atmospheric pressure, an additional gas valve in the reactor upstream is open in order to increase the reactor gas pressure and to generate outward flow to the ambient environment through the exit nozzle.
  • Step 5 ( FIG. 7E ): Between t 4 and t 5 , once the majority of reactive materials are sprayed onto a target surface, the seal 707 is then closed, while the gas pumping is resumed. Once the gas pressure in the reactor drops below desired set point after sufficient gas pumping, the cycle repeats from step 1 to step 5 with the repetition rate between 1 Hz and 100 Hz.
  • the above described pulsed plasma spray allows the various in-situ plasma treatments such as deposition, surface modification, surface layer removal and patterning, for large objects and the target materials that cannot be contained in the plasma reactor. Furthermore, since the pulsed plasma generates little thermal heat, the pulsed plasma spray can be applied to any heat sensitive materials such as glass, plastics, polymers, fabric, paper, fiberglass, and composite materials. For example, the pulsed plasma spray can apply protective coatings on the heat sensitive large scale glass reinforced plastic structure materials such as wind turbine blades and marine vessel body.
  • FIG. 8 shows Paschen curve data for the radio frequency pulsed inductive plasma reactor for common carrier gases such as helium (He), neon (Ne), argon (Ar), hydrogen (H 2 ) and nitrogen (N 2 ), indicating that high voltage at the antenna (shown along the vertical axis) is needed to achieve rapid gas breakdown at high gas pressures.
  • common carrier gases such as helium (He), neon (Ne), argon (Ar), hydrogen (H 2 ) and nitrogen (N 2 ), indicating that high voltage at the antenna (shown along the vertical axis) is needed to achieve rapid gas breakdown at high gas pressures.
  • FIG. 9 show computer simulation results with breakdown delay time as a function of azimuthal electrical strength of the antenna for gas pressure in argon using 1 MHz RF power. More particularly, FIG. 9 shows breakdown delay time as a function of azimuthal electrical field strength of the antenna for gas pressure in argon using 1 MHz RF power.
  • the results are from a one-dimensional particle-in-cell (PIC) simulation with Monte Carlo collision (MCC) treatment for electron gas collisions including ionization, excitation, and elastic momentum and energy transfer collision.
  • PIC particle-in-cell
  • MCC Monte Carlo collision
  • a XPDC1 code described in J. P. Verboncoeur, M. V. Alves, V. Vahedi, and C. K. Birdsall, J. Comput. Phys.
  • the simulation starts with an initially uniform plasma density of 1 ⁇ 10 6 cm ⁇ 3 in the reactor volume and the breakdown is defined when the plasma density is increased by 1,000 folds to 1 ⁇ 10 9 cm ⁇ 3 from the avalanche ionization with the energy transfer from the RF electric fields to the plasma.
  • the maximum breakdown delay time is chosen at 10 ⁇ s. As described above, rapid breakdown is important for pulsed RF plasma source operation.
  • the data points indicating 10 ⁇ s breakdown delay time are the case when no breakdown is achieved within the first 10 ⁇ s after the RF power is applied to the system.
  • the results from the computer simulation agree in general with the Paschen curve for argon shown in FIG. 8 .
  • FIGS. 10A-10D shows the time history of rf pulsed plasma generation at four different gas pressures of argon, 1.2 torr, 3.2 torr, 6.5 torr and 9.8 torr.
  • the rf voltage on the antenna is shown by trace 1, which is measured using high voltage probe with 1,000 ⁇ voltage division.
  • the rf current across the antenna is shown using trace 3, which is measured using Pearson current monitor with 1 kA/1V sensitivity.
  • the plasma light emission is shown using trace 2, which is measured by a fast photodiode with 50 ohm termination.
  • the reactor size is 48 mm diameter and an 8-turn antenna was constructed with the high voltage insulated 12 gauge wire, resulting in a vacuum inductance of 4 ⁇ H.
  • Rf switching power system operates with the switch voltages of +130 V and ⁇ 130V at the IGBT switches in a half bridge configuration.
  • the rf switching frequency was chosen at 800 kHz and no dynamic tuning was performed after breakdown.
  • the rf switching system Once the rf switching system is turned on, it takes approximately 50 ⁇ s to reach a peak rf voltage of 16 kV, a peak to peak value, at the antenna. It is note that this turn on time for the series circuit can be controlled and reduced by adjusting the maximum IGBT surge current. After the series resonance circuit reaches its peak voltage, the breakdown occurs in the reactor from the electron avalanche.
  • the delay time is only 7 ⁇ s, while it increases to 20 ⁇ s at 3.2 torr, 53 ⁇ s at 6.5 torr, 100 ⁇ s at 9.8 torr, showing the technical challenge related to the rapid high pressure gas breakdown using rf pulse power.
  • the discharge can be sustained by maintaining rf pulse power to the antenna.
  • the plasma loading changes the resonance circuit property after breakdown and the de-tuning of resonance is observed from the significant reduction in antenna voltage and current.
  • FIGS. 11A-11C show examples of a resonance circuit that may be used in the pulsed plasma reactor.
  • FIG. 11A shows an example of a serial resonance circuit 1100 that may be used to generate the pulsed RF power to the antenna.
  • the series resonance circuit 1100 may include RF power 1102 , a series capacitor Cs 1104 , an RF antenna Ls 1106 and a resistor Rs 1108 (for plasma loading and parasitic resistance) that are interconnected to each other in series as shown in FIG. 11A .
  • FIG. 11B shows an example of a parallel resonance circuit 1110 .
  • the parallel resonance circuit 1110 may include RF power 1112 , a parallel capacitor Cp 1114 , an RF antenna Ls 1116 and a resistor Rp 1118 (for plasma loading and parasitic resistance) in which the capacitor Cp, antenna and resistor are connected in parallel to the RF power.
  • FIG. 11C shows an example of a hybrid resonance circuit 1120 that has one RF power source and two antennas (R s, plasma and R p, plasma ).
  • the hybrid resonance circuit 1120 may include RF power 1122 , a parallel capacitor Cp 1124 in parallel with the RF power, parallel RF antenna Lp 1126 for plasma sustainment and resistor Rp 1128 in series with each other and in parallel with the RF power and the capacitor.
  • the hybrid resonance circuit 1120 may also include a series capacitor Cs 1130 and Ls and R plasma in series with each other and both in parallel with the RF power. In the hybrid resonance circuit, an initial breakdown occurs via the series resonance network using the first antenna and the plasma sustainment occurs via the parallel resonance network using the second antenna.

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WO2014151895A2 (fr) 2014-09-25

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