WO2017087233A1 - Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma - Google Patents
Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma Download PDFInfo
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- WO2017087233A1 WO2017087233A1 PCT/US2016/061134 US2016061134W WO2017087233A1 WO 2017087233 A1 WO2017087233 A1 WO 2017087233A1 US 2016061134 W US2016061134 W US 2016061134W WO 2017087233 A1 WO2017087233 A1 WO 2017087233A1
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- 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
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/44—Plasma torches using an arc using more than one torch
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- 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
- C23C16/44—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
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- 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
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
- H01J37/32568—Relative arrangement or disposition of electrodes; moving means
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- 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
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
- H01J37/32577—Electrical connecting means
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- 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
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
- H01J37/32596—Hollow cathodes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
- C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
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- 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
- H05H2245/00—Applications of plasma devices
- H05H2245/40—Surface treatments
Definitions
- Hollow cathode plasma sources are commonly used in the art for coating and surface treatment applications. These plasma sources comprise one or more hollow cathodes electrically connected to a source of power. Several different types of hollow cathodes may be used in these plasma sources, including point sources or linear hollow cathodes.
- Power sources used in hollow cathode plasma sources are typically configured to supply one of direct current, alternating current, or pulsed current (i.e., current having a square or rectangular waveform where the duty cycle is less than 100%) to the hollow cathodes.
- Bipolar power sources i.e. two phase power supplies
- embodiments of the present invention include, but are not limited to, improved operational life of a plasma source, improved deposition rate, and improved time of active plasma generation. Additionally, embodiments of the present invention result in increased disassociation energy in the precursor gas or gasses used, which leads to denser coatings when using plasma-enhanced chemical vapor deposition.
- a plasma source includes at least three hollow cathodes, including a first hollow cathode, a second hollow cathode, and a third hollow cathode. Each hollow cathode has a plasma exit region.
- the plasma source also includes a source of power capable of producing multiple output waves, including a first output wave, a second output wave, and a third output wave. The first output wave and the second output wave are out of phase, the second output wave and the third output wave are out of phase, and the first output wave and the third output wave are out of phase.
- Each hollow cathode is electrically connected to the source of power such that the first hollow cathode is electrically connected to the first output wave, the second hollow cathode is electrically connected to the second output wave, and the third hollow cathode is electrically connected to the third output wave. Electric current flows between the at least three hollow cathodes that are out of electrical phase.
- the plasma source is capable of generating a plasma between the hollow cathodes.
- a method of producing a plasma includes providing at least three hollow cathodes, including a first hollow cathode, a second hollow cathode, and a third hollow cathode. Each hollow cathode has a plasma exit region.
- the method also includes providing a source of power capable of producing multiple output waves, including a first output wave, a second output wave, and a third output wave. The first output wave and the second output wave are out of phase, the second output wave and the third output wave are out of phase, and the first output wave and the third output wave are out of phase.
- Each hollow cathode is electrically connected to the source of power such that the first hollow cathode is electrically connected to the first output wave, the second hollow cathode is electrically connected to the second output wave, and the third hollow cathode is electrically connected to the third output wave.
- Electric current flows between the at least three hollow cathodes that are out of electrical phase.
- a plasma is generated between the hollow cathodes.
- the method further includes providing a substrate and forming a coating on the substrate using plasma-enhanced chemical vapor deposition.
- the plasma generated by the plasma source includes active electron emission for at least substantially 80% of a period of the multiple output waves; in other embodiments, the plasma source includes active electron emission for at least substantially 90%, or at least substantially 100%, of a period of the multiple output waves.
- the at least three hollow cathodes are out of electrical phase by a phase angle different from 180°. In some embodiments, the at least three hollow cathodes are out of electrical phase by a phase angle of 120°. In some embodiments, each adjacent pair of the at least three hollow cathodes is out of electrical phase by the same phase angle as each other adjacent pair of the at least three hollow cathodes. In some embodiments, the at least three hollow cathodes are linear hollow cathodes. In some embodiments, the at least three hollow cathodes each include elongated cavities. In some embodiments, the plasma exit region for each of the at least three hollow cathodes includes a plurality of plasma exit orifices. In some embodiments, the plasma exit region for each of the at least three hollow cathodes includes a plasma exit slot.
- the at least three hollow cathodes are each electrically insulated such that only interior surfaces of the hollow cathode and the plasma exit region are electron- emitting and -accepting. In some embodiments, virtually all the generated plasma flows through the plasma exit region of each of the at least three hollow cathodes.
- the current flow is comprised of electrons derived from secondary electron emission. In some embodiments, the current flow is comprised of electrons derived from thermionic-emitted electrons.
- the at least three hollow cathodes are linearly arranged. In some embodiments, the at least three hollow cathodes are configured to direct each of the plasma exit regions to a common line. In some embodiments, a distance between each pair of the at least three hollow cathodes is the same distance. In some embodiments, the electrical current flowing between the at least three hollow cathodes that are out of electrical phase produces an electric potential difference (e.g., a peak-to-peak electric potential difference) between the at least three hollow cathodes. In some embodiments, the electric potential difference is at least 50V between any two of the at least three hollow cathodes.
- the electric potential difference is at least 200V between any two of the at least three hollow cathodes.
- the multiple output waves comprise square waves whereby the electric potential difference (e.g., peak-to-peak electric potential difference) is reduced relative to sinusoidal waves for the same overall power input.
- the source of power is in the form of AC electrical energy. In some embodiments, the source of power is in the form of pulsed electrical energy.
- the generated plasma is substantially uniform over its length in the substantial absence of magnetic-field driven closed circuit electron drift.
- the plasma is made substantially uniform over its length from about 0.1 m to about 1 m.
- the plasma is made substantially uniform over its length from about 1 m to about 4 m.
- the frequencies of each of the multiple output waves are equal and are in the range from about 1kHz to about 500MHz.
- the frequencies of each of the multiple output waves are equal and are in the range from about 1kHz to about lMHz.
- the frequencies of each of the multiple output waves are equal and are in the range from about 10kHz to about 200kHz.
- the frequencies of each of the multiple output waves are equal and are in the range from about 20kHz to about 100kHz.
- the electrons from an emitting surface are confined by the hollow cathode effect.
- the electrons from an emitting surface of each of the at least three hollow cathodes are not confined by magnetic fields.
- at least one of the multiple output waves produced by the source of power is configured to power a plurality of the at least three hollow cathodes.
- FIG. 1 illustrates a three-phase sinusoidal waveform according to exemplary
- FIG. 2 illustrates voltage and current plots between a pair of hollow cathodes in a bipolar hollow cathode plasma source.
- FIG. 3 illustrates a cross-sectional view of a conventional bipolar hollow cathode plasma source at different points in time.
- FIG. 4 illustrates regions of plasma off-time in a conventional bipolar hollow cathode plasma source.
- FIG. 5 illustrates voltage and current plots between pairs of hollow cathodes in a multiphase hollow cathode plasma source according to exemplary embodiments of the present invention.
- FIG. 6 illustrates a cross-sectional view of a multiphase hollow cathode plasma source at different points in time according to exemplary embodiments of the present invention.
- FIG. 7 illustrates a method according to exemplary embodiments of the present invention.
- FIG. 8 illustrates a coating formed by methods according to exemplary embodiments of the present invention.
- FIG. 9 illustrates a multiphase hollow cathode plasma source including hollow cathodes having a plasma exit region according to exemplary embodiments of the present invention.
- FIG. 10 illustrates a multiphase hollow cathode plasma source including hollow cathodes having a slot-like, restricted plasma exit region according to exemplary embodiments of the present invention.
- FIG. 11 illustrates a multiphase hollow cathode plasma source including six hollow cathodes and six phases according to exemplary embodiments of the present invention.
- FIG. 12 illustrates a multiphase hollow cathode plasma source including six hollow cathodes and three phases according to exemplary embodiments of the present invention.
- FIG. 13 illustrates a multiphase hollow cathode plasma source including three equidistant hollow cathodes according to exemplary embodiments of the present invention.
- FIG. 14A illustrates electron density of the plasma formation in and around the hollow cathodes in a bipolar hollow cathode plasma source.
- FIG. 14B illustrates electron density of the plasma formation in and around the hollow cathodes in a multiphase hollow cathode plasma source according to exemplary embodiments of the present invention.
- FIG. 15A illustrates ion density of the plasma formation in and around the hollow cathodes in a bipolar hollow cathode plasma source.
- FIG. 15B illustrates ion density of the plasma formation in and around the hollow cathodes in a multiphase hollow cathode plasma source according to exemplary embodiments of the present invention.
- FIG. 16A illustrates ion absorption along the wall of a hollow cathode cavity in both a bipolar hollow cathode plasma source and a multiphase hollow cathode plasma source according to exemplary embodiments of the present invention.
- FIG. 16B illustrates an index along a wall of a hollow cathode cavity as shown in the graph of FIG. 16A.
- a 1 sin 2nft + ⁇ ⁇ and A 2 sin 2nft + ⁇ 2 the phase difference between the two waves is defined as the difference of phase angles ⁇ 2 ⁇ ⁇ Note that this definition makes the phase difference depend on which wave is considered the first wave and which wave is considered the second wave. That is, if the order is changed, the sign of the phase difference will change.
- the wave that has a larger phase angle is said to be the leading wave, and the wave with a smaller phase angle is said to be the lagging wave.
- the leading wave is considered to be the first wave, and the phase difference is ⁇ , then considering the lagging wave as the first wave will lead to a phase difference of - ⁇ .
- this specification will not treat the sign of the phase difference with much significance, and will not consider the order of the waves as significant.
- ⁇ is expressed in radians in the formula above, this application will generally discuss (as a matter of convenience) phase angle or phase difference in degrees.
- phase angle ⁇ can be expressed as a number between -180° (or - ⁇ radians) and +180° (or + ⁇ radians).
- the phase difference is independent of amplitude A and is properly defined only between two waves that have the same frequency /.
- phase difference is a property between two waves. Two waves that have a phase difference with respect to each other may also be referred to as being offset, or phase-offset, from each other.
- phase difference can be defined for square waves, pulse waves, and other waveforms.
- Thermionic is taken to mean electron emission from a surface where emission is greatly accelerated by an elevated surface temperature. Thermionic temperatures are generally about 600° C or greater.
- FIG. 1 illustrates a three-phase sinusoidal waveform according to embodiments of the present invention.
- the three different sinusoidal waves (A, B, C) in waveform plot 100 are each out of phase by ⁇ 120° with respect to each other. Specifically, pairs (A, B) and (B, C) are each out of phase by +120° and pair (A, C) is out of phase by -120°.
- FIG. 2 illustrates voltage and current plots between a pair of hollow cathodes in a bipolar hollow cathode plasma source. Time points ti, t 2 , t 3 , t 4 , t 5 , and t 6 are indicated on voltage plot 202 and current plot 204 and denote various points of interest.
- FIG. 3 illustrates a cross-sectional view of a conventional bipolar hollow cathode plasma source at different points in time.
- Bipolar hollow cathode arrangement 300 includes hollow cathodes 302, 304 and a bipolar power source 310. When power is supplied by power source 310, a plasma 320 is generated between hollow cathodes 302, 304.
- Voltage plot 202 and current plot 204 indicate, respectively, the voltage and current between hollow cathodes 302, 304.
- Power source 310 provides an alternating current, and hollow cathodes 302, 304 alternately serve as cathode and anode.
- hollow cathodes 302, 304 are in antiphase (i.e., out of phase by 180°).
- Time points ti, t 2 , t 3 , , t 5 , and t 6 are indicated on voltage plot 202 and current plot 204 and denote various points of interest, which correspond to the different views of hollow cathode arrangement 300 shown in FIG. 3.
- the view corresponding to 3 ⁇ 4 shows the point where the alternating voltage input and resulting current both reach a zero value. At this point, plasma is not being actively generated.
- the view corresponding to t 2 shows the point where the potential difference between hollow cathodes 302, 304 reaches a maximum and plasma 320 is ignited.
- the view corresponding to t 3 shows the point of maximum current, where plasma 320 is fully established between the two hollow cathodes 302, 304.
- the view corresponding to t 4 shows the bipolar hollow cathode arrangement 300 at a point where current is equal to the current at t 2 , where a plasma 320 of diminished intensity (compared to, for example, the view corresponding to t 3 ) exists.
- the view corresponding to t 5 shows the next zero crossing, where plasma generation has once again ceased.
- the view corresponding to t 6 shows the continued cycle with plasma 320 again being generated, and where hollow cathode 302 and hollow cathode 304 have switched roles (cathode or anode) as compared to t 2 .
- the bipolar power supply initially drives a first electron emitting surface to a negative voltage, allowing plasma formation, while the second electron emitting surface is driven to a positive voltage in order to serve as an anode for the voltage application circuit. This then drives the first electron emitting surface to a positive voltage and reverses the roles of cathode and anode. As one of the electron emitting surfaces is driven negative, a discharge forms within the corresponding cavity. The other cathode then forms an anode, causing electron current to flow from the cathodic hollow cathode to the anodic hollow cathode.
- FIG. 4 illustrates regions of plasma off-time in a conventional bipolar hollow cathode plasma source. Specifically, FIG. 4 identifies the regions of time along the voltage plot 202 and current plot 204 where insufficient potential difference exists between the hollow cathodes for active plasma formation. In the non-plasma-generating regions 402, 404, and 406, the bipolar hollow cathode arrangement 300 ceases to generate plasma for approximately 25% of each wave period.
- an advantage of embodiments of the present invention is that by maintaining sufficient potential difference between hollow cathodes for plasma generation, embodiments of the present invention are capable of reducing or eliminating the period of time where there is no plasma being formed.
- FIG. 5 illustrates voltage and current plots between pairs of hollow cathodes in a multiphase hollow cathode plasma source according to embodiments of the present invention.
- Time points t 10 , tn, t 12 , ti 3 , ti 4 , and ti 5 are indicated on voltage plots 502, 506, 510 and current plots 504, 508, 512 and denote various points of interest.
- FIG. 6 illustrates a cross-sectional view of a multiphase hollow cathode plasma source at different points in time according to embodiments of the present invention.
- Multiphase hollow cathode arrangement 600 includes hollow cathodes 602, 604, 606 and a multiphase power source 610.
- a plasma 620 is generated between hollow cathodes 602, 604, 606.
- plasma 620 is generated between each pair of hollow cathodes 602, 604; 604, 606; and 602, 606.
- Voltage plots 502, 506, 510 and current plots 504, 508, 512 (as shown in FIG.
- FIG. 5 indicate, respectively, the voltage and current between hollow cathode pairs 602, 604 (labeled “A-B” in FIG. 5); 604, 606 (labeled “B-C” in FIG. 5); and 602, 606 (labeled “A-C” in FIG. 5) (hollow cathode pairs as shown in FIG. 6).
- Power source 610 provides an alternating current, and hollow cathodes 602, 604, 606 alternately serve as cathode and anode. In this arrangement, hollow cathode pairs 602, 604 and 604, 606 are out of phase by +120° and hollow cathode pair 602, 606 is out of phase by -120°.
- Time points 1 ⁇ 2, tn, t 12 , ti 3 , ti 4 , and t 15 are indicated on voltage plots 502, 506, 510 and current plots 504, 508, 512 and denote various points of interest, which correspond to the different views of hollow cathode
- the plasma generated between any pair of hollow cathodes will be affected, in part, by the distance between the pair of hollow cathodes.
- the distance between adjacent pairs of hollow cathodes e.g., hollow cathode pairs 602, 604 and 604, 606
- the distance between non-adjacent hollow cathodes e.g. hollow cathodes 602, 606
- the distance between hollow cathodes is process dependent. As distance increases, the voltage required for plasma formation increases.
- the distance between hollow cathodes is less than 500mm, or less than 400mm, or less than 200mm. In some embodiments, the distance between hollow cathodes is about 100mm.
- the plasma generated will also be affected, in part, by the voltage and current between the pair of hollow cathodes.
- the plasma density may not be uniform, in part due to the difference in voltage and current between different pairs of hollow cathodes.
- this non-uniformity will not be substantial, because the non-uniformities occur only during a short time span and the higher and lower plasma density areas switch many times before the substrate will have moved appreciably.
- the substrate moves beneath the plasma source and passes under each hollow cathode, the substrate will be equally treated.
- Multiphase power source 610 may include a single power source or multiple power sources. Specifically, multiphase power source 610 is capable of generating multiple output waves (e.g., waves A, B, and C in waveform plot 100), where the multiple output waves (and hence, the hollow cathodes that those waves power) are each phase-shifted from one another with respect to time. In some embodiments, adjacent hollow cathodes e.g. hollow cathode pairs 602, 604 and 604, 606) are each phase shifted by the same phase angle from each other (e.g. 120° for a three-phase power source, 90° for a four-phase power source, 72° for a five-phase
- each adjacent pair is out of phase by 60°, then the non- adjacent pair consisting of the first and third hollow cathodes in the line would be out of phase by 120° and the non-adjacent pair consisting of the first and the fourth hollow cathodes in the line would be out of phase by 180°.
- the view corresponding to 1 ⁇ 2 shows the point where current flow between hollow cathodes 602 and 604 is at a maximum, while current flow between hollow cathodes 604 and 606 is approximately half of the maximum value.
- current flow between hollow cathodes 602 and 604 becomes zero while current begins flowing between hollow cathodes 602 and 606.
- current flow between hollow cathodes 604 and 606 reaches its maximum value.
- the cycle continues in the view corresponding to t 12 , when current flow between hollow cathodes 602 and 606 reaches a maximum value and current again begins to flow between hollow cathodes 602 and 604, though in the opposite direction from that depicted in the view corresponding to t 10 .
- the view corresponding to t 13 depicts the opposite end of the cycle from the view corresponding to 1 ⁇ 2, where maximum current flows between hollow cathode 602 and 604, while approximately half of the maximum current flows between hollow cathodes 604 and 606.
- the current flows of the view corresponding to t 13 are in the opposite directions of those in the view corresponding to t 10 , with the hollow cathodes that previously served as cathodes now serving as anodes.
- the view corresponding to t 14 depicts the opposite current flow situation of what was described in the view corresponding to tn, and the view corresponding to t 15 shows the opposite current flow situation of what was described in the view corresponding to ti 2 .
- One characteristic of the multiphase hollow cathode arrangement 600 depicted in FIG. 6 is that at each point when current flow approaches zero between any two hollow cathodes, the voltage difference and current flow between other hollow cathode pairs is nonzero. With this arrangement, it is possible to create a plasma device which does not experience the previously mentioned plasma off-time of conventional plasma sources driven by bipolar power. That is, embodiments of the present invention effectively avoid the non-plasma generating regions 402, 404, 406 inherent in the prior art bipolar hollow cathode arrangement 300, as discussed above.
- improved plasma characteristics may be obtained, including a device which maintains current flow and the resultant plasma generation for the entirety of its operational time, thereby producing continuous plasma generation.
- a device which maintains current flow and the resultant plasma generation for the entirety of its operational time thereby producing continuous plasma generation.
- the plasma off-time may be from substantially 0% to around 20%, depending on design parameters.
- the plasma off-time may be substantially 20% (or alternatively, active plasma generation for 80% of a period of the waves); the plasma off-time may be substantially 10% (or alternatively, active plasma generation for 90% of a period of the waves); the plasma off-time may also be substantially 0% (or alternatively, active plasma generation for 100% of a period of the waves). Because there is a decay time associated with plasma— i.e., even after voltage drops to zero between a pair of hollow cathodes, plasma may still be present for a short time thereafter, even though it is not being actively generated— this application refers to active plasma generation as the time where there is active electron emission.
- hollow cathodes 602, 604, 606 may include elongated cavities.
- the hollow cathodes may include a plasma exit region, and the plasma exit region may include a single plasma exit orifice or a plurality of plasma exit orifices or an plasma exit slot or some combination of these plasma exit regions.
- the hollow cathodes are each electrically insulated such that only interior surfaces of the hollow cathode and the plasma exit region are electron-emitting and -accepting. In some embodiments, virtually all the continuously generated plasma flows through the plasma exit region of each of the hollow cathodes.
- current flow is comprised of secondary electron emission or thermionic-emitted electrons or some combination of these current flows.
- an electric potential difference causes current to flow between the hollow cathodes. In some embodiments, this potential difference is at least 50V or at least 200V between any two of the hollow cathodes.
- the multiphase power source that produces multiple output waves produces multiple output waves comprised of square waves, whereby the electric potential difference is reduced relative to sinusoidal waves.
- the multiphase power source is in the form of AC electrical energy or in the form of pulsed electrical energy or some combination of these forms of electrical energy.
- the plasma that is generated is substantially uniform over its length in the substantial absence of magnetic-field driven closed circuit electron drift.
- the plasma is made substantially uniform over its length from about 0.1m to about lm or from about lm to about 4m.
- the frequencies of each of the multiple output waves are equal and are in the range of from about 1kHz to about lMHz or from about 10kHz to about 200kHz or from about 20kHz to about 100kHz.
- the electrons emitted from an emitting surface are confined by the hollow cathode effect. In some embodiments, the electrons emitted from an emitting surface are not confined by magnetic fields.
- One factor influencing electron current is the temperature of hollow cathode cavity walls.
- electron emission is dominated by secondary electron emission.
- the impacting ion kinetic energy along with a negative voltage potential induces electrons to be emitted from wall surfaces.
- these "cold" hollow cathodes are run with cavity wall temperatures from 50°C to 500°C.
- cooling methods are applied.
- water cooling channels are built into the hollow cathode structure. Operating voltage for cold hollow cathode discharges is typically from 300 volts to 1000 volts.
- hollow cathodes may be run in thermionic mode.
- hollow cathode cavity wall temperatures usually range from 1000°C to 2000°C.
- Thermionic hollow cathodes may incorporate heaters around cavity walls to help raise temperature or, more simply, may rely on plasma energy transfer to heat cavity walls.
- hot cavities are thermally insulated to reduce conductive or radiative heat loss.
- Operating voltage for thermionic hollow cathode discharges is typically from 10 volts to 300 volts or more commonly from 10 volts tolOO volts.
- PECVD processes with sufficiently high deposition rates depend on plasmas that have undergone some method of densification.
- the hollow cathode effect is a specific method of electron densification and confinement making use of enclosed or partially enclosing electric fields. Gas phase free electrons are trapped by enclosing negative fields and exhibit oscillating movement between the surrounding or facing negatively biased walls.
- Electron oscillations result in long electron path lengths which in turn result in high probability of gas phase collisions. These collisions ionize the gas molecules creating additional electrons and positive ions. The positive ions are accelerated to and collide with the negatively biased hollow cathode walls. The positive ion-wall collisions result in further electron generation through secondary electron emission.
- Literature indicates hollow cathode plasmas are generally denser plasmas than those derived from magnetic confinement such as is used in closed drift electron confinement processes (e.g., magnetron sputtering).
- FIG. 6 Another advantage of the embodiment in FIG. 6, as well as other embodiments of the present invention, is that by including additional hollow cathodes a wider plasma is generated, which results in improved PECVD deposition rate.
- FIG. 7 illustrates a method according to embodiments of the present invention.
- the multiphase hollow cathode arrangement 600 (and other hollow cathode arrangements described and enabled by this disclosure) may be used to generate a continuous plasma.
- a method 700 of producing a plasma includes providing at least three hollow cathodes (step 702). Each hollow cathode has a plasma exit region. The method also includes providing a source of power capable of producing multiple output waves (step 704). Each hollow cathode is electrically connected to the source of power. The multiple output waves produced by the source of power are each phase-shifted from one another with respect to time to cause each hollow cathode to be out of electrical phase with the other hollow cathodes.
- the method further includes providing a substrate (step 706) and forming a coating on the substrate using plasma-enhanced chemical vapor deposition (step 708).
- the dashed boxes around steps 706 and 708 in FIG. 7 indicate that these steps are optional.
- Forming a coating on the substrate using plasma-enhanced chemical vapor deposition (PECVD) may include providing precursor gasses, process gasses, reactant gasses, or a combination of these, into the hollow cathode cavities or through manifolds adjacent to the hollow cathodes. Those of skill in the art will recognize that other steps applicable to PECVD may also be included.
- FIG. 8 illustrates a coating formed by methods according to embodiments of the present invention.
- Coating 802 is formed on top of substrate 804, creating a coating-substrate combination 800.
- substrate 804 is glass.
- substrate 804 may include plastic, metal, semiconductor material, or other suitable material for use in a PECVD process.
- coating 802 may be a single layer or film or may include a plurality of layers or films.
- coating 802 may be a low- emissivity coating and substrate 804 may be a glass window, such that coating-substrate combination 800 is suitable for architectural use.
- coating 802 may be another coating for a specific application, such as an anti-fog coating for use in refrigerator doors or a transparent conductive oxide coating for use in photovoltaic cells.
- FIG. 9 illustrates a multiphase hollow cathode plasma source including hollow cathodes having a plasma exit region according to embodiments of the present invention.
- Linear multiphase hollow cathode arrangement 600 (shown in FIG. 9) includes hollow cathodes 602, 604, 606 and multiphase power source 610.
- Each hollow cathode 602, 604, 606 is powered from the multiphase power source 610 by alternating or pulsed power such that each hollow cathode is phase offset from one another.
- Each hollow cathode 602, 604, 606 includes a hollow cathode cavity 904 and plasma outlet 902. In the embodiment shown in FIG.
- hollow cathodes 602, 604, 606 include two spaced-apart side regions and a top region, defining the cavity 904, and an open bottom region defining the plasma outlet 902.
- a reactant gas (or process gas or precursor gas or a combination of these gasses) may be present in hollow cathode cavity 904 of each hollow cathode 602, 604, 606.
- a reactant gas (or process gas or precursor gas or a combination of these gasses) may also be present in a reaction region 910.
- reaction region 910 may include a substrate, such as substrate 804, and in some embodiments, a coating may be formed on the substrate in reaction region 910.
- FIG. 10 illustrates a multiphase hollow cathode plasma source including hollow cathodes having a slot-like, restricted plasma exit region according to embodiments of the present invention.
- the embodiment of FIG. 10 is an alteration of the embodiment of FIG. 9, where plasma outlet 902 is replaced by a slot-like plasma outlet 1002.
- Each hollow cathode 602, 604, 606 includes a hollow cathode cavity 904 and plasma outlet 1002.
- hollow cathodes 602, 604, 606 include two spaced-apart side regions and a top region spaced apart from a bottom region, such that plasma outlet 1002 is defined by a slot in the bottom region.
- the plasma outlet 1002 allows for higher gas pressure inside of the hollow cathodes 602, 604, 606 when process gas is inside the hollow cathode cavity 904.
- a multiphase plasma source can include three hollow cathodes, each phase shifted from each other, i.e. three-phase, three-hollow-cathode embodiments.
- three-phase, three-hollow-cathode embodiments One of skill in the art will recognize that other
- an n-phase hollow cathode arrangement may include m hollow cathodes, where n is less than or equal to m. For a system with m hollow cathodes, there will be (TM) pairs of hollow cathodes (irrespective of order).
- Multiphase hollow cathode arrangement 1100 includes hollow cathodes 1102, 1104, 1106, 1108, 1110, 1112 connected to a multiphase power source 1110 configured to power each hollow cathode with a separate phase-offset wave 1120, 1122, 1124, 1126, 1128, 1130.
- adjacent hollow cathode pairs are each phase shifted from one another by the same phase angle ⁇ e.g. by 60°). Adjacent hollow cathode pairs, as shown in FIG.
- non-adjacent pairs 1102, 1108; 1104, 1110; and 1106, 1112 are each in antiphase with respect to each other. There are 10 non-adjacent pairs in the embodiment of FIG. 11
- Hollow cathode arrangement 1200 includes hollow cathodes 1102, 1104, 1106, 1108, 1110, 1112 connected to multiphase power source 1210.
- Multiphase power source 1210 produces three phase-offset waves 1220, 1222, 1224.
- wave 1220 powers hollow cathodes 1102, 1108
- wave 1222 powers hollow cathodes 1104, 1110
- wave 1224 powers hollow cathodes 1106, 1112.
- each wave 1220, 1222, 1224 is offset by the same phase angle (e.g., 120°).
- non- adjacent pairs 1102, 1108; 1104, 1110; and 1106, 1112 are each in phase with respect to each other, since there is a single wave 1220, 1222, 1224 powering each pair.
- the phase difference of each pair of hollow cathodes in FIG. 12, where adjacent pairs are phase shifted by 120°, is shown in the table below.
- FIG. 13 illustrates a multiphase hollow cathode plasma source including three equidistant hollow cathodes.
- Arrangement 1300 includes three hollow cathodes 602, 604, 606 with plasma outlets 1002 each directed to a common line (note that because FIG. 13 is a cross-sectional view, it appears that each of the outlets is directed to a common point).
- the embodiment shown in FIG. 13 can also include additional hollow cathodes, in various geometric configurations, such that the plasma outlets of each of the hollow cathodes (or some subset of the hollow cathodes) are directed to a common line (or a set of common lines).
- the plasma outlets of each of the hollow cathodes or some subset of the hollow cathodes
- the distance between each of the hollow cathodes is equal.
- FIG. 13 shows a distance between hollow cathode pair 602, 604 being substantially the same as a distance between each of hollow cathode pair 602, 606 and hollow cathode pair 604, 606.
- a distance between hollow cathode pairs may be measured from the center of a hollow cathode, from the plasma outlet of a hollow cathode, or from some other point in, on, or near a hollow cathode.
- the embodiment of FIG. 13, or similar embodiments may be used, for example, to coat two-dimensional substrates such as wire or optical fiber coating.
- two-dimensional substrates may be coated uniformly by passing these elongated substrates through the line of common direction.
- FIGs. 14A and 14B illustrate electron density of the plasma formation in and around the hollow cathodes in both a bipolar hollow cathode plasma source and a multiphase hollow cathode plasma source according to embodiments of the present invention. As the figures illustrate, for comparable levels of electron density outside of the hollow cathode cavities, in the reaction region— as between the bipolar (FIG. 14A) and multiphase plasma sources (FIG.
- the electron density inside the hollow cathode cavities is significantly greater for the bipolar plasma source relative to the multiphase plasma source.
- FIGs. 15 A and 15B illustrate ion density of the plasma formation in and around the hollow cathodes in both a bipolar hollow cathode plasma source and a multiphase hollow cathode plasma source according to embodiments of the present invention.
- FIGs. 15A and 15B illustrate, for comparable levels of ion density outside of the hollow cathode cavities, in the reaction region— as between the bipolar (FIG. 15A) and multiphase plasma sources (FIG.
- the ion density inside the hollow cathode cavities is significantly greater for the bipolar plasma source relative to the multiphase plasma source.
- FIG. 16A illustrates ion absorption along the wall of a hollow cathode cavity in both a bipolar hollow cathode plasma source and a multiphase hollow cathode plasma source according to embodiments of the present invention.
- the ion absorption along the wall of a hollow cathode cavity is significantly greater for the bipolar plasma source relative to the multiphase plasma source.
- the figure also illustrates that the ion absorption is at a minimum at the corners of the hollow cathode cavity (index values 8, 63, 89, 144).
- the absorption rate is approximately 88% less for the multiphase arrangement compared to the bipolar arrangement (this value will vary depending on, for example, power levels used during operation of the plasma source).
- FIG. 16B illustrates an index along a wall of a hollow cathode cavity as shown in the graph of FIG. 16A. Specifically, the values shown along the wall of the hollow cathode cavity 600 in FIG. 16B correspond to values on the x axis of FIG. 16A ("Index along cavity wall").
- FIGs. 14-16B were generated as the results of a simulation of both a bipolar hollow cathode arrangement (similar to arrangement 300) and a multiphase hollow cathode arrangement (similar to arrangement 600).
- the bipolar arrangement comprises two linear hollow cathodes 1402a, 1404a (in antiphase) located in a vacuum chamber 1430.
- Precursor gas flows through the precursor manifold 1410.
- Plasma is formed in reaction region 1420.
- the multiphase arrangement comprises three linear hollow cathodes 1402b, 1404b, 1406b (each phase offset from each other by 120°), located in a vacuum chamber 1430.
- Precursor gas flows through the precursor manifolds 1410. Plasma is formed in reaction region 1420.
- Argon gas was used as the process gas in the hollow cathode cavities.
- other process gasses can also be used, including without limitation Oxygen, Nitrogen, Argon, Helium, Krypton, Neon, Xenon, Hydrogen, Fluorine, Chlorine, and mixtures thereof.
- Reactive gasses include H2, H20, H202, N2, N02, N20, NH3, CH4, CO, C02, SH2, other sulfur based gases, halogens, bromines, phosphorous based gases, or mixtures thereof.
- the level of wear (as indicated by plasma and ion density and ion absorption) inside the hollow cathode cavities is significantly less for a three-phase arrangement according to embodiments of the present invention. In embodiments of the present invention, this may lead to a longer operational life of the hollow cathodes relative to a bipolar plasma source. Operational life will depend on what process the plasma source is being used for, among other factors.
- the expected operational run-life improvement for a three-phase three-hollow-cathode arrangement is approximately 60% greater as compared to the conventional bipolar arrangement. In some embodiments, this may equate to approximately 200 hours of additional life, for example, an operational life of 500 hours over a baseline of 300 hours. This advantage is attributable to the multiphase power arrangement, and is not a result of merely adding additional hollow cathodes.
- the inventors have found that the amount of sputtering of the hollow cathode cavity surfaces is related to the absorption of reactive ions on the hollow cathode cavity surfaces as determined by numerical simulation.
- the simulation software that was used for simulating gas flows and gas discharges is a program called PIC-MC that has been developed by the Fraunhofer-Institute for Surface Engineering and Thin Films 1ST, Braunschweig, Germany.
- the software combines the simulation of gas flows, magnetic fields, and plasma.
- For the gas flow simulation it uses the Direct Simulation Monte Carlo (DSMC), for the magnetic field simulation it uses the Boundary Element Method (BEM) and for the plasma simulation it uses the Particle in Cell - Monte Carlo method (PIC-MC).
- DSMC Direct Simulation Monte Carlo
- BEM Boundary Element Method
- PIC-MC Particle in Cell - Monte Carlo method
- the simulations were made on a pseudo 2D model which is a transversal 1.016 mm thick slice of the hollow cathode plasma source.
- Pseudo-2D means that the slice has a small thickness and a periodic condition is applied on each plane in the transversal direction.
- the simulation yields data regarding number and velocity of the different gas phase species (atoms, ions, molecules and electrons) throughout the space they occupy. From this data certain values can be calculated, such as densities and fluxes, where a flux is the rate of movement of gas phase species across a unit area (unit: mol-m -2 -s -1 ).
- Another useful calculation is the flux that is absorbed on a certain surface. Given a certain sticking coefficient of the cathode cavity material, the ion absorption on its surface can be calculated from the ion flux directed at it.
- the inventors found that the formation of debris and thus the cavity surface sputtering observed on real plasma sources was related to the level of ionized plasma species absorbed by the hollow cathodes' cavity surfaces according to the simulation model.
- Argon absorption is an easily derived property from the plasma simulation that was used. Further, argon absorption is an effective gauge of the ion energy and particle flux that is incident to the electrode surface. Those skilled in the art will understand that the ion energy and particle flux are the major driving factors behind the physical process of sputtering or electrode erosion. Debris generation occurs when the balance of sputter rate versus deposition of sputtered material from nearby surfaces is biased toward a net deposition. This effect can be observed in FIGs. 16A and 16B, which indicate reduced sputtering and net deposition in the corners of the rectangular electrodes, where ion absorption was found (through simulation) to be lowest. [0082] Accordingly, although the actual sputtering value is not measured by the simulation, the inventors have used the argon absorption values as an indicator of the sputtering or electrode erosion from the multiphase embodiment described here.
- LOW levels of ionized plasma species absorbed by the hollow cathodes' cavity surfaces mean that the level of cavity sputtering is low and debris formation is low.
- the bipolar plasma source resulted in increased sputtering and wear of the majority of the electrode surface, where both the bipolar and multiphase plasma sources had equal plasma energy in the process chamber.
- the additional sputtered material from the bipolar plasma source can also result in increased debris when it is deposited on surfaces which are not undergoing intense sputtering, such as the corners of the electrode cavities and surfaces external to the plasma source (which are at floating or ground potential and not subject to sputtering). The nature and amount of this debris will be heavily dependent upon the combination of electrode surface material and plasma gas.
- the electron density has a major influence on surface treatment or coating efficiency, with high electron densities leading to high surface treatment or coating efficiencies.
- the electron density was determined in the vacuum chamber on a line set at a distance of 2.54 mm from the chamber structure that supports the plasma source and averaged.
- the inventors surprisingly found that the intensity of electron density in a reaction region outside the hollow cathodes was similar for both a three-phase, three-hollow-cathode arrangement and a two-phase, two-hollow-cathode arrangement. This is surprising because, for example, the three-phase, three-hollow-cathode arrangement produces plasma concentrated on a larger area and experiences less wear inside the hollow cathodes than the two-phase, two-hollow cathode arrangement.
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JP2018544766A JP2018535532A (en) | 2015-11-16 | 2016-11-09 | Plasma device driven by polyphase alternating current or pulsed current and method for generating plasma |
EA201891175A EA201891175A1 (en) | 2015-11-16 | 2016-11-09 | PLASMA DEVICE, MADE INTO ACTION BY MULTIPHASE VARIABLE OR PULSED ELECTRIC CURRENT, AND A METHOD FOR GETTING A PLASMA |
MX2018006095A MX2018006095A (en) | 2015-11-16 | 2016-11-09 | Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma. |
KR1020187017067A KR20180095530A (en) | 2015-11-16 | 2016-11-09 | Plasma device driven by multi-phase ac or pulse current and plasma generation method |
CN201680078860.4A CN108463575A (en) | 2015-11-16 | 2016-11-09 | The plasma device driven by multiphase alternating or pulse current and the method for generating plasma |
BR112018009864A BR112018009864A8 (en) | 2015-11-16 | 2016-11-09 | plasma device driven by multiple alternating phase or pulsed electric current and method of producing a plasma |
SG11201804129YA SG11201804129YA (en) | 2015-11-16 | 2016-11-09 | Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma |
EP16866871.3A EP3377673A4 (en) | 2015-11-16 | 2016-11-09 | Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma |
PH12018501049A PH12018501049A1 (en) | 2015-11-16 | 2018-05-16 | Plasma device driven by multiple-phase alternating or pulsed electrical current and method of producing a plasma |
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US14/942,737 | 2015-11-16 | ||
US14/942,673 US9721764B2 (en) | 2015-11-16 | 2015-11-16 | Method of producing plasma by multiple-phase alternating or pulsed electrical current |
US14/942,673 | 2015-11-16 |
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JP (1) | JP2018535532A (en) |
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Cited By (3)
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RU2680318C1 (en) * | 2018-08-31 | 2019-02-19 | Общество С Ограниченной Ответственностью "Трипл-Сп" | Ac high-voltage electric arc plasma torch cooling system and the ac high-voltage electric arc plasma torch with cooling system (embodiments) |
RU2775363C1 (en) * | 2021-10-06 | 2022-06-30 | Общество с ограниченной ответственностью «Трипл-СП» | Ac electric arc plasma torch |
CN115355504A (en) * | 2022-08-15 | 2022-11-18 | 浙江大学台州研究院 | Multiphase alternating current plasma torch and solid waste treatment device |
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KR20180095530A (en) | 2018-08-27 |
SG11201804129YA (en) | 2018-06-28 |
BR112018009864A8 (en) | 2019-02-26 |
PH12018501049A1 (en) | 2019-01-28 |
JP2018535532A (en) | 2018-11-29 |
CN108463575A (en) | 2018-08-28 |
EP3377673A4 (en) | 2019-07-31 |
BR112018009864A2 (en) | 2018-11-13 |
EP3377673A1 (en) | 2018-09-26 |
EA201891175A1 (en) | 2018-12-28 |
MX2018006095A (en) | 2018-11-12 |
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