CN108463575A - The plasma device driven by multiphase alternating or pulse current and the method for generating plasma - Google Patents

The plasma device driven by multiphase alternating or pulse current and the method for generating plasma Download PDF

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Publication number
CN108463575A
CN108463575A CN201680078860.4A CN201680078860A CN108463575A CN 108463575 A CN108463575 A CN 108463575A CN 201680078860 A CN201680078860 A CN 201680078860A CN 108463575 A CN108463575 A CN 108463575A
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Prior art keywords
hollow cathode
plasma
output wave
hollow
phase
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CN201680078860.4A
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Chinese (zh)
Inventor
J·钱伯斯
P·马诗威茨
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AGC Glass Europe SA
AGC Inc
AGC Flat Glass North America Inc
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AGC Glass Europe SA
Asahi Glass Co Ltd
AGC Flat Glass North America Inc
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Priority claimed from US14/942,673 external-priority patent/US9721764B2/en
Priority claimed from US14/942,737 external-priority patent/US9721765B2/en
Application filed by AGC Glass Europe SA, Asahi Glass Co Ltd, AGC Flat Glass North America Inc filed Critical AGC Glass Europe SA
Publication of CN108463575A publication Critical patent/CN108463575A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Plasma Technology (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

A kind of plasma source and the method for generating plasma are provided.The plasma source includes at least three hollow cathodes, and at least three hollow cathode includes the first hollow cathode, the second hollow cathode and third hollow cathode, and each hollow cathode has plasma exit region.The plasma source includes the power supply that can generate multiple output waves, the multiple output wave includes the first output wave, the second output wave and third output wave, wherein described first output wave and the second output wave out-phase, second output wave and the third output wave out-phase, and first output wave and the third output wave out-phase.Each hollow cathode is electrically connected to the power supply, so that first hollow cathode is electrically connected to first output wave, second hollow cathode is electrically connected to second output wave, and the third hollow cathode is electrically connected to the third output wave.

Description

The plasma device and generation plasma driven by multiphase alternating or pulse current Method
Background technology
Hollow-cathode plasma source is commonly used in coating and surface-treatment applications in the art.These plasma sources One or more hollow cathodes including being electrically connected to power supply.It can be used in these plasma sources several different types of Hollow cathode, including point source or linear hollow cathode.
The power supply used in hollow-cathode plasma source is typically configured to hollow cathode supply DC current, hands over One in time-dependent current or pulse current (that is, electric current of the square waveform or square waveform with wherein duty ratio less than 100%) It is a.At present alternation or pulse current are provided to hollow-cathode plasma source using bipolar power supply (i.e. two-phase is powered).
Cause the mainly life in single region using DC current during the operation of linear hollow-cathode plasma source At plasma, rather than plasma is generated in the whole length of linear hollow cathode.Although using the one of DC current The plasma source of a little types can effectively utilize magnet to generate uniform plasma, but this cannot utilize linear sky The heart-yin is extremely realized.However, the uniformity of height (can not be by using DC current in linear hollow-cathode plasma source To realize) for many applications (such as using plasma enhanced chemical vapor deposition coating glass) it is required.
The present inventor previously had found, in hollow-cathode plasma source, used two-phase (bipolar) alternation or pulse power Uniform linear plasma may be implemented.However, being lacked with some using two-phase electric power in hollow-cathode plasma source Point.For example, due to the alternation of electric power, in certain part at runtime, cannot be actively generated by plasma source etc. from Daughter (is not present active electronic to emit).For typically applying, wherein this time of plasma cannot be actively generated About the 25% of power-up period.Another disadvantage is that causing to exist on plasma source due to the use of two-phase power supply notable Abrasion, it reduce the service lives of plasma source.
Therefore, this field needs to overcome the plasma source of these and other disadvantage of known plasma source.
Invention content
Below commonly assigned application describe such as the various hollow cathodes in embodiment for use in the present invention from Daughter source, the commonly assigned application are：The U. S. application of number 12/535,447 is now the U.S. of number 8,652,586 Patent；The U. S. application of number 14/148,612；The U. S. application of number 14/148,606；The U.S. Shen of number 14/486,726 Please；The U. S. application of number 14/486,779；PCT/US14/068919；PCT/US14/68858.Each of these applications All integrally it is incorporated herein.
The advantages of the embodiment of the present invention includes but not limited to the service life for improving plasma source, improves deposition rate And improve the time that active plasma generates.In addition, the embodiment of the present invention makes used precursor gas or more Dissipation energy in kind gas increases, this makes it possible to realize when using plasma enhanced chemical vapor deposition finer and close Coating.
According to the first aspect of the invention, a kind of plasma source is provided.The plasma source includes at least three Hollow cathode, at least three hollow cathode include the first hollow cathode, the second hollow cathode and third hollow cathode.Each Hollow cathode has plasma exit region.The plasma source further includes power supply, and the power supply can generate multiple defeated Go out wave, the multiple output wave includes the first output wave, the second output wave and third output wave.First output wave and described Second output wave is out-phase, and second output wave and the third output wave are out-phase, and first output wave It is out-phase with the third output wave.Each hollow cathode is electrically connected to the power supply, so that first hollow cathode It is electrically connected to first output wave, second hollow cathode is electrically connected to second output wave, and the third is empty The heart-yin pole is electrically connected to the third output wave.Electric current flows between at least three hollow cathode of different electric phase.Institute Plasma can be generated between the hollow cathode by stating plasma source.
According to the second aspect of the invention, a kind of method generating plasma is provided.The method includes being provided to Few three hollow cathodes, at least three hollow cathode include the first hollow cathode, the second hollow cathode and the hollow the moon of third Pole.Each hollow cathode has plasma exit region.The method further includes providing power supply, and the power supply can generate more A output wave, the multiple output wave include the first output wave, the second output wave and third output wave.First output wave and Second output wave is out-phase, and second output wave and the third output wave are out-phase, and described first defeated It is out-phase to go out wave and the third output wave.Each hollow cathode is electrically connected to the power supply, so that described first is hollow Cathode is electrically connected to first output wave, and second hollow cathode is electrically connected to second output wave, and described Three hollow cathodes are electrically connected to the third output wave.Electric current flows between at least three hollow cathode of different electric phase It is dynamic.Plasma generates between the hollow cathode.In some embodiments, the method further includes providing substrate simultaneously And coating is formed on the substrate using plasma enhanced chemical vapor deposition.
(any aspect according to the present invention) in some embodiments, the plasma generated by the plasma source exists Include that active electronic emits at least basic the 80% of the period of the multiple output wave；In other embodiments, it is described it is equal from Daughter source includes that active electronic is sent out at least basic the 90% of the period of the multiple output wave or at least basic 100% It penetrates.
In some embodiments, at least three hollow cathode is with the different electric phase in the phase angle different from 180 °.One In a little embodiments, at least three hollow cathode is with the different electric phase in 120 ° of phase angle.In some embodiments, it is described at least Each phase adjacency pair hollow cathode in three hollow cathodes and each other phase adjacency pairs at least three hollow cathode are empty The heart-yin pole is with the different electric phase in identical phase angle.In some embodiments, at least three hollow cathode is linear hollow the moon Pole.In some embodiments, at least three hollow cathode includes each elongated cavity.In some embodiments, described The plasma exit region of each hollow cathode at least three hollow cathodes includes multiple plasma exit holes. In some embodiments, the plasma exit region of each hollow cathode at least three hollow cathode include it is equal from Daughter exit slot.
In some embodiments, at least three hollow cathode is respectively electrically insulated, so that the only hollow cathode Inner surface and the plasma exit region be that electron emission and electronics receive.In some embodiments, Ji Husuo There is the plasma exit region for each hollow cathode that the plasma of generation flows through at least three hollow cathode. In some embodiments, electric current flowing includes the electronics from secondary.In some embodiments, electric current flowing includes Electronics from thermionic emission electronics.
In some embodiments, at least three hollow cathode is linearly arranged.In some embodiments, it is described extremely Few three hollow cathodes are configured to each in the plasma exit region being directed toward common wire.In some embodiments In, at least three hollow cathode is all identical distance per the distance between a pair of of hollow cathode.In some implementations In example, the electric current flowed between at least three hollow cathode of different electric phase is between at least three hollow cathode Generate potential difference (for example, peak-peak potential difference).In some embodiments, any two at least three hollow cathode Potential difference between hollow cathode is at least 50V.In some embodiments, any two at least three hollow cathode Potential difference between hollow cathode is at least 200V.In some embodiments, the multiple output wave includes square wave, thus for Identical totality electric power input, potential difference (for example, peak-peak potential difference) are reduced relative to sine wave.In some embodiments, The power supply is in the form of AC electric energy.In some embodiments, the power supply is in the form of pulse electric energy.
In some embodiments, it in the case where the closed circuit electronics for being substantially not present field drives drifts about, is generated Plasma be substantially homogeneous over its length.In some embodiments, plasma over its length from about 0.1m to About 1m is substantially homogeneous.In some embodiments, plasma is over its length substantially homogeneous from about 1m to about 4m. In some embodiments, the frequency of each in the multiple output wave is equal and between from about 1kHz to about 500MHz In the range of.In some embodiments, the frequency of each in the multiple output wave is equal and between from about In the range of 1kHz to about 1MHz.In some embodiments, the frequency of each in the multiple output wave be it is equal and And between in the range of from about 10kHz to about 200kHz.In some embodiments, the frequency of each in the multiple output wave Rate is equal and between in the range of from about 20kHz to about 100kHz.In some embodiments, the electricity from emitting surface Son is constrained by hollow cathode effect.In some embodiments, each at least three hollow cathode is hollow The electronics of the emitting surface of cathode is not constrained by magnetic field.In some embodiments, the multiple output waves generated by the power supply At least one of be configured at least three hollow cathode multiple hollow cathodes power supply.
Description of the drawings
The attached drawing for being incorporated herein and being formed the part of this specification illustrates the various embodiments of the disclosure, and It is further used for explaining the principle of the disclosure together with this description and those skilled in the relevant art is enable to manufacture and make With embodiment disclosed herein.In the accompanying drawings, similar reference numeral indicates identical or functionally similar element.
Fig. 1 illustrates the three phase sine waveform of exemplary embodiment according to the present invention.
Fig. 2 illustrates the voltage and current curve between a pair of of hollow cathode in bipolar hollow-cathode plasma source.
Fig. 3 illustrates the viewgraph of cross-section for the bipolar hollow-cathode plasma source of tradition located in different time points.
Fig. 4 illustrates the region of tradition bipolar hollow-cathode plasma source plasma turn-off time.
Fig. 5 illustrates pairs of hollow in the multiphase hollow-cathode plasma source of exemplary embodiment according to the present invention Voltage and current curve between cathode.
Fig. 6 illustrates the multiphase hollow cathode discharge plasma of exemplary embodiment according to the present invention located in different time points The viewgraph of cross-section in body source.
The method that Fig. 7 illustrates exemplary embodiment according to the present invention.
Fig. 8 illustrates the coating formed by the method for exemplary embodiment according to the present invention.
What Fig. 9 illustrated exemplary embodiment according to the present invention includes the hollow cathode with plasma exit region Multiphase hollow-cathode plasma source.
What Figure 10 illustrated exemplary embodiment according to the present invention includes going out with slit-like, restricted plasma The multiphase hollow-cathode plasma source of the hollow cathode in mouth region domain.
Figure 11 illustrates the multiphase for including six hollow cathodes and six phases of exemplary embodiment according to the present invention Hollow-cathode plasma source.
Figure 12 illustrates the multiphase for including six hollow cathodes and three phases of exemplary embodiment according to the present invention Hollow-cathode plasma source.
Figure 13 illustrates hollow the moon of multiphase for including three equidistant hollow cathodes of exemplary embodiment according to the present invention Pole plasma source.
Figure 14 A illustrate in the hollow cathode in bipolar hollow-cathode plasma source and its around the plasma that is formed The electron density of body.
Figure 14 B illustrate hollow in the multiphase hollow-cathode plasma source of exemplary embodiment according to the present invention In cathode and its surrounding formed plasma electron density.
Figure 15 A illustrate in the hollow cathode in bipolar hollow-cathode plasma source and its around the plasma that is formed The ion concentration of body.
Figure 15 B illustrate hollow in the multiphase hollow-cathode plasma source of exemplary embodiment according to the present invention In cathode and its surrounding formed plasma ion concentration.
Figure 16 A illustrate exemplary embodiment according to the present invention bipolar hollow-cathode plasma source and multiphase it is hollow Along the Ions Absorption of hollow cathode cavity wall in the two of cathode plasma source.
Figure 16 B are illustrated as shown in the curve graph of Figure 16 A along the index of hollow cathode cavity wall.
Specific implementation mode
Consider sine waveWherein A is amplitude, and f is frequency, andIt is phase angle.Phase angleRefer to The oscillating position being scheduled at time t=0.About two sine wavesWithTwo waves Between phase difference be defined as the difference at phase angleIt is worth noting that, this is defined so that phase difference depends on Which wave is considered as first wave and which wave is considered as the second wave.That is, if change sequence, phase difference Symbol will change.Wave with larger phase angle is referred to as leading wave, and the wave with smaller phase angle is referred to as retarded wave.Such as Fruit leading wave is considered as first wave, and phase difference isSo consider that retarded wave will cause the phase difference to be as first waveIn general, this specification will not regard the symbol of phase difference as the sequence for being very important, and will not thinking wave It is important.Although being indicated with radian in above formulaBut the application (for convenience) will generally be come as unit of degree Phase angle or phase difference are discussed.Because sine wave has the cycle or the period of lucky 360 ° (or 2 π radians), it is possible to by phase Parallactic angleThe number being expressed as between -180 ° (or-π radians) and+180 ° (or+π radians).Phase difference is unrelated with amplitude A, and And it is only properly defined between two waves with identical frequency f.
At two wave phase angles having the sameIn the case of, it is known as same phase there is no phase difference and the wave (same phase relative to each other).Do not have identical phase angle in two wavesIn the case of, the wave is known as out-phase (phase For being mutually out of phase).In the case where phase difference is 180 °, the two waves are known as reverse phase (reverse phase relative to each other) 's.Phase difference is the attribute between two waves.Having dephased two waves relative to each other can also be known as each other partially It is moving or phase shifted from one another.Those of ordinary skill in the art will also be appreciated that can for square wave, impulse wave and other waveforms To define phase difference.
When two hollow cathodes are powered by two waves of out-phase, it is (opposite will to be known as those hollow cathodes by the application In each other) with given phase angle phase offset, what the given phase angle was defined as powering to the hollow cathode The phase difference of two waves.Therefore, the wave or the hollow cathode (interchangeably) can be known as phase shifted from one another.It is standby Selection of land, if two same phases of wave, two hollow cathodes will (interchangeably) be known as same phase.
" thermionic " refers to being greatly speeded up from surface emitting electronics because of raised surface temperature wherein emitting. Thermionic temperature is typically about 600 DEG C or bigger.
" secondary electron " or " secondary electron electric current " refers respectively to due to the particle bombardment surface of solids from the surface of solids Launching electronics and the therefore electric current of generation.Electron emitting surface according to an embodiment of the invention can generate plasma Body, and the surface is further hit by electronics or ion.Electronics or ionic bombardment electron emitting surface cause from the electronics Emitting surface emits secondary electron.Secondary is important, because secondary electron flowing helps to create densification Plasma.
Fig. 1 illustrates three phase sine waveform according to an embodiment of the invention.Three in wavy curve 100 it is different just String wave (A, B, C) is each relative to each other with ± 120 ° of out-phase.Specifically, (A, B) pair and (B, C) is to each different with+120 ° Phase, and (A, C) to -120 ° of out-phase.
Fig. 2 illustrates the song of the voltage and current between a pair of of hollow cathode in bipolar hollow-cathode plasma source Line.Time point t1、t2、t3、t4、t5And t6It is instructed on voltage curve 202 and current curve 204 and indicates various concerns Point.
Fig. 3 illustrates the viewgraph of cross-section for the bipolar hollow-cathode plasma source of tradition located in different time points.It is bipolar Hollow cathode arrangement 300 includes hollow cathode 302,304 and bipolar power supply 310.When being powered by power supply 310, in hollow cathode 302, plasma 320 is generated between 304.Voltage curve 202 and current curve 204 indicate respectively hollow cathode 302,304 it Between voltage and current.Power supply 310 provides alternating current, and hollow cathode 302,304 acts alternately as cathode and anode. In the arrangement, hollow cathode 302,304 reverse phases (that is, with 180 ° of out-phase).Time point t1、t2、t3、t4、t5And t6In voltage curve 202 and current curve 204 on be instructed to and indicate various focus, the time point corresponds to hollow the moon shown in Fig. 3 The different views of pole arrangement 300.
Corresponding to t1View show the input of alternating voltage at which and the current both generated reach zero point (when Between point).At this point, plasma will not be actively generated.Corresponding to t2View show hollow cathode 302,304 at which Between potential difference reach maximum value and cause the point of plasma 320.Corresponding to t3View show maximum current point, At which plasma 320 has been completely set up between two hollow cathodes 302,304.Corresponding to t4View show at which Electric current is equal to t2The electric current at place and there are remitted its fury (with for example corresponding to t3View compare) plasma 320 point The bipolar hollow cathode arrangement 300 at place.Corresponding to t5View show next zero crossing, plasma generates again at which Secondary stopping.Corresponding to t6View show that again in which generates plasma 320 and and t2Compared to hollow cathode 302 and hollow Cathode 304 changing role (cathode or anode) successive (continuation) cycle.
Briefly describe the role transforming between cathode and anode.Bipolar power supply (power supply) is initially by the first electron emitting surface Driving is to negative voltage, and to allow plasma to be formed, while the second electron emitting surface is driven to positive voltage to serve as The anode of voltage applying circuit.And then the first electron emitting surface is driven to positive voltage and reverses the angle of cathode and anode Color.When one in electron emitting surface is driven to negative, electric discharge is formed in corresponding cavity.Another (hollow) cathode Anode is then formed, to cause electronic current to flow to from the hollow cathode of cathode the hollow cathode of anode.
Fig. 4 illustrates the region of the plasma turn-off time in the bipolar hollow-cathode plasma source of tradition.It is specific and Speech, Fig. 4 identify the time zone along voltage curve 202 and current curve 204, at the time zone, are present in sky Potential difference between the heart-yin pole is formed insufficient for active plasma.In non-plasma formation zone 402,404 and 406 In, bipolar hollow cathode arrangement 300 stops generating plasma on about the 25% of each wave period.On the contrary, the present invention The advantages of embodiment, is, of the invention by maintaining the potential difference for being sufficient to make plasma to generate between hollow cathode Embodiment can reduce or eliminate the period for not forming plasma.
Fig. 5 illustrate the pairs of hollow cathode in multiphase hollow-cathode plasma source according to an embodiment of the invention it Between voltage and current curve.Time point t10、t11、t12、t13、t14And t15It is bent in voltage curve 502,506,510 and electric current It is instructed on line 504,508,512 and indicates various focus.
Fig. 6 illustrates the multiphase hollow-cathode plasma source according to an embodiment of the invention located in different time points Viewgraph of cross-section.Multiphase hollow cathode arrangement 600 includes hollow cathode 602,604,606 and polyphase source 610.When by power supply When 610 power supply, plasma 620 is generated between hollow cathode 602,604,606.Specifically, plasma 620 is each pair of Hollow cathode 602,604；604、606；It is generated between 602,606.Voltage curve 502,506,510 and current curve 504, 508,512 (as shown in Figure 5) indicate respectively hollow cathode pair 602,604 (being labeled as " A-B " in Figure 5)；604,606 (in Fig. 5 Middle label is B-C ")；Voltage between 602,606 (in Figure 5 be labeled as " A-C ") (hollow cathode as shown in FIG. 6 to) And electric current.Power supply 610 provides alternating current, and hollow cathode 602,604,606 acts alternately as cathode and anode.In the row In cloth, hollow cathode pair 602,604 and 604,606 is with+120 ° of out-phase, and hollow cathode pair 602,606 is with -120 ° of out-phase.When Between point t10、t11、t12、t13、t14And t15It is instructed on voltage curve 502,506,510 and current curve 504,508,512 And indicate various focus, the time point corresponds to the different views of hollow cathode shown in fig. 6 arrangement 600.
The plasma generated between any pairs of hollow cathode will be partially defined by between the pairs of hollow cathode Distance influence.In some embodiments, adjacent pairs of hollow cathode (for example, hollow cathode pair 602,604 and 604, The distance between 606) be it is identical or essentially identical, and non-conterminous hollow cathode (for example, hollow cathode 602,606) it Between distance be more than the distance between phase adjacency pair (adjacent pairs of hollow cathode).If the distance between pairs of hollow cathode is too Greatly, then plasma may not be formed between them.As the skilled person will recognize, between hollow cathode away from From being to rely on technique.As distance increases, plasma forms required voltage and increases.In some embodiments, hollow The distance between cathode is less than 500mm, or is less than 400mm, or is less than 200mm.In some embodiments, between hollow cathode Distance about 100mm.Although plasma, which is formed, to be occurred in the case of relatively large distance, for typical technique and confession For electric (power supply), maximum distance may be 500mm.Magnetic field can also influence effective interval.
The plasma of generation will also be partially defined by the influence of the voltage and current between the pairs of hollow cathode.Example Such as, although plasma can be formed between multipair hollow cathode, be partly due to different pairs of hollow cathodes it Between voltage and current on difference, the density of plasma may be simultaneously uneven.For example, for using plasma enhancing For use in chemical vapor deposition (method) coated substrate, this inhomogeneities will be inessential, because inhomogeneities is only In short time span occur and substrate by significantly move before, the region meeting of higher and lower plasma density Repeatedly switching.In addition, for inline coating processes, because substrate moves below plasma source and in each hollow cathode Below by so substrate will be handled on an equal basis.
Polyphase source 610 may include single power supply or multiple power supplys.Specifically, polyphase source 610 can generate it is more A output wave (for example, wave A, B and C in wavy curve 100), wherein (and therefore, those waves are supplied the multiple output wave The hollow cathode of electricity) each of about time phase shift relative to each other.In some embodiments, adjacent hollow cathode (for example, hollow cathode pair 602,604 and 604,606) is each relative to each other with identical phase angle (for example, for three-phase electricity 120 ° for source, 90 ° for four phase power supplys, 72 ° for five phase power supplys, 60 ° for six phase power supplys, for n For phase power supply) phase shift.For three hollow cathode linear embodiment of three-phase (i.e. hollow cathode is arranged into line), if Each adjacent hollow cathode pair 602,604 and 604,606 will with 120 ° of out-phase, then non-conterminous hollow cathode pair 602,606 With -120 ° of out-phase.For four phases, four hollow cathode linear embodiment, if each phase adjacency pair (adjacent pairs of hollow cathode) with 60 ° of out-phase, then being made of first and third hollow cathode in the line non-conterminous to (non-conterminous pairs of hollow cathode) Will with 120 ° of out-phase, and by the line first and the 4th hollow cathode form it is non-conterminous to (it is non-conterminous in pairs it is hollow Cathode) it will be with 180 ° of out-phase.
Corresponding to t10View show that the electric current flowing at which between hollow cathode 602 and 604 is empty in maximum value Electric current flowing between the heart-yin pole 604 and 606 is about the point (time point) of the half of maximum value.Corresponding to t11View in, Electric current flowing between hollow cathode 602 and 604 becomes zero, and electric current starts to flow between hollow cathode 602 and 606. The same point (t11) at, the electric current flowing between hollow cathode 604 and 606 reaches its maximum value.Corresponding to t12View In, when the electric current flowing between hollow cathode 602 and 606 reaches maximum value and electric current is started again in 602 He of hollow cathode Between 604 flowing (although along with corresponding to t10View in discribed side in the opposite direction) when, cycle continue.It is corresponding In t13View depict the cycle with corresponding to t10The opposite endpoint of view, wherein maximum current is in hollow cathode It is flowed between 602 and 604, and the approximately half of of maximum current is flowed between hollow cathode 604 and 606.Corresponding to t13Regard The electric current flowing of figure along with corresponding to t10View in side in the opposite direction, wherein previously having served as the hollow cathode of cathode Now act as anode.Corresponding to t14View depict with correspond to t11View described in electric current flowing situation it is opposite Electric current flowing situation, and correspond to t15View show with correspond to t12View described in electric current flowing feelings The opposite electric current flowing situation of condition.
One feature of 600 (and in other embodiments of the invention) of multiphase hollow cathode arrangement depicted in figure 6 It is, at each point (time point) when the electric current flowing between any two hollow cathode is close to zero, other hollow cathodes pair Between voltage difference and electric current flowing be not zero.By this arrangement, can create do not suffer from it is previously described by bipolar power The plasma device of the plasma turn-off time in the traditional plasma source of driving.That is, as discussed above, The embodiment of the present invention efficiently avoids intrinsic non-plasma in the bipolar hollow cathode arrangement 300 of the prior art and generates Region 402,404,406.It can be obtained according to an embodiment of the invention by including at least three hollow cathodes and polyphase source The plasma characteristics that must improve, including maintenance electric current flowing and resulting plasma within its whole service time Body generates to generate the device that continuous plasma generates.It is empty by using at least three phase offset waves and at least three The heart-yin pole will be substantially absent from the plasma turn-off time in the case where the wave is generated by AC power.For Pulse power depends on design parameter, and the plasma turn-off time can be with basically 0% to 20% or so.For example, using tool There are the pulse power and at least three hollow cathodes of at least three phase offset waves, plasma turn-off time that can be substantially 20% (or alternatively, there are the generations of active plasma on the 80% of the period of the wave)；The plasma turn-off time Can be substantially 10% (or alternatively, there are the generations of active plasma on the 90% of the period of the wave)；Deng from The daughter turn-off time can also be substantially 0% (or alternatively, exist on the 100% of the period of the wave actively it is equal from Daughter generates).Because in the presence of die-away time associated with plasma (that is, even if voltage between a pair of of hollow cathode It drops to after zero, exists in the short time that plasma still can be thereafter, although the plasma is not actively to be given birth to At), the generation of active plasma is known as that there are the times that active electronic emits by the application.
In some embodiments, hollow cathode 602,604,606 is (or described in this specification or realized by this specification The arrangement of any other hollow cathode) may include elongated cavity.Hollow cathode may include plasma exit region, and And the plasma exit region may include individual plasma outlet opening or multiple plasma exit holes or plasma Some of body exit slot or these plasma exit regions combine.In some embodiments, respectively electricity is exhausted for hollow cathode Edge, so that only the inner surface of hollow cathode and plasma exit region are that electron emission and electronics receive.One In a little embodiments, plasma exit that nearly all plasma flow continuously generated passes through each in hollow cathode Region.In some embodiments, electric current flowing includes the electronics or these electric current flowings of secondary or thermionic emission Some combination.In some embodiments, potential difference causes electric current to be flowed between hollow cathode.In some embodiments, exist Between any two in hollow cathode, which is at least 50V or at least 200V.In some embodiments, it generates more The polyphase source generation of a output wave includes multiple output waves of square wave, and thus potential difference is reduced relative to sine wave.Multiphase Power supply is in the form of AC electric energy or some of the form of pulse electric energy or these electrical energy forms combine.In some embodiments, exist In the case of the closed circuit electronics drift for being substantially absent from field drives, the plasma generated is base over its length This is uniform.In some embodiments, plasma is over its length basic from about 0.1m to about 1m or from about 1m to about 4m Uniformly.In some embodiments, the frequency of each in multiple output waves is equal and between from about 1kHz to about 1MHz or from about 10kHz to about 200kHz or in the range of from about 20kHz to about 100kHz.In some embodiments, from transmitting The electronics of surface emitting is constrained by hollow cathode effect.In some embodiments, the electronics emitted from emitting surface is not by magnetic The constraint of field.
A factor for influencing electronic current is the temperature of hollow cathode cavity wall.Cavity wall temperature is less than 1000 wherein DEG C hollow cathode setting in, electron emission is dominated by secondary.When cavity wall is by ion bombardment, knock-on ion Kinetic energy induces electronics together with negative voltage potential and emits from wall surface.Typically, these " cold " hollow cathodes from 50 DEG C to It is run at a temperature of 500 DEG C of cavity wall.In general, in order to maintain hollow cathode structure at these tem-peratures, using cooling side Method.In general, water cooling passageway is built in hollow cathode structure.The operation voltage of cold hollow cathode discharge is typically from 300 Volt is to 1000 volts.
Alternatively, hollow cathode can be run under thermion pattern.In order to make thermionic electron emission, hollow the moon The temperature of pole cavity wall is generally between in the range of from 1000 DEG C to 2000 DEG C.Thermion hollow cathode can be around cavity wall In conjunction with heater to help to improve temperature, or more simply, heating cavities wall can be carried out by energy of plasma transmission.One As for, hot cavity be thermal insulation with reduce conduction or radiation heat loss.The operation voltage allusion quotation of thermion hollow cathode discharge Type from 10 volts to 300 volt, or more commonly from 10 volts to 100 volt.
The commercially useful pecvd process with sufficiently high deposition rate depends on and has gone through some densifications The plasma of method.The hollow cathode effect is to realize electron dense peace treaty using closing or partially enclosed electric field The ad hoc approach of beam.Gas phase free electron is born field by closing and is captured, and around or between opposite negative bias wall Show oscillating movement.Electronic leads to long electron path length, this leads to the high probability of gas phase collisions in turn.These are touched Hitting makes ionizing gas molecules, to generate additional electronics and cation.Cation it is accelerated and with hollow the moon of negative bias Pole wall collision.The collision of cation-wall causes further to be electronically generated by secondary realization.Document indicates hollow the moon Pole plasma is usually than being originated from for example for the magnetic confinement of closed drift electron confinement technique (for example, magnetron sputtering) The finer and close plasma of plasma.
Another advantage of embodiment and other embodiments of the invention in Fig. 6 is, by including additional hollow the moon Pole generates wider plasma, this causes PECVD deposition rates to be improved.
Fig. 7 illustrates method according to an embodiment of the invention.Multiphase hollow cathode arrangement 600 (and pass through the disclosure Description and the other hollow cathodes arrangement realized) it can be used for generating continuous plasma.Generate the method 700 of plasma Including providing at least three hollow cathode (steps 702).Each hollow cathode has plasma exit region.The method Further include that the power supply (step 704) that can generate multiple output waves is provided.Each hollow cathode is electrically connected to the power supply.By Multiple output waves that the power supply generates are each about time phase shift relative to each other, to cause each hollow cathode and its The different electric phase of its hollow cathode.Electric current flows between at least three hollow cathodes of different electric phase.Plasma is in hollow the moon It is continuously generated between pole.In some embodiments, the method further includes providing substrate (step 706) and use Gas ions enhance chemical vapor deposition (method) and form coating (step 708) in substrate.Around step 706 and 708 in Fig. 7 Dotted line frame indicates that these steps are optional.Painting is formed in substrate using plasma enhanced chemical vapor deposition (PECVD) Layer may include providing the combination of precursor gas, process gas, reaction gas or these gases, and make it into hollow cathode In cavity or pass through the manifold adjacent with hollow cathode.Those skilled in the art will appreciate that can also include being applicable to Other steps of PECVD.
Fig. 8 illustrates the coating formed by method according to an embodiment of the invention.It is formd on the top of substrate 804 Coating 802, to create coating-substrate combination 800.In some embodiments, substrate 804 is glass.In other embodiments In, substrate 804 may include plastics, metal, semi-conducting material or other suitable materials used in the pecvd process.One In a little embodiments, coating 802 can be single layer or film, or may include multiple layers or film.In some embodiments, coating 802 can be low emissivity coatings, and substrate 804 can be windowpane, so that coating-substrate combination 800 is suitable for building Build purposes.In some embodiments, coating 802 can be other coatings for specific application, such as the anti-of refrigerator doors Mist coating or transparent conductive oxide coating for photovoltaic cell.
Fig. 9 illustrate it is according to an embodiment of the invention include the hollow cathode with plasma exit region multiphase Hollow-cathode plasma source.(shown in Fig. 9) linearly multiphase hollow cathode arrangement 600 includes hollow cathode 602,604,606 With polyphase source 610.Each hollow cathode 602,604,606 is powered by alternation or pulse power from polyphase source 610, so that Obtain each hollow cathode phase shifted from one another.Each hollow cathode 602,604,606 includes hollow cathode cavity 904 and plasma Body outlet 902.In the embodiment shown in fig. 9, hollow cathode 602,604,606 includes two of restriction cavity 904 spaced apart Lateral side regions and top area and limit plasma exit 902 open bottom region.Reaction gas (or process gas Or the combination of precursor gas or these gases) it can reside in the hollow cathode cavity of each hollow cathode 602,604,606 In 904.Reaction gas (or combination of process gas or precursor gas or these gases) is also present in conversion zone 910 In.In some embodiments, conversion zone 910 may include substrate, such as substrate 804, and in some embodiments, can be with Coating is formed in substrate in conversion zone 910.When being powered by polyphase source 610, electronics is alternately in each hollow the moon It is flowed between pole 602,604,606, to generate the plasma that outflow plasma exit 902 enters in conversion zone 910.
It includes with slit-like, restricted plasma exit region that Figure 10, which is illustrated according to an embodiment of the invention, Hollow cathode multiphase hollow-cathode plasma source.The embodiment of Figure 10 is the change case of the embodiment of Fig. 9, it is medium from Daughter outlet 902 is replaced by slit-like plasma exit 1002.Each hollow cathode 602,604,606 includes hollow cathode Cavity 904 and plasma exit 1002.In the embodiment shown in fig. 10, hollow cathode 602,604,606 is including between two The lateral side regions separated and the top area being spaced apart with bottom section, so that plasma exit 1002 is by bottom section Slit limit.When process gas is in hollow cathode 904 inside of cavity, the permission of plasma exit 1002 hollow cathode 602, 604, there is higher gas pressure in 606 inside.
As described above, multi-phasic plasma source according to an embodiment of the invention may include three hollow cathodes (each of described three hollow cathodes relative to each other phase shift), i.e. three-phase, three hollow cathode embodiments.Art technology And in general personnel are it will be recognized that other embodiments (such as four phases, five phases or six phase embodiments) are possible, can be with The arrangement of multiphase hollow cathode is provided for n phases embodiment (wherein n is more than 2).Made using additional hollow cathode and phase shift wave Obtain the plasma with desired characteristic that can be created for given technique or purposes.Such as the embodiment in Fig. 9 and Figure 10 Shown (and as described below), according to an embodiment of the invention, the arrangement of n phase hollow cathodes may include m sky The heart-yin pole, wherein n are less than or equal to m.For the system with m hollow cathode, it will existTo hollow cathode (no matter How is sequence).Thus, for example, being similar in Fig. 5 for voltage and current song shown in three hollow cathode embodiments to show The representative voltage and current curve of line, forIt will need 15 voltage curves and 15 electric current songs Line.In the case where hollow cathode is linearly arranged, there will be m-1 adjacent hollow cathodes pair.As the common skill of this field Art personnel can be simplified what is understood from the disclosure with the multiple hollow cathodes of less phase driven and be wanted to polyphase source It asks, and can also change the characteristic of the plasma generated as the function of time.
It includes six hollow cathodes and hollow the moon of multiphase of six phases that Figure 11, which is illustrated according to an embodiment of the invention, Pole plasma source.That is, in this embodiment, m=6 and n=6.Multiphase hollow cathode arrangement 1100 includes connection To the hollow cathode 1102,1104,1106,1108,1110,1112 of polyphase source 1110, the polyphase source 1110 is configured It powers to each hollow cathode at the phase offset wave 1120,1122,1124,1126,1128,1130 of independent (separation). In one embodiment, adjacent hollow cathode is translated to each with identical phase angle (for example, 60 °) phase with one another.Such as Figure 11 Shown, adjacent hollow cathode is to including hollow cathode pair 1102,1104；1104、1106；1106、1108；1108,1110 and 1110、1112.The wherein phase adjacency pair (adjacent pairs of hollow cathode) shown in Figure 11 is in the embodiment of 60 ° of out-phase, not phase Adjacency pair (non-conterminous pairs of hollow cathode) 1102,1108；1104、1110；With 1106,1112 each reverse phases relative to each other. It is non-conterminous right in the presence of 10 in the embodiment in figure 11Show in following table The phase difference of each pair of hollow cathode in Figure 11 is gone out, wherein phase adjacency pair (adjacent pairs of hollow cathode) is with 60 ° of phase shifts.
Table 1：
It is right Offset
1102,1104 60°
1102,1106 120°
1102,1108 180°
1102,1110 -120°
1102,1112 -60°
1104,1106 60°
1104,1108 120°
1104,1110 180°
1104,1112 -120°
1106,1108 60°
1106,1110 120°
1106,1112 180°
1108,1110 60°
1108,1112 120°
1110,1112 60°
It includes six hollow cathodes and hollow the moon of multiphase of three phases that Figure 12, which is illustrated according to an embodiment of the invention, Pole plasma source.That is, in this embodiment, m=3 and n=6.Hollow cathode arrangement 1200 is more including being connected to The hollow cathode 1102,1104,1106,1108,1110,1112 of phase power supply 1210.It is inclined that polyphase source 1210 generates three phases Move wave 1220,1222,1224.In this embodiment, wave 1220 is powered to hollow cathode 1102,1108；Wave 1222 is to hollow the moon Pole 1104,1110 powers；And wave 1224 is powered to hollow cathode 1106,1112.In some embodiments, each wave 1220, 1222, it 1224 is deviated with identical phase angle (for example, 120 °).In the embodiment shown in fig. 12, non-conterminous to (non-conterminous Pairs of hollow cathode) 1102,1108；1104、1110；With 1106,1112 each phases same relative to each other, because of single wave 1220, it 1222,1224 powers to every a pair.The phase difference of each pair of hollow cathode in Figure 12 is shown in following table, Wherein phase adjacency pair (adjacent pairs of hollow cathode) is with 120 ° of phase shifts.
Table 2：
It is right Offset
1102,1104 120°
1102,1106 –120°
1102,1108 0°
1102,1110 120°
1102,1112 –120°
1104,1106 120°
1104,1108 –120°
1104,1110 0°
1104,1112 120°
1106,1108 120°
1106,1110 –120°
1106,1112 0°
1108,1110 120°
1108,1112 –120°
1110,1112 120°
Figure 13 illustrates the multiphase hollow-cathode plasma source for including three equidistant hollow cathodes.Arrangement 1300 includes three A hollow cathode 602,604,606, wherein plasma exit 1002 each all point to common wire (note that because Figure 13 is horizontal Section view, so each appeared in outlet is directed toward common point).It is real shown in Figure 13 as will be apparent that It can also includes the additional hollow cathode under various geometric configurations to apply example, so that hollow cathode (or hollow cathode Some subsets) in the plasma exit of each be directed toward common wire (or one group of common wire).In some embodiments, hollow In cathode (adjacent and non-conterminous) each the distance between it is equal.For example, Figure 13 shows hollow cathode pair 602,604 The distance between the distance between every a pair in hollow cathode pair 602,606 and hollow cathode pair 604,606 it is essentially identical. It in some embodiments, can be from the center of hollow cathode, from the plasma exit of hollow cathode or from hollow cathode, sky The heart-yin is extremely upper or hollow cathode near a certain other points measure hollow cathodes to the distance between.The embodiment of Figure 13 is similar Embodiment for example can be used to coat two-dimentional substrate, such as conducting wire or fibre coating.For example, can be by keeping these elongated Substrate is evenly coated with two-dimentional substrate across the direction of common wire.
Figure 14 A and Figure 14 B illustrate bipolar hollow-cathode plasma source and multiphase according to an embodiment of the invention is empty In the plasma source the two of the heart-yin pole in hollow cathode and its around formed plasma electron density.For bipolar Between (Figure 14 A) and multi-phasic plasma source (Figure 14 B) outside comparable hollow cathode cavity, the electronics in conversion zone it is close Degree is horizontal, as shown, relative to multi-phasic plasma source, the electron density in the hollow cathode cavity in Bipolar plasmakinetic source Notable bigger.
Figure 15 A and Figure 15 B illustrate bipolar hollow-cathode plasma source and multiphase according to an embodiment of the invention is empty In the plasma source the two of the heart-yin pole in hollow cathode and its around formed plasma ion concentration.For bipolar Between (Figure 15 A) and multi-phasic plasma source (Figure 15 B) outside comparable hollow cathode cavity, the ion in conversion zone it is close Degree is horizontal, as shown, relative to multi-phasic plasma source, the ion concentration in the hollow cathode cavity in Bipolar plasmakinetic source Notable bigger.
Figure 16 A illustrate bipolar hollow-cathode plasma source and multiphase hollow cathode according to an embodiment of the invention etc. Along the Ions Absorption of hollow cathode cavity wall in plasma source the two.As shown, relative to multi-phasic plasma source, it is bipolar The notable bigger of the Ions Absorption along hollow cathode cavity wall of plasma source.The figure is additionally illustrated in hollow cathode cavity Corner's (exponential quantity 8,63,89,144), Ions Absorption are minimum.According to the figure, compared with bipolar arrangement, the absorption of multiphase arrangement Rate is smaller and is about its 88% (value will change according to used level of power during the operation of such as plasma source).
Figure 16 B are illustrated such as the curve of Figure 16 A index shown in the drawings along hollow cathode cavity wall.It is specific and It says, corresponds to the value in the x-axis of Figure 16 A (" along cavity wall along value shown in hollow cathode cavity wall 600 in Figure 16 B Index ").
Figure 14-16B are (similar as bipolar hollow cathode arrangement (being similar to arrangement 300) and the arrangement of multiphase hollow cathode Both 600) it is generated in arrangement simulation result.For example, with reference to figure 14A and Figure 15 A, bipolar arrangement includes being located at vacuum chamber Two linear hollow cathode 1402a, 1404a (reverse phase) in room 1430.Precursor gas flows through presoma manifold 1410.Deng from Daughter is formed in conversion zone 1420.Referring now to Figure 14 B and Figure 15 B, multiphase arrangement includes being located in vacuum chamber 1430 Three linear hollow cathode 1402b, 1404b, 1406b (each relative to each other with 120 ° of phase offsets).Precursor gas Flow through presoma manifold 1410.Plasma is formed in conversion zone 1420.Emulation setting is described further below.Hollow Use argon gas as process gas in cathode cavity.According to an embodiment of the invention, other process gas can also be used, including But it is not limited to oxygen, nitrogen, argon, helium, krypton, neon, xenon, hydrogen, fluorine, chlorine and its mixture.Reaction gas include H2, H2O, H2O2, N2, Or mixtures thereof NO2, N2O, NH3, CH4, CO, CO2, SH2, other sulfenyl gases, halogen, bromine, phosphorus base gas.
Specifically, from Figure 14-16B it is evident that for two-phase and three-phase arrangement between phase same level hollow cathode Plasma density in external plasma generating area, the hollow cathode of three-phase arrangement according to an embodiment of the invention Abrasion (loss) in cavity is horizontal significantly lower (as indicated by plasma and ion concentration and Ions Absorption).At this In the embodiment of invention, this can enable the service lives relative to Bipolar plasmakinetic source with longer hollow cathode.It removes Outside other factors, service life will be used for which kind of technique (process) depending on plasma source.For related to glass coating Typical PECVD applications, compared with the bipolar arrangement of tradition, the expectation service life of three hollow cathode of three-phase arrangement is larger and carry It is high by about 60%.In some embodiments, this additional lifetime that can be equal to about 200 hours, for example, in 300 hours bases The service life of accurate (baseline) upper 500 hour.The advantage is attributable to polyphase electric power arrangement, rather than just the additional sky of increase The result of the heart-yin pole.
It has been found by the present inventors that the sputtering amount of hollow cathode cavity surface with such as determined by numerical simulation it is hollow The absorption of reactive ion on cathode cavity surface is related.
The simulation software that gentle body electric discharge is flowed for emulating gas is the Fraunhofer surface by Braunschweig, Germany The program for being referred to as PIC-MC that engineering is developed with film IST research institutes.Software combination gas flowing, magnetic field and plasma Emulation.For gas flow simulations, the software uses Straight simulation Monte Carlo (DSMC), described for magnetic field simulation Software uses Element BEM (BEM), and plasma is emulated, and the software uses particle grid-Monte Carlo (Particle in Cell-Monte Carlo) method (PIC-MC).
Emulation carries out on pseudo- 2D models, and the puppet 2D models are the transverse directions of hollow-cathode plasma source 1.016mm slab.Pseudo- 2D, which refers to slice, has small thickness, and is applied with week in each plane in a lateral direction Phase property condition.
For emulation, many different plasmas for forming gas can be used；Previous argon has been used in example. The time is calculated in order to limit, selects Si2H6As coating precursor, and following two reactions are selected in its possible reaction：
Si2H6+e‐→Si2H4 ++2H+2e‐(1)
Si2H6+e‐→SiH3+SiH2+H+e‐(2)
Do not include hydrogen species in simulations.
For each given input parameter collection, emulation generate about different gas phase species (atom, ion, molecule and Electronics) quantity and speed in the entire space that they are occupied data.Certain values can be calculated from the data, such as close Degree and flux, wherein flux is the rate travel (unit of gas phase species on unit area：mol·m-2·s-1)。
Another useful calculating is the flux absorbed on a certain surface.It is assumed that cathode cavity material has certain adherency Coefficient, the Ions Absorption on cathode cavity material surface can be calculated by the ionic flux for being directed toward it.By will be bipolar hollow The operation result of cathode is associated with emulation data, the inventors discovered that, the fragment observed on actual plasma body source It is formed and the therefore sputtering of cavity surface and the ionization etc. by being absorbed according to the cavity surface of the hollow cathode of simulation model The level of gas ions species is related.
It is the attribute for being easy to obtain in emulating from used plasma that argon, which absorbs,.In addition, argon absorption is to be incident on electricity The particle flux of pole surface and effective gauge of ion energy.It will be appreciated by those skilled in the art that ion energy and particle Flux is the major driving factor of the physical process behind of sputtering or electrode corrosion.When the sputtering material of sputter rate and neighbouring surface Balanced deflection between the deposition of material occurs fragment and generates when net deposition.It is observed that the effect in Figure 16 A and Figure 16 B Fruit, Figure 16 A and Figure 16 B instructions sputtering and net deposition in the turning of rectangular electrode reduce, in the corner, Ions Absorption quilt It was found that (passing through emulation) is minimum.
Therefore, although practical sputtering value is not measured by emulation, the present inventor has used argon absorption value as this The sputtering of multiphase embodiment described in text or the index of electrode corrosion.
The low-level ionixedpiston species absorbed by the cavity surface of hollow cathode refer to the water of cavity sputtering Flat low and fragment forms low.As shown in Figure 16 A and Figure 16 B, Bipolar plasmakinetic source leads to the sputtering of most of electrode surface Increase with abrasion, wherein both Bipolar plasmakinetic source and multi-phasic plasma source have equal plasma in processing chamber Physical efficiency amount.Additional sputter material from Bipolar plasmakinetic source is deposited on the turning of such as electrode cavity and plasma at it Outside source surface (its be in floating or earth potential and be not subjected to sputtering) may be used also when not undergoing on the surface sputtered strongly Fragment can be caused to increase.The property quality and quantity of the fragment will depend critically upon the combination of electrode surface material and plasma gas.
Another important amount is the electron density generated.Electron density has main shadow to surface treatment or coating efficiency It rings, wherein high electron density leads to high surface processing efficiency or high coating efficiency.In this emulation, electron density is in vacuum chamber In determining and be averaged in the line group at the distance of the chamber structure 2.54mm in distance support plasma source.
Inventors have surprisingly found that compared with the configuration of two hollow cathodes with 180 degree phase shift, work as use When three hollow cathodes of each phase shift with 120 degree, by the ionixedpiston object of cathode cavity Surface absorption The horizontal of kind reduces.
According to this embodiment of the invention, inventors have surprisingly found that, for three hollow cathode of three-phase arrangement and two-phase The intensity of both two hollow cathodes arrangements, the electron density in conversion zone outside hollow cathode is similar.This is to make us Surprised, because for example compared with two hollow cathode of two-phase is arranged, the arrangement of three hollow cathode of three-phase generates to collect in larger area In plasma and inside hollow cathode experience compared with less wear.
As those skilled in the art will recognize from the present disclosure that, hollow cathode and polyphase electric power input permitted Mostly other combinations are possible, wherein specific arrangement is designed to be suitble to specific application.
Although various embodiments are described above, it is understood that, their merely exemplary presentations, without It is limitation.Therefore, the width of the disclosure and range should not be limited by any of above exemplary embodiment.In addition, unless at this It is otherwise dictated in text or significantly with contradicted by context, otherwise the disclosure includes the above-mentioned member in all possible variation Any combinations of part.
In addition, although the technique illustrated in described above and attached drawing is shown as series of steps, this is only It is for illustrative purposes and carries out.It is therefore contemplated that arriving, some steps can be added, it is convenient to omit some steps, Ke Yichong The sequence of new alignment step, and some steps can be performed in parallel.

Claims (69)

1. a kind of plasma source comprising：
At least three hollow cathodes, at least three hollow cathode include the first hollow cathode, the second hollow cathode and third Hollow cathode, each hollow cathode have plasma exit region；And
Power supply, the power supply can generate multiple output waves, the multiple output wave include the first output wave, the second output wave and Third output wave, wherein first output wave and the second output wave out-phase, second output wave and the third are defeated Go out wave out-phase, and first output wave and the third output wave out-phase；
Wherein each hollow cathode is electrically connected to the power supply, so as to be electrically connected to described first defeated for first hollow cathode Go out wave, second hollow cathode is electrically connected to second output wave, and the third hollow cathode be electrically connected to it is described Third output wave；
Wherein electric current flows between at least three hollow cathode of different electric phase；And
The wherein described plasma source can generate plasma between the hollow cathode.
2. plasma source according to claim 1,
The plasma wherein generated by the plasma source the multiple output wave period it is at least basic Include that active electronic emits on 80%.
3. plasma source according to claim 1,
The plasma wherein generated by the plasma source the multiple output wave period it is at least basic Include that active electronic emits on 90%.
4. plasma source according to claim 1,
The plasma wherein generated by the plasma source the multiple output wave period it is at least basic Include that active electronic emits on 100%.
5. plasma source according to claim 1, wherein at least three hollow cathode is with the phase different from 180 ° The different electric phase of parallactic angle.
6. plasma source according to claim 1, wherein at least three hollow cathode is different with 120 ° of phase angle Electric phase.
7. plasma source according to claim 1, wherein each phase adjacency pair at least three hollow cathode is empty The heart-yin pole is with each other phase adjacency pair hollow cathodes at least three hollow cathode with the different electric phase in identical phase angle.
8. plasma source according to claim 1, wherein at least three hollow cathode is linear hollow cathode.
9. plasma source according to claim 1, wherein at least three hollow cathode each include it is elongated Cavity.
10. plasma source according to claim 1, wherein each hollow the moon at least three hollow cathode The plasma exit region of pole includes multiple plasma exit holes.
11. plasma source according to claim 1, wherein each hollow the moon at least three hollow cathode The plasma exit region of pole includes plasma exit slit.
12. plasma source according to claim 1, wherein at least three hollow cathode is respectively electrically insulated, so that It is that electron emission and electronics receive to obtain the only inner surface of the hollow cathode and the plasma exit region.
13. plasma source according to claim 1, wherein the plasma flow of nearly all generation by it is described extremely The plasma exit region of each hollow cathode in few three hollow cathodes.
14. plasma source according to claim 1, wherein electric current flowing include the electronics from secondary.
15. plasma source according to claim 1, wherein electric current flowing include the electricity from thermionic emission electronics Son.
16. plasma source according to claim 1, wherein at least three hollow cathode is linearly arranged.
17. plasma source according to claim 1, wherein be configured to will be described etc. at least three hollow cathode Each in gas ions exit region is directed toward common wire.
18. plasma source according to claim 1, wherein every a pair of hollow the moon at least three hollow cathode The distance between pole is identical distance.
19. plasma source according to claim 1, wherein between at least three hollow cathode of different electric phase The electric current of flowing is the result of the potential difference between at least three hollow cathode.
20. plasma source according to claim 19, wherein any two at least three hollow cathode is empty Potential difference between the heart-yin pole is at least 50V.
21. plasma source according to claim 19, wherein any two at least three hollow cathode is empty Potential difference between the heart-yin pole is at least 200V.
22. plasma source according to claim 1, wherein the multiple output wave includes square wave, thus for identical Overall electric power input, potential difference is reduced relative to sine wave.
23. plasma source according to claim 1, wherein the power supply is in the form of AC electric energy.
24. plasma source according to claim 1, wherein the power supply is in the form of pulse electric energy.
25. plasma source according to claim 1, wherein in the closed circuit electric float for being substantially not present field drives In the case of shifting, the plasma generated is substantially homogeneous over its length.
26. plasma source according to claim 1, wherein the plasma is over its length from about 0.1m to about 1m It is substantially homogeneous.
27. plasma source according to claim 1, wherein the plasma is over its length from about 1m to about 4m It is substantially homogeneous.
28. plasma source according to claim 1, wherein the frequency of each output wave in the multiple output wave It is equal and between in the range of from about 1kHz to about 500MHz.
29. plasma source according to claim 1, wherein the frequency of each output wave in the multiple output wave It is equal and between in the range of from about 1kHz to about 1MHz.
30. plasma source according to claim 1, wherein the frequency of each output wave in the multiple output wave It is equal and between in the range of from about 10kHz to about 200kHz.
31. plasma source according to claim 1, wherein the frequency of each output wave in the multiple output wave It is equal and between in the range of from about 20kHz to about 100kHz.
32. plasma source according to claim 1, wherein the electronics from emitting surface is by hollow cathode effect Constraint.
33. plasma source according to claim 1, wherein each at least three hollow cathode is empty The electronics of the emitting surface of the heart-yin pole is not constrained by magnetic field.
34. plasma source according to claim 1, wherein in the multiple output wave generated by the power supply extremely A few output wave is configured to the power supply of multiple hollow cathodes at least three hollow cathode.
35. a kind of method generating plasma comprising：
At least three hollow cathodes are provided, at least three hollow cathode include the first hollow cathode, the second hollow cathode and Third hollow cathode, each hollow cathode have plasma exit region；And
Power supply is provided, the power supply can generate multiple output waves, and the multiple output wave includes the first output wave, the second output Wave and third output wave, wherein first output wave and the second output wave out-phase, second output wave and described Three output wave out-phase, and first output wave and the third output wave out-phase；
Wherein each hollow cathode is electrically connected to the power supply, so as to be electrically connected to described first defeated for first hollow cathode Go out wave, second hollow cathode is electrically connected to second output wave, and the third hollow cathode be electrically connected to it is described Third output wave；
Wherein electric current flows between at least three hollow cathode of different electric phase；And
Wherein plasma is generated between the hollow cathode.
36. according to the method for claim 35,
The wherein described plasma includes that active electronic emits at least basic the 80% of the period of the multiple output wave.
37. according to the method for claim 35,
The wherein described plasma includes that active electronic emits at least basic the 90% of the period of the multiple output wave.
38. according to the method for claim 35,
The wherein described plasma includes that active electronic emits at least basic the 100% of the period of the multiple output wave.
39. according to the method for claim 35, wherein at least three hollow cathode is with the phase angle different from 180 ° Different electricity phase.
40. according to the method for claim 35, wherein at least three hollow cathode is with the different electric phase in 120 ° of phase angle Position.
41. according to the method for claim 35, wherein each hollow the moon of phase adjacency pair at least three hollow cathode Pole is with each other phase adjacency pair hollow cathodes at least three hollow cathode with the different electric phase in identical phase angle.
42. according to the method for claim 35, wherein at least three hollow cathode is linear hollow cathode.
43. according to the method for claim 35, wherein at least three hollow cathode each includes elongated cavity.
According to the method for claim 35,44. wherein each hollow cathode at least three hollow cathode Plasma exit region includes multiple plasma exit holes.
According to the method for claim 35,45. wherein each hollow cathode at least three hollow cathode Plasma exit region includes plasma exit slit.
46. according to the method for claim 35, wherein at least three hollow cathode is respectively electrically insulated, so that only The inner surface of the hollow cathode and the plasma exit region are that electron emission and electronics receive.
47. according to the method for claim 35, wherein the plasma flow of nearly all generation passes through described at least three The plasma exit region of each hollow cathode in a hollow cathode.
48. according to the method for claim 35, wherein electric current flowing includes the electronics from secondary.
49. according to the method for claim 35, wherein electric current flowing includes the electronics from thermionic emission electronics.
50. according to the method for claim 35, wherein at least three hollow cathode is linearly arranged.
51. according to the method for claim 35, wherein at least three hollow cathode is configured to the plasma Each in body exit region is directed toward common wire.
52. according to the method for claim 35, wherein at least three hollow cathode per a pair of of hollow cathode it Between distance be identical distance.
53. according to the method for claim 35, wherein being flowed between at least three hollow cathode of different electric phase Electric current be the potential difference between at least three hollow cathode result.
54. method according to claim 53, wherein any two hollow cathode at least three hollow cathode Between potential difference be at least 50V.
55. method according to claim 53, wherein any two hollow cathode at least three hollow cathode Between potential difference be at least 200V.
56. according to the method for claim 35, wherein the multiple output wave includes square wave, thus for identical totality Electric power input, the potential difference are reduced relative to sine wave.
57. according to the method for claim 35, wherein the power supply is in the form of AC electric energy.
58. according to the method for claim 35, wherein the power supply is in the form of pulse electric energy.
59. according to the method for claim 35, wherein in the closed circuit electronics drift for being substantially not present field drives In the case of, the plasma continuously generated is substantially homogeneous over its length.
60. according to the method for claim 35, wherein the plasma is over its length base from about 0.1m to about 1m This is uniform.
61. according to the method for claim 35, wherein the plasma is over its length basic from about 1m to about 4m Uniformly.
62. according to the method for claim 35, wherein the frequency of each output wave in the multiple output wave is phase Deng and between in the range of from about 1kHz to about 500MHz.
63. according to the method for claim 35, wherein the frequency of each output wave in the multiple output wave is phase Deng and between in the range of from about 1kHz to about 1MHz.
64. according to the method for claim 35, wherein the frequency of each output wave in the multiple output wave is phase Deng and between in the range of from about 10kHz to about 200kHz.
65. according to the method for claim 35, wherein the frequency of each output wave in the multiple output wave is phase Deng and between in the range of from about 20kHz to about 100kHz.
66. according to the method for claim 35, wherein the electronics from emitting surface is constrained by hollow cathode effect.
67. according to the method for claim 35, wherein each hollow the moon at least three hollow cathode The electronics of the emitting surface of pole is not constrained by magnetic field.
68. according to the method for claim 35, wherein in the multiple output wave generated by the power supply at least one A output wave is configured to the power supply of multiple hollow cathodes at least three hollow cathode.
69. according to the method for claim 35, further comprising：
Substrate is provided；
Coating is formed on the substrate using plasma enhanced chemical vapor deposition.
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