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) are currently used to provide alternating or pulsed current to a hollow cathode plasma source.
The use of direct current during operation of a linear hollow cathode plasma source causes plasma to be generated primarily in a single area, rather than throughout the entire length of the linear hollow cathode. Although some types of plasma sources using direct current can effectively utilize magnets to generate a uniform plasma, this cannot be done with linear hollow cathodes. However, a high degree of uniformity (not achievable by the use of direct current in a linear hollow cathode plasma source) is necessary for many applications, such as coating glass using plasma-enhanced chemical vapor deposition.
The inventors previously discovered that, in a hollow cathode plasma source, using two-phase (bipolar) alternating or pulsed power can achieve a uniform linear plasma. However, the use of two-phase power in hollow cathode plasma sources has some disadvantages. For example, due to the alternation of the power, a plasma is not actively generated (i.e., there is no active electron emission) by the plasma source for some portion of the operational time. For typical applications, this time where plasma is not being actively generated is approximately 25% of a period of the power supply. Another disadvantage is that there is significant wear on the plasma source due to the use of the two-phase power source, which decreases the operational life of the plasma source.
Thus, there is a need in the art for plasma sources that overcome these and other disadvantages of known plasma sources.
The following commonly-assigned applications describe various hollow cathode plasma sources, such as may be used in embodiments of the present invention: U.S. application Ser. No. 12/535,447, now U.S. Pat. No. 8,652,586; U.S. application Ser. No. 14/148,612; U.S. application Ser. No. 14/148,606; U.S. application Ser. No. 14/486,726; U.S. application Ser. No. 14/486,779; PCT/US14/068919; PCT/US14/68858. Each of these applications is incorporated herein by reference in its entirety.
Advantages of 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.
According to a first aspect of the invention, a plasma source is provided. The 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.
According to a second aspect of the invention, a method of producing a plasma is provided. The method 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. In some embodiments, the method further includes providing a substrate and forming a coating on the substrate using plasma-enhanced chemical vapor deposition.
In some embodiments (according to any of the aspects of the present invention), 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.
In some embodiments, 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.
In some embodiments, 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. In some embodiments, 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.
In some embodiments, 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. In some embodiments, the electric potential difference is at least 200V between any two of the at least three hollow cathodes. In some embodiments, 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. In some embodiments, 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.
In some embodiments, the generated plasma is substantially uniform over its length in the substantial absence of magnetic-field driven closed circuit electron drift. In some embodiments, the plasma is made substantially uniform over its length from about 0.1 m to about 1 m. In some embodiments, the plasma is made substantially uniform over its length from about 1 m to about 4 m. In some embodiments, the frequencies of each of the multiple output waves are equal and are in the range from about 1 kHz to about 500 MHz. In some embodiments, the frequencies of each of the multiple output waves are equal and are in the range from about 1 kHz to about 1 MHz. In some embodiments, the frequencies of each of the multiple output waves are equal and are in the range from about 10 kHz to about 200 kHz. In some embodiments, the frequencies of each of the multiple output waves are equal and are in the range from about 20 kHz to about 100 kHz. In some embodiments, the electrons from an emitting surface are confined by the hollow cathode effect. In some embodiments, the electrons from an emitting surface of each of the at least three hollow cathodes are not confined by magnetic fields. In some embodiments, 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.
The accompanying drawings, which are incorporated herein and form part of the specification, illustrate various embodiments of the present disclosure and, together with the description, further serve to explain the principles of the disclosure and to enable a person skilled in the pertinent art to make and use the embodiments disclosed herein. In the drawings, like reference numbers indicate identical or functionally similar elements.
Consider a sine wave A sin 2πft+φ, where A is the amplitude, f is the frequency, and φ is the phase angle. The phase angle φ specifies where the oscillation is at time t=0. With respect to two sine waves A1 sin 2πft+φ1 and A2 sin 2πft+2, the phase difference between the two waves is defined as the difference of phase angles φ2−φ1. 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. If the leading wave is considered to be the first wave, and the phase difference is φ, then considering the lagging wave as the first wave will lead to a phase difference of −φ. Generally 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. Although φ 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. Since a sine wave has a cycle or period of exactly 360° (or 2π radians), the phase angle φ can be expressed as a number between −180° (or −π radians) and +180° (or +π radians). The phase difference is independent of amplitude A and is properly defined only between two waves that have the same frequency f.
Where the two waves share the same phase angle φ, there is no phase difference and the waves are said to be in phase (with respect to each other). Where the two waves do not share the same phase angle φ, the waves are said to be out of phase (with respect to each other). Where the phase difference is 180°, the two waves are said to be antiphase (with respect to each other). 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. One of ordinary skill in the art will also recognize that phase difference can be defined for square waves, pulse waves, and other waveforms.
When two hollow cathodes are being powered by two waves that are out of phase, this application will refer to those hollow cathodes as being phase offset (with respect to each other) by a given phase angle, defined as the phase difference of the two waves powering the hollow cathodes. Thus, either the waves or the hollow cathodes can be said (interchangeably) to be phase offset from each other. Alternatively, if the two waves are in phase, the two hollow cathodes will (interchangeably) be referred to as being in phase.
“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.
“Secondary electron” or “secondary electron current” is taken to mean electron emission from a solid surface as a result of bombardment of that surface by a particle and the current that is created as a result, respectively. Electron emitting surfaces in accordance with embodiments of the present invention can generate a plasma and the surfaces are, in turn, further impinged upon by electrons or ions. The impingement of the electron emitting surfaces by electrons, or ions, results in secondary electrons emitted from the electron emitting surfaces. Secondary electron emission is important because secondary electron flow aids in creating a densified plasma.
The view corresponding to t1 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 t2 shows the point where the potential difference between hollow cathodes 302, 304 reaches a maximum and plasma 320 is ignited. The view corresponding to t3 shows the point of maximum current, where plasma 320 is fully established between the two hollow cathodes 302, 304. The view corresponding to t4 shows the bipolar hollow cathode arrangement 300 at a point where current is equal to the current at t2, where a plasma 320 of diminished intensity (compared to, for example, the view corresponding to t3) exists. The view corresponding to t5 shows the next zero crossing, where plasma generation has once again ceased. The view corresponding to t6 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 t2.
The switching of roles between cathode and anode is briefly described. 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.
The plasma generated between any pair of hollow cathodes will be affected, in part, by the distance between the pair of hollow cathodes. In some embodiments, the distance between adjacent pairs of hollow cathodes (e.g., hollow cathode pairs 602, 604 and 604, 606) is the same, or substantially the same, while the distance between non-adjacent hollow cathodes (e.g. hollow cathodes 602, 606) is greater than the distance between adjacent pairs. If the distance between a pair of hollow cathodes is too large, plasma may not be formed between them. As will be recognized by one of skill in the art, distance between hollow cathodes is process dependent. As distance increases, the voltage required for plasma formation increases. In some embodiments, the distance between hollow cathodes is less than 500 mm, or less than 400 mm, or less than 200 mm. In some embodiments, the distance between hollow cathodes is about 100 mm. Although plasma formation can occur for larger distances, for typical processes and power supplies, a maximum distance might be 500 mm. Magnetic fields can also influence effective spacing ranges.
The plasma generated will also be affected, in part, by the voltage and current between the pair of hollow cathodes. For example, although plasma may be forming between multiple pairs 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. For use in coating a substrate using plasma-enhanced chemical vapor deposition, for example, 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. Further, for inline coating processes, because 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 power source, 60° for a six-phase power source, 360°/n for an n-phase power source). For a three-phase three-hollow-cathode linear embodiment (i.e. hollow cathodes are arranged in a line), if each adjacent hollow cathode pair 602, 604 and 604, 606 is out of phase by 120°, then non-adjacent hollow cathode pair 602, 606 would be out of phase by −120°. For a four-phase four-hollow-cathode linear embodiment, if 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 t10 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. In the view corresponding to t11, current flow between hollow cathodes 602 and 604 becomes zero while current begins flowing between hollow cathodes 602 and 606. At this same point (t11), current flow between hollow cathodes 604 and 606 reaches its maximum value. The cycle continues in the view corresponding to t12, 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 t10. The view corresponding to t13 depicts the opposite end of the cycle from the view corresponding to t10, 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 t13 are in the opposite directions of those in the view corresponding to t10, with the hollow cathodes that previously served as cathodes now serving as anodes. The view corresponding to t14 depicts the opposite current flow situation of what was described in the view corresponding to t11, and the view corresponding to t15 shows the opposite current flow situation of what was described in the view corresponding to t12.
One characteristic of the multiphase hollow cathode arrangement 600 depicted in
In some embodiments, hollow cathodes 602, 604, 606 (or any other hollow cathode arrangement described in or enabled by this specification) 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. In some embodiments, 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. In some embodiments, current flow is comprised of secondary electron emission or thermionic-emitted electrons or some combination of these current flows. In some embodiments, 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. In some embodiments, 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. In some embodiments, the plasma that is generated is substantially uniform over its length in the substantial absence of magnetic-field driven closed circuit electron drift. In some embodiments, the plasma is made substantially uniform over its length from about 0.1 m to about 1 m or from about 1 m to about 4 m. In some embodiments, the frequencies of each of the multiple output waves are equal and are in the range of from about 1 kHz to about 1 MHz or from about 10 kHz to about 200 kHz or from about 20 kHz to about 100 kHz. In some embodiments, 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. In a hollow cathode setup with cavity wall temperature below 1000° C., electron emission is dominated by secondary electron emission. As cavity walls are bombarded by ions, the impacting ion kinetic energy along with a negative voltage potential induces electrons to be emitted from wall surfaces. Typically, these “cold” hollow cathodes are run with cavity wall temperatures from 50° C. to 500° C. Generally, to maintain hollow cathode structures at these temperatures, cooling methods are applied. Often, 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.
Alternatively, hollow cathodes may be run in thermionic mode. For thermionic electron emission to occur, 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. Generally, 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 to 100 volts.
Commercially useful 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).
Another advantage of the embodiment in
As described above, a multiphase plasma source according to embodiments of the invention can include three hollow cathodes, each phase shifted from each other, i.e. three-phase, three-hollow-cathode embodiments. One of skill in the art will recognize that other embodiments are possible, such as four-, five-, or six-phase embodiments, and that in general, a multiphase hollow cathode arrangement can be provided for an n-phase embodiment, where n is greater than 2. Using additional hollow cathodes and phase-shifted waves enables the creation of a plasma with the desired characteristics for a given process or use. As the embodiments in
Specifically, it is apparent from
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 IST, 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).
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.
For the simulations many different plasma forming gasses can be used; in the previous examples argon was used. In order to limit the computation time Si2H6 was chosen as coating precursor and among its possible reactions the following two were selected:
Si2H6+e−→Si2H4++2H+2e− (1)
Si2H6+e−→SiH3+SiH2+H+e− (2)
Hydrogen species were not included in the simulations.
For each given set of input parameters 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. By correlating results from the operation of bipolar hollow cathodes with simulation data 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
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. As shown in
Another important quantity is the electron density generated. 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. In the present simulations 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 level of ionized plasma species absorbed by the cathode cavity surfaces was reduced when three hollow cathodes were used each with a phase shift of 120 degrees as compared to a configuration with two hollow cathodes with a phase shift of 180 degrees.
According to this embodiment of the present invention, 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.
Many other combinations of hollow cathodes and multiphase power inputs are possible with the specific arrangements being designed to suit a particular application, as one of ordinary skill in the art will appreciate from the present disclosure.
While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of the present disclosure should not limited by any of the above-described exemplary embodiments. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.
Additionally, while the processes described above and illustrated in the drawings are shown as a sequence of steps, this was done solely for the sake of illustration. Accordingly, it is contemplated that some steps may be added, some steps may be omitted, the order of the steps may be re-arranged, and some steps may be performed in parallel.
This application is a continuation of U.S. application Ser. No. 14/942,737, filed Nov. 16, 2015. The content of this application is incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
2920235 | Bell et al. | Jan 1960 | A |
3253180 | Huber | May 1966 | A |
3381157 | Ferreira | Apr 1968 | A |
3813549 | Di Stefano et al. | May 1974 | A |
4017808 | Fein et al. | Apr 1977 | A |
4196233 | Bitzer et al. | Apr 1980 | A |
4419203 | Harper et al. | Dec 1983 | A |
4422014 | Glaser | Dec 1983 | A |
4702784 | Naoumidis et al. | Oct 1987 | A |
4916356 | Ahern et al. | Apr 1990 | A |
5028791 | Koshiishi et al. | Jul 1991 | A |
5070811 | Feuerstein et al. | Dec 1991 | A |
5113790 | Geisler et al. | May 1992 | A |
5185132 | Horiike et al. | Feb 1993 | A |
5286534 | Kohler et al. | Feb 1994 | A |
5302422 | Nowak et al. | Apr 1994 | A |
5369337 | Yanagi | Nov 1994 | A |
5399254 | Geisler et al. | Mar 1995 | A |
5437778 | Hedgcoth | Aug 1995 | A |
5581155 | Morozov et al. | Dec 1996 | A |
5593539 | Kubota et al. | Jan 1997 | A |
5609690 | Watanabe | Mar 1997 | A |
5614248 | Schiller et al. | Mar 1997 | A |
5614273 | Goedicke et al. | Mar 1997 | A |
5627435 | Jansen et al. | May 1997 | A |
5846608 | Neumann et al. | Dec 1998 | A |
5874807 | Neger et al. | Feb 1999 | A |
5897753 | Schatz et al. | Apr 1999 | A |
5908602 | Bardos et al. | Jun 1999 | A |
5939829 | Schoenbach et al. | Aug 1999 | A |
5985378 | Paquet | Nov 1999 | A |
6082293 | Kawashima | Jul 2000 | A |
6140773 | Anders et al. | Oct 2000 | A |
6146462 | Yializis et al. | Nov 2000 | A |
6174450 | Patrick et al. | Jan 2001 | B1 |
6177148 | Walther et al. | Jan 2001 | B1 |
6293222 | Paquet | Sep 2001 | B1 |
6388381 | Anders | May 2002 | B2 |
6444945 | Maschwitz | Sep 2002 | B1 |
6489854 | Chen | Dec 2002 | B1 |
6508911 | Han et al. | Jan 2003 | B1 |
6528947 | Chen et al. | Mar 2003 | B1 |
6750600 | Kaufman | Jun 2004 | B2 |
6768079 | Kosakai | Jul 2004 | B2 |
6800336 | Förnsel et al. | Oct 2004 | B1 |
6849854 | Sainty | Feb 2005 | B2 |
6899054 | Bárdos et al. | May 2005 | B1 |
6902814 | Takahashi et al. | Jun 2005 | B2 |
6924223 | Yamasaki et al. | Aug 2005 | B2 |
7241360 | Shabalin et al. | Jul 2007 | B2 |
7307383 | Takeuchi et al. | Dec 2007 | B2 |
7322313 | Mayumi et al. | Jan 2008 | B2 |
7327089 | Madocks | Feb 2008 | B2 |
7411352 | Madocks | Aug 2008 | B2 |
7411353 | Rutberg et al. | Aug 2008 | B1 |
7543546 | Shibata et al. | Jun 2009 | B2 |
7649316 | Rueger et al. | Jan 2010 | B2 |
7976907 | Hofrichter et al. | Jul 2011 | B2 |
8143788 | Hofer et al. | Mar 2012 | B2 |
8328982 | Babayan et al. | Dec 2012 | B1 |
8356575 | Sasaki et al. | Jan 2013 | B2 |
8409459 | Denpoh et al. | Apr 2013 | B2 |
8476587 | Jones et al. | Jul 2013 | B2 |
8652586 | Maschwitz | Feb 2014 | B2 |
8697197 | Savas et al. | Apr 2014 | B2 |
8926920 | Morfill et al. | Jan 2015 | B2 |
9443703 | Morgner et al. | Sep 2016 | B2 |
9533914 | Mahieu et al. | Jan 2017 | B2 |
9704692 | Leeser | Jul 2017 | B2 |
9721765 | Chambers et al. | Aug 2017 | B2 |
9735020 | Hudson | Aug 2017 | B2 |
10068743 | Goerbing | Sep 2018 | B2 |
20020000779 | Anders | Jan 2002 | A1 |
20020194833 | Gallimore et al. | Dec 2002 | A1 |
20030113479 | Fukuda et al. | Jun 2003 | A1 |
20040033385 | Kaushal et al. | Feb 2004 | A1 |
20050016456 | Taguchi et al. | Jan 2005 | A1 |
20050016458 | Zhang et al. | Jan 2005 | A1 |
20050035731 | Secheresse et al. | Feb 2005 | A1 |
20050040037 | Walton et al. | Feb 2005 | A1 |
20050106094 | Kondo | May 2005 | A1 |
20050115933 | Kong et al. | Jun 2005 | A1 |
20050208215 | Eguchi et al. | Sep 2005 | A1 |
20050221022 | Wang et al. | Oct 2005 | A1 |
20060030134 | Kim et al. | Feb 2006 | A1 |
20060177599 | Madocks | Aug 2006 | A1 |
20060208649 | Rueger et al. | Sep 2006 | A1 |
20070002515 | Hino et al. | Jan 2007 | A1 |
20070017636 | Gate et al. | Jan 2007 | A1 |
20070123041 | Anzai et al. | May 2007 | A1 |
20070163440 | Kim et al. | Jul 2007 | A1 |
20080073557 | German et al. | Mar 2008 | A1 |
20080106202 | Du et al. | May 2008 | A1 |
20090004836 | Singh | Jan 2009 | A1 |
20090032393 | Madocks | Feb 2009 | A1 |
20090071403 | Choi et al. | Mar 2009 | A1 |
20090071406 | Choi et al. | Mar 2009 | A1 |
20090183771 | Sunnomiya et al. | Jul 2009 | A1 |
20090218212 | Denpoh | Sep 2009 | A1 |
20100028238 | Maschwitz | Feb 2010 | A1 |
20100044579 | Holmes et al. | Feb 2010 | A1 |
20100186671 | Hein et al. | Jul 2010 | A1 |
20100225234 | Tseng et al. | Sep 2010 | A1 |
20110005682 | Savas et al. | Jan 2011 | A1 |
20110006040 | Savas et al. | Jan 2011 | A1 |
20110135843 | Niira et al. | Jun 2011 | A1 |
20110192348 | Tseng et al. | Aug 2011 | A1 |
20110212624 | Hudson | Sep 2011 | A1 |
20110226611 | Madocks | Sep 2011 | A1 |
20110297532 | Chakraborty et al. | Dec 2011 | A1 |
20120164353 | Madocks | Jun 2012 | A1 |
20120199469 | Rasheed et al. | Aug 2012 | A1 |
20120225218 | Savas et al. | Sep 2012 | A1 |
20120258555 | Holland et al. | Oct 2012 | A1 |
20120289054 | Holland et al. | Nov 2012 | A1 |
20120313517 | Rueger et al. | Dec 2012 | A1 |
20130112670 | Yokogawa et al. | May 2013 | A1 |
20130333618 | Cox | Dec 2013 | A1 |
20130337657 | Savas et al. | Dec 2013 | A1 |
20140099451 | Mahieu et al. | Apr 2014 | A1 |
20140216343 | Maschwitz | Aug 2014 | A1 |
20140220361 | Maschwitz | Aug 2014 | A1 |
20140272459 | Daugherty et al. | Sep 2014 | A1 |
20140354149 | Morgner et al. | Dec 2014 | A1 |
20150002021 | Maschwitz | Jan 2015 | A1 |
20150004330 | Maschwitz | Jan 2015 | A1 |
20150152542 | Deppisch | Jun 2015 | A1 |
20150235814 | Kawahara et al. | Aug 2015 | A1 |
20160024657 | Sakamoto et al. | Jan 2016 | A1 |
20170004955 | Leeser | Jan 2017 | A1 |
20170040145 | Brandon | Feb 2017 | A1 |
20170178869 | Chambers et al. | Jun 2017 | A1 |
20180025892 | Biquet et al. | Jan 2018 | A1 |
Number | Date | Country |
---|---|---|
1598049 | Feb 2005 | CN |
1831190 | Sep 2006 | CN |
1860587 | Nov 2006 | CN |
102099505 | Jun 2011 | CN |
102497721 | Jun 2012 | CN |
102677022 | Sep 2012 | CN |
102771192 | Nov 2012 | CN |
102816987 | Dec 2012 | CN |
103042317 | Apr 2013 | CN |
103493602 | Jan 2014 | CN |
103534383 | Jan 2014 | CN |
103632911 | Mar 2014 | CN |
105427014 | Mar 2016 | CN |
199 02 146 | Aug 2000 | DE |
201391765 | Apr 2014 | EA |
0727508 | Aug 1996 | EP |
0881865 | Dec 1998 | EP |
0886310 | Dec 1998 | EP |
1035561 | Sep 2000 | EP |
1913624 | Oct 2011 | EP |
1 257 015 | Dec 1971 | GB |
S-59228338 | Dec 1984 | JP |
S61-238962 | Oct 1986 | JP |
61251021 | Nov 1986 | JP |
S63-297560 | Dec 1988 | JP |
H4-180557 | Jun 1992 | JP |
H4-358076 | Dec 1992 | JP |
H5-226258 | Sep 1993 | JP |
H7-73994 | Mar 1995 | JP |
H11-335868 | Dec 1999 | JP |
3061288 | Apr 2000 | JP |
2001035692 | Feb 2001 | JP |
2002-121670 | Apr 2002 | JP |
2002-143795 | May 2002 | JP |
2003-193239 | Jul 2003 | JP |
2004-533703 | Nov 2004 | JP |
2005-5065 | Jan 2005 | JP |
2005-68444 | Mar 2005 | JP |
2005-243892 | Sep 2005 | JP |
2005-302681 | Oct 2005 | JP |
2006-164683 | Jun 2006 | JP |
2007-026781 | Feb 2007 | JP |
2007-280641 | Oct 2007 | JP |
2008-4814 | Jan 2008 | JP |
2008-112580 | May 2008 | JP |
2009-502554 | Jan 2009 | JP |
2009-534797 | Sep 2009 | JP |
2010-021140 | Jan 2010 | JP |
2010530115 | Sep 2010 | JP |
2011-530155 | Dec 2011 | JP |
2013-520836 | Jun 2013 | JP |
2013-0251367 | Dec 2013 | JP |
2014-518947 | Aug 2014 | JP |
2008-0024693 | Mar 2008 | KR |
10-1179650 | Sep 2012 | KR |
2239532 | Nov 2004 | RU |
200304343 | Sep 2003 | TW |
I233144 | May 2005 | TW |
I235408 | Jul 2005 | TW |
I244673 | Dec 2005 | TW |
200714742 | Apr 2007 | TW |
I294257 | Mar 2008 | TW |
9616531 | May 1996 | WO |
02079815 | Oct 2002 | WO |
2005-047180 | May 2005 | WO |
2007015779 | Feb 2007 | WO |
2012160145 | Nov 2012 | WO |
2015022621 | Feb 2015 | WO |
2016089424 | Jun 2016 | WO |
2016089427 | Jun 2016 | WO |
2016104076 | Jun 2016 | WO |
Entry |
---|
Garcia-Cespedes, et al., “Carbon nanotubes grown by asymmetric bipolar pulsed-DC PECVD”, Diamond and Related Materials, vol. 16, pp. 1131-1135, Jan. 25, 2007. |
PCT International Search Report and Written Opinion, issued in PCT/US 09/52679 dated Sep. 28, 2009, 12 pages. |
L. Bardos, et al., “Linear Arc Discharge (LAD)—Radio Frequency Hollow Cathode Plasma Source for Low Pressure Processing,” 1996 Society of Vacuum Coaters, 39th Annual Technical Conference Proceedings (1996), ISSN 0737-5921, pp. 128-132. |
L. Bardos, et al., “PECVD by Hollow Cathodes,” 1998 Society of Vacuum Coaters, 41st Annual Technical Conference Proceedings (1998), ISSN 0737-5921, pp. 315-320. |
A. Belkind, et al., “Linear Plasma Source for Reactive Etching and Surface Modification,” 1995 Society of Vacuum Coaters, 38th Annual Technical Conference Proceedings (1995), ISSN 0737-5921, pp. 432-436. |
A. E. Delahoy, et al., “Transparent and semitransparent conducting film deposition by reactive-environment, hollow cathode sputtering,” American Vacuum Society, J. Vac. Sci, Technol. A 23(4), Jul./Aug. 2005, pp. 1215-1220. |
J. Madocks, et al., “Large Area Plasma Enhanced Chemical Vapor Deposition of SiO2 on Glass and Plastic,” 2007 Society of Vacuum Coaters, 50th Annual Technical Conference Proceedings (2007), ISSN 0737-5921, pp. 233-238. |
A.A. Pradhan, et al., “High Deposition Rate Reactive Sputtering with Hollow Cathode,” 2002 Society of Vacuum Coaters, 45th Annual Technical Conference Proceedings (2002), ISSN 0737-5921, pp. 96-100. |
C. M. Horwitz, “Silicon deposition in diode and hollow-cathode systems,” 1989 American Vacuum Society, J. Vac. Sci. Technol. B 7 (3), May/Jun. 1989, pp. 443-449. |
S.K. Deb, “The Role of Vacuum Coatings in Cost-Effective Photovoltaic Technologies,” Society of Vacuum Coaters, 51st Annual Technical Conference Proceedings, Apr. 19-24, 2008, ISSN 0737-5921, pp. 101-106. |
Japanese Office Action issued in JP 2011-522159 dated Jun. 25, 2013, including English language translation, 8 pages. |
Argentine Office Action issued in AR 072911 A1, dated Jun. 11, 2013, 4 pages. |
Eurasian Office Action issued in EA 201100298 dated Mar. 16, 2013, 2 pages. |
Philippine Office Action issued in PH 1/2011/500255 dated Jul. 16, 2013, 1 page. |
Japanese Office Action issued in JP 2011-522159 dated Mar. 18. 2014, including English language translation, 8 pages. |
M. Mildner et al., “13.56 MHz hollow cathode jet matrix plasma source for large area surface coating,” Surface and Coatings Technology, vol. 112, pp. 366-372, XP000983344 (1999). |
Extended European Search Report, issued in EP 09805431.5 dated Aug. 4, 2014, 16 pages. |
Taiwanese Office Action, issued in TW 098126292 dated Mar. 23, 2015, including English language translation, 41 pages. |
Korean Office Action, issued in KR 10-2011-7005282 dated Aug. 22, 2015, including English language translation, 21 pages. |
Chinese Office Action, issued in CN 2009801395606 dated Dec. 29, 2014, including English language translation, 9 pages. |
D. Child et al., “Enhanced Hollow Cathode Plasma Source for Low Pressure Electron-Beam Deposition Processes”, 2014 Society of Vacuum Coaters 505/856-7188, ISSN 0737-5921, May, 2014, 6 pages. |
B. Buchholtz, “Physics of Ion Beam Sources” 7 pages. |
International Search Report and Written Opinion, issued in PCT/US2014/068919 dated Feb. 24, 2015, 13 pages. |
International Search Report and Written Opinion, issued in PCT/US14/68858 dated Mar. 5, 2015, 12 pages. |
M. Proschek et al., “The effect of phase difference between powered electrodes on RF plasmas”, Plasma Sources Sci. Technol. 14, 2005, 407-411. |
United Arab Emirates Office Action issued in UAE 119/2011 dated Apr. 10, 2016, 17 pages. |
Chinese Office Action, issued in CN 201410641340.2 dated Jun. 2, 2016, including English language translation, 11 pages. |
Japanese Office Action, issued in JP 2015-134085 dated Aug. 23, 2016, including English language translation, 9 pages. |
Japanese Office Action, issued in JP 2015-134098 dated Aug. 30, 2016, including English language translation, 10 pages. |
Japanese Office Action, issued in JP 2015-134106 dated Aug. 30, 2016, including English language translation, 10 pages. |
Japanese Office Action, issued in JP 2015-134112 dated Aug. 2, 2016, including English language translation, 5 pages. |
Japanese Office Action, issued in JP 2015-134116 dated Aug. 30, 2016, including English language translation, 10 pages. |
European Search Report, issued in EP 09805431.5 dated Apr. 8, 2016, 6 pages. |
Taiwanese Office Action, issued in TW 10521126650, dated Sep. 9, 2016, 10 pages. |
Taiwanese Office Action, issued in TW 10521126670, dated Sep. 9, 2016, 9 pages. |
Chinese Office Action, issued in CN 201510505370.5 dated Nov. 28, 2016, including English language translation, 22 pages. |
International Search Report and Written Opinion, issued in PCT/US2016/061134 dated Jan. 9, 2017, 24 pages. |
International Search Report and Written Opinion, issued in PCT/US2016/060979 dated Jan. 9, 2017, 16 pages. |
Taiwanese Office Action, issued in TW 105103045, dated Dec. 30, 2016, including English language translation, 7 pages. |
Japanese Office Action, issued in JP 2015-134116 dated Mar. 28, 2017, including English language translation, 9 pages. |
Non-final Office Action, issued in U.S. Appl. No. 14/486,779, dated Mar. 24, 2017, 80 pages. |
Non-final Office Action, issued in U.S. Appl. No. 14/148,606, dated Apr. 6, 2017, 36 pages. |
Non-final Office Action, issued in U.S. Appl. No. 14/975,286, dated Apr. 7, 2017, 61 pages. |
Non-final Office Action, issued in U.S. Appl. No. 14/975,415, dated Apr. 14, 2017, 69 pages. |
Final Office Action, issued in U.S. Appl. No. 14/486,726, dated May 17, 2017, 38 pages. |
Chinese Office Action issued in CN 201510505383.2 dated May 17, 2017, including English language translation, 24 pages. |
Chinese Office Action issued in CN 201510505381.3 dated Jun. 5, 2017, including English language translation, 19 pages. |
Chinese Office Action issued in CN 201510505370.5 dated Jul. 21, 2017, including English language translation, 23 pages. |
Japanese Office Action issued in JP 2015-134112 dated Jul. 4, 2017, including English language translation, 5 pages. |
First Examination Report issued in Indian Patent Application No. 357/MUMNP/2011 dated Aug. 21, 2017, including English language translation, 10 pages. |
Office Action issued for U.S. Appl. No. 14/942,737, dated Sep. 22, 2016, 53 pages. |
Office Action issued in U.S. Appl. No. 14/486,779 dated Sep. 28, 2017, 8 pages. |
Office Action issued in U.S. Appl. No. 14/486,726 dated Oct. 6, 2017, 15 pages. |
Office Action issued in U.S. Appl. No. 14/148,606 dated Oct. 10, 2017, 18 pages. |
Office Action issued in U.S. Appl. No. 14/975,415 dated Oct. 19, 2017, 17 pages. |
Office Action issued in U.S. Appl. No. 14/975,286 dated Oct. 23, 2017, 17 pages. |
Notification of Reasons for Rejection issued in Japanese Application No. 2015-134116 dated Oct. 24, 2017, along with English translation, 9 pages. |
Notification issued in Eurasian Patent Application No. 201400544 dated Dec. 7, 2017, 4 pages. |
Office Action issued for Chinese Patent Application No. 201510505383.2 dated Feb. 1, 2018, along with English translation (4 pages). |
Office Action issued for Chinese Patent Application No. 201510505383.3 dated Feb. 1, 2018, along with English translation (15 pages). |
Office Action issued for Chinese Patent Application No. 201510505370.5 dated Feb. 5, 2018, along with English translation (23 pages). |
Office Action issued in U.S. Appl. No. 14/148,606 dated Apr. 5, 2018 (18 pages). |
Communication issued in European Patent Application No. 09805431.5 dated Apr. 12, 2018 (10 pages). |
Office Action issued for U.S. Appl. No. 14/975,415 dated May 4, 2018, 18 pages. |
Office Action issued for Japanese Patent Application No. 2017-093637 dated May 29, 2018, along with English translation, 10 pages. |
Office Action issued for U.S. Appl. No. 14/486,726 dated Jun. 22, 2018, 48 pages. |
Office Action issued for U.S. Appl. No. 14/975,286 dated Jun. 28, 2018, 44 pages. |
Examination Report, in corresponding Philippine Application No. 1/2015/500540, dated May 8, 2018, 2 pages. |
Extended European Search Report dated Jul. 3, 2018, issued in European Patent Application No. 14907243.1, 10 pages. |
Extended European Search Report dated Jul. 16, 2018, issued in European Patent Application No. 14907576.4, 9 pages. |
Office Action issued for Japanese Patent Application No. 2017-146662 dated Aug. 7, 2018, along with English translation, 6 pages. |
Office Action issued for Japanese Patent Application No. 2015-134106 dated Aug. 28, 2018, along with English translation, 13 pages. |
Office Action issued for Japanese Patent Application No. 2017-529720 dated Sep. 25, 2018, along with English translation, 12 pages. |
Office Action issued for U.S. Appl. No. 15/532,855 dated Oct. 12, 2018, 19 pages. |
Office Action issued for Eurasian Patent Application No. 201791237 dated Dec. 26, 2018, along with English translation, 4 pages. |
Office Action issued for Chinese Patent Application No. 201510505370.5 dated Dec. 14, 2018, along with English translation, 6 pages. |
Office Action issued for U.S. Appl. No. 15/532,845 dated Dec. 31, 2018, 33 pages. |
Office Action issued for Japanese Patent Application No. 2017-529717 dated Nov. 27, 2018, along with English translation, 4 pages. |
Office Action issued for U.S. Appl. No. 14/975,415 dated Dec. 13, 2018, 16 pages. |
Office Action issued for Eurasian Patent Application No. 201791234 dated Dec. 11, 2018, along with English translation, 2 pages. |
Office Action issued for Chinese Patent Application No. 201480084542.X dated Dec. 29, 2018, along with English translation, 24 pages. |
Office Action issued for Chinese Patent Application No. 20148004528.X dated Feb. 28, 2019, along with English translation, 18 pages. |
Office Action issued for Japanese Patent Application No. 2017-146662 dated Mar. 26, 2019, along with English translation, 11 pages. |
Examination Report, in corresponding Philippine Patent Application No. 1/2015/500539, dated Apr. 10, 2019, 5 pages. |
Office Action issued for U.S. Appl. No. 15/532,855 dated May 2, 2019, 57 pages. |
Office Action issued for Japanese Patent Application No. 2018-532069 dated May 28, 2019, along with English translation, 15 pages. |
Office Action issued in Brazillian Patent Application No. PI0916880-0 dated May 28, 2019, 7 pages. |
Extended European Search Report issued in European Patent Application No. 16866871.3, dated Jul. 3, 2019, 10 pages. |
Substantive Examination Report issued in Philippine Patent Application No. 1/2015/500541, dated Jul. 5, 2019, 7 pages. |
Office Action issued for U.S. Appl. No. 15/532,845 dated Jul. 9, 2019, 67 pages. |
Extended European Search Report issued in European Patent Application No. 16876262.3, dated Jul. 19, 2019, 11 pages. |
Office Action issued for Japanese Patent Application No. 2017-529720 dated Jul. 23, 2019, along with English translation, 17 pages. |
Office Action issued in Chinese Patent Application No. 201680078860.4, dated Aug. 1, 2019, with English translation, 31 pages. |
Office Action issued in Indonesian Patent Application No. P-00201702394 dated Aug. 19, 2019 (no English translation), 3 pages. |
Office Action issued in Eurasian Patent Application No. 201791234, dated Aug. 27, 2019, with English translation, 3 pages. |
Office Action issued in connection with Eurasian Patent Application No. 201791237, dated Aug. 29, 2019, with English translation, 3 pages. |
Office Action issued in Chinese Patent Application No. 201480084542.X, dated Sep. 11, 2019, with English translation, 22 pages. |
Office Action issued in Chinese Patent Application No. 201680081988.6, dated Sep. 25, 2019, with English translation, 35 pages. |
Office Action issued in Indonesian Patent Application No. P-00201704208, dated Oct. 8, 2019 (no English translation), 3 pages. |
Office Action issued in Eurasian Patent Application No. 201891175, dated Oct. 16, 2019, (no English translation), 2 pages. |
Number | Date | Country | |
---|---|---|---|
20170309458 A1 | Oct 2017 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 14942737 | Nov 2015 | US |
Child | 15645774 | US |