EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`
`References cited herein:
` U.S. Pat. No. 6,853,142 (“’142 Patent”)
`
` D.V. Mozgrin, et al, High-Current Low-Pressure Quasi-Stationary Discharge in a
`Magnetic Field: Experimental Research, Plasma Physics Reports, Vol. 21, No. 5, 1995
`(“Mozgrin”)
`
` U.S. Pat. No. 6,190,512 (“Lantsman”)
`
` A. A. Kudryavtsev, et al, Ionization relaxation in a plasma produced by a pulsed inert-gas
`discharge, Sov. Phys. Tech. Phys. 28(1), January 1983 (“Kudryavtsev”)
`
` Dennis M. Manos & Daniel L. Flamm, Plasma Etching: An Introduction, Academic Press
`1989 (“Manos”)
`
` Milton Ohring, The Material Science of Thin Films, Academic Press, 1992 (“Ohring”)
`
` Donald L. Smith, Thin-Film Deposition: Principles & Practice, McGraw Hill, 1995
`(“Smith”)
`
`
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`[1pre.] An apparatus for
`generating a strongly-ionized
`plasma in a chamber, the
`apparatus comprising:
`
`The combination of Mozgrin and Lantsman discloses an
`apparatus for generating a strongly-ionized plasma in a
`chamber.
`
`‘142 Patent at claim 18 (“wherein the peak plasma density
`of the strongly-ionized plasma is greater than about
`1012 cm˗3”)
`
`Mozgrin at Fig 1
`
`Mozgrin at 400, right col, ¶ 4 (“To study the high-current
`forms of the discharge, we used two types of devices: a
`planar magnetron and a ystem with specifically shaped
`hollow electrodes.”)
`
`Mozgrin at 401, right col, ¶2 (“For pre-ionization … the
`initial plasma density in the 109 – 1011 cm-3 range.”)
`
`Mozgrin at 409, left col, ¶ 4 (“The implementation of the
`high-current magnetron discharge (regime 2) in sputtering
`… plasma density (exceeding 2x1013 cm-3).”)
`
`Mozgrin at 409, left col, ¶5 (“The high-current diffuse
`discharge (regime 3) is useful for producing large-volume
`
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`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`[1a.] an ionization source that
`generates a weakly-ionized
`plasma from a feed gas, the
`weakly-ionized plasma reducing
`the probability of developing an
`electrical breakdown condition in
`the chamber;
`
`uniform dense plasmas ni  1.5x1015cm-3…”).
`
`The combination of Mozgrin and Lantsman discloses an
`ionization source that generates a weakly-ionized plasma
`from a feed gas, the weakly-ionized plasma reducing the
`probability of developing an electrical breakdown
`condition in the chamber.
`
`‘142 Patent at 5:18-19 (“The weakly-ionized plasma is
`also referred to as a pre-ionized plasma.”)
`
`‘142 Patent at claim 17 (“wherein the peak plasma density
`of the weakly-ionized plasma is less than about
`1012 cm˗3”)
`
`Mozgrin at Figs. 1, 2, 3, 6, 7
`
`Mozgrin at 402, right col, ¶2 (“Figure 3 shows typical
`voltage and current oscillograms.… Part I in the voltage
`oscillogram represents the voltage of the stationary
`discharge (pre-ionization stage).”)
`
`Mozgrin at 401, right col, ¶2 (“[f]or pre-ionization, we
`used a stationary magnetron discharge; … provided the
`initial plasma density in the 109 – 1011 cm˗3 range.”)
`
`Mozgrin at 400, right col, ¶ 3 (“We investigated the
`discharge regimes in various gas mixtures at 10-3 – 10
`torr…”)
`
`402, ¶ spanning left and right cols (“We studied the high-
`current discharge in wide ranges of discharge
`current…and operating pressure…using various gases
`(Ar, N2, SF6, and H2) or their mixtures of various
`composition…”)
`
`Mozgrin at 401, left col, ¶ 1 (“The [plasma] discharge had
`an annular shape and was adjacent to the cathode.”)
`
`Mozgrin at 406, right col, ¶3 (“pre-ionization was not
`necessary; however, in this case, the probability of
`discharge transferring to arc mode increased.”)
`
`Mozgrin at 400, left col, ¶ 3 (“Some experiments on
`magnetron systems of various geometry showed that
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`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`[1b.] a power supply that supplies
`power to the weakly-ionized
`plasma though an electrical pulse
`applied across the weakly-ionized
`plasma, the electrical pulse
`having a magnitude and a rise-
`time that is sufficient to increase
`the density of the weakly-ionized
`plasma to generate a strongly-
`ionized plasma; and
`
`discharge regimes which do not transit to arcs can be
`obtained even at high currents.”)
`
`Background:
`
`Manos at 231 (“We shall … [include] information on
`unipolar arcs. These are a problem…”)
`
`Manos at 237 (“When such an arc occurs, the metal
`object is melted at the arc spot. The metal is explosively
`released…. How does one prevent such an arc? There
`are several methods…”)
`
`The combination of Mozgrin and Lantsman discloses a
`power supply that supplies power to the weakly-ionized
`plasma though an electrical pulse applied across the
`weakly-ionized plasma, the electrical pulse having a
`magnitude and a rise-time that is sufficient to increase the
`density of the weakly-ionized plasma to generate a
`strongly-ionized plasma.
`
`‘142 Patent at 1:41-43 (“Magnetron sputtering systems
`use magnetic fields that are shaped to trap and to
`concentrate secondary electrons, which are produced by
`ion bombardment of the target surface.”)
`
`‘142 Patent at 1:37-40 (“The plasma is replenished by
`electron-ion pairs formed by the collision of neutral
`molecules with secondary electrons generated at the target
`surface.”)
`
`Mozgrin at Figs. 1, 2, 3
`
`Mozgrin at 402, right col, ¶ 2 (“Part 1 in the voltage
`oscillogram represents the voltage of the stationary
`discharge (pre-ionization stage).”)
`
`Mozgrin at 401, right col, ¶ 1 (“Thus, the supply unit was
`made providing square voltage and current pulses with
`[rise] times (leading edge) of 5 – 60 µs…”)
`
`[1c.] a gas line that supplies feed
`gas to the strongly-ionized
`plasma, the feed gas diffusing the
`strongly-ionized plasma, thereby
`
`The combination of Mozgrin and Lantsman discloses a
`gas line that supplies feed gas to the strongly-ionized
`plasma, the feed gas diffusing the strongly-ionized
`plasma, thereby allowing additional power from the
`
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`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`pulsed power supply to be absorbed by the strongly-
`ionized plasma.
`
`It would have been obvious to one of ordinary skill to
`continue to add the feed gas in Mozgrin during production
`of the strongly-ionized plasma (i.e., during either of
`regions 2 or 3). Such addition of the feed gas would have
`both diffused the strongly-ionized plasma and allowed
`additional power from Mozgrin’s repeating voltage pulses
`to be absorbed by the strongly-ionized plasma.
`
`‘142 Patent at 2:21-34 (“FIG. 1 illustrates a cross-
`sectional view of a known plasma generating apparatus
`100…. A feed gas from feed gas source 109, such as an
`argon gas source, is introduced into the vacuum chamber
`104 through a gas inlet 110. The gas flow is controlled by
`a valve 112.”)
`
`Mozgrin at Figs. 1 and 3
`
`Mozgrin at ¶ spanning pp. 403-404 (“The … repetition
`frequency was 10 Hz….”).
`
`Mozgrin at 401, left col, ¶ 4 (“[A]pplying a square voltage
`pulse to the discharge gap which was filled up with either
`neutral or pre-ionized gas.”)
`
`
`
`Lantsman at Fig. 6
`
`allowing additional power from
`the pulsed power supply to be
`absorbed by the strongly-ionized
`plasma.
`
`
`Lantsman at 3:9-13 (“[A]t the beginning of processing,
`this switch is closed and gas is introduced into the
`
`
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`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`chamber. When the plasma process is completed, the gas
`flow is stopped….”)
`
`Lantsman at 4:36-38 (“To end processing, primary supply
`10 is disabled, reducing the plasma current and deposition
`on the wafer. Then, gas flow is terminated….”)
`
`Lantsman at 5:39-42 (“Sometime thereafter, gas flow is
`initiated and the gas flow and pressure (trace 48) begin to
`ramp upwards toward normal processing levels.”)
`
`Lantsman at 5:42-45
`
`Lantsman at 2:48-51 (“This secondary power supply ‘pre-
`ignites’ the plasma so that when the primary power supply
`is applied, the system smoothly transitions to final plasma
`development and deposition.”)
`
`It would have been obvious to one of ordinary skill to
`continue to apply the feed gas during Mozgrin’s regions 1
`and 2 as taught by Lantsman. Such a continuous
`introduction of feed gas balances gas withdrawn by the
`vacuum system (e.g., as shown in the drawings from
`Ohring and Smith, copied below) so as to maintain a
`desired pressure.
`
`One of ordinary skill would have been motivated to
`combine Mozgrin and Lantsman. Both Mozgrin and
`Lantsman are directed to sputtering using plasma. See
`Mozgrin at 409, left col, ¶ 4 (“The implementation of the
`high-current magnetron discharge (regime 2) in sputtering
`or layer-deposition technologies provides an enhancement
`in the flux of deposited materials and plasma density….”);
`see also Lantsman at 1:6-8 (“This invention relates to
`reduction of device damage in plasma processes,
`including DC (magnetron or non-magnetron) sputtering,
`and RF sputtering.”). Both references also relate to
`sputtering systems that use two power supplies, one for
`pre-ionization and one for deposition. See Lantsman at
`4:45-47 (“[T]he secondary [power] supply 32 is used to
`pre-ignite the plasma, whereas the primary [power] supply
`10 is used to generate deposition.”); see Mozgrin at Fig. 2.
`(showing the “high-voltage supply unit” and the
`“stationary discharge supply unit”)
`
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`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`
`Moreover, both Mozgrin and Lantsman are concerned
`with generating plasma while avoiding arcing. See
`Mozgrin at 400, right col, ¶ 3 (“The main purpose of this
`work was to study experimentally a high-power
`noncontracted quasi-stationary discharge in crossed fields
`of various geometry and to determine their parameter
`ranges.”); see also Lantsman at 1:51-59 (“Furthermore,
`arcing which can be produced by overvoltages can cause
`local overheating of the target, leading to evaporation or
`flaking of target material into the processing chamber and
`causing substrate particle contamination and device
`damage…. Thus, it is advantageous to avoid voltage
`spikes during processing whenever possible.”).
`
`Summarizing, Mozgrin and Lantsman relate to the same
`application. Further, one of ordinary skill would have
`been motivated to use Lantsman’s continuous gas flow in
`Mozgrin so as to maintain a desired pressure in the
`chamber. Finally, use of Lantsman’s continuous gas flow
`in Mozgrin would have been a combination of old
`elements in which each element behaved as expected.
`The combination of Mozgrin and Lantsman therefore
`teaches the function required by the “means for
`diffusing…”
`
`Background:
`Ohring at Fig. 3-13
`
`Smith at Fig. 3-1
`
`
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`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`2. The apparatus of claim 1
`wherein the power supply applies
`the electrical pulse across the
`weakly-ionized plasma to excite
`atoms in the weakly-ionized
`plasma and to generate secondary
`electrons, the secondary electrons
`ionizing the excited atoms,
`thereby creating the strongly-
`ionized plasma.
`
`
`The combination of Mozgrin, Lantsman, and Kudryavtsev
`discloses the power supply applies the electrical pulse
`across the weakly-ionized plasma to excite atoms in the
`weakly-ionized plasma and to generate secondary
`electrons, the secondary electrons ionizing the excited
`atoms, thereby creating the strongly-ionized plasma.
`
`See evidence cited in claim 1.
`
`‘142 Patent at 1:41-43 (“Magnetron sputtering systems
`use magnetic fields that are shaped to trap and to
`concentrate secondary electrons, which are produced by
`ion bombardment of the target surface.”)
`
`‘142 Patent at 1:37-40 (“The plasma is replenished by
`electron-ion pairs formed by the collision of neutral
`molecules with secondary electrons generated at the target
`surface.”)
`
`Mozgrin at Figs. 1, 2, 3
`
`Mozgrin at 402, right col, ¶ 2 (“Part 1 in the voltage
`oscillogram represents the voltage of the stationary
`discharge (pre-ionization stage).”)
`
`Mozgrin at 401, right col, ¶ 1 (“Thus, the supply unit was
`made providing square voltage and current pulses with
`[rise] times (leading edge) of 5 – 60 µs…”)
`
`Mozgrin at 401, ¶ spanning left and right cols
`(“[d]esigning the [pulsed supply] unit, we took into
`account the dependences which had been obtained in
`[Kudryavtsev] of ionization relaxation on pre-ionization
`parameters, pressure, and pulse voltage amplitude.”)
`
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`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`
`Mozgrin 403, right col, ¶4 (“Regime 2 was characterized
`by intense cathode sputtering due to both high energy and
`density of ion flow.”)
`
`Kudryavtsev at Figs. 1, 6
`
`Kudryavtsev at 34, right col, ¶ 4 (“[s]ince the effects
`studied in this work are characteristic of ionization
`whenever a field is suddenly applied to a weakly ionized
`gas, they must be allowed for when studying emission
`mechanisms in pulsed gas lasers, gas breakdown, laser
`sparks, etc.”)
`
`Kudryavtsev at 31, right col, ¶ 6 (“For nearly stationary n2
`[excited atom density] values … there is an explosive
`increase in ne [plasma density]. The subsequent increase
`in ne then reaches its maximum value, equal to the rate of
`excitation [equation omitted], which is several orders of
`magnitude greater than the ionization rate during the
`initial stage.”)
`
`Kudryavtsev at 31, right col, ¶ 7 (“The behavior of the
`increase in ne with time thus enables us to arbitrarily
`divide the ionization process into two stages, which we
`will call the slow and fast growth stages. Fig. 1 illustrates
`the relationships between the main electron currents in
`terms of the atomic energy levels during the slow and fast
`stages.”)
`
`Kudryavtsev at Abstract (“in a pulsed inert-gas discharge
`plasma at moderate pressures… [i]t is shown that the
`electron density increases explosively in time due to
`accumulation of atoms in the lowest excited states.”)
`
`Kudryavtsev at Equation 1
`
`Kudryavtsev at 30, right col, last ¶ (“n2, and ne are the
`atomic densities in the … first excited states and the
`electron density, respectively … 2e [is] the rate
`coefficient[]….”)
`
`See evidence cited in limitation [1pre] of claim 1.
`It would have been obvious to one of ordinary skill to
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`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`combine Mozgrin with Kudryavtsev. Mozgrin itself cites
`Kudryavtsev. Moreover, Mozgrin explicitly notes that it
`was designed in accordance with Kudryavtsev. Mozgrin
`at 401, ¶ spanning left and right columns (“Designing the
`[pulsed supply] unit, we took into account the
`dependences which had been obtained in
`[Kudryavtsev].”). Further, Kudryavtsev states, “[s]ince
`the effects studied in this work are characteristic of
`ionization whenever a field is suddenly applied to a
`weakly ionized gas, they must be allowed for when
`studying emission mechanisms in pulsed gas lasers, gas
`breakdown, laser sparks, etc.” Kudryavtsev at 34, right
`col, ¶ 4. Because Mozgrin applies voltage pulses that
`“suddenly generate an electric field,” one of ordinary skill
`reading Mozgrin would have been motivated to consider
`Kudryavtsev to further appreciate the effects of applying
`Mozgrin’s pulse.
`
`Background:
`Ohring at 104 (“Microscopically, positive gas ions in the
`discharge strike the cathode plate and eject neutral target
`atoms…. In addition, other particles (secondary electrons,
`desorbed gases, and negative ions) … are emitted from
`the target.”)
`
`The combination of Mozgrin and Lantsman discloses a
`method for generating a strongly-ionized plasma in a
`chamber.
`
`See evidence cited in claim 1 preamble.
`
`[10pre.] A method for generating
`a strongly-ionized plasma in a
`chamber, the method comprising:
`
`[10a.] ionizing a feed gas to form
`a weakly-ionized plasma that
`reduces the probability of
`developing an electrical
`breakdown condition in the
`chamber;
`
`The combination of Mozgrin and Lantsman discloses
`ionizing a feed gas to form a weakly-ionized plasma that
`reduces the probability of developing an electrical
`breakdown condition in the chamber.
`
`See evidence cited in claim 1(a)
`
`[10b.] supplying power to the
`weakly-ionized plasma by
`applying an electrical pulse across
`the weakly-ionized plasma, the
`electrical pulse having a
`magnitude and a rise-time that is
`
`The combination of Mozgrin and Lantsman discloses
`supplying power to the weakly-ionized plasma by
`applying an electrical pulse across the weakly-ionized
`plasma, the electrical pulse having a magnitude and a rise-
`time that is sufficient to increase the density of the
`weakly-ionized plasma to generate a strongly-ionized
`
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`
`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`sufficient to increase the density
`of the weakly-ionized plasma to
`generate a strongly-ionized
`plasma; and
`
`plasma.
`
`See evidence cited in claim 1(b)
`
`[10c.] diffusing the strongly-
`ionized plasma with additional
`feed gas thereby allowing the
`strongly-ionized plasma to absorb
`additional energy from the power
`supply.
`
`The combination of Mozgrin and Lantsman discloses
`diffusing the strongly-ionized plasma with additional feed
`gas thereby allowing the strongly-ionized plasma to
`absorb additional energy from the power supply.
`
`See evidence cited in claim 1(c)
`
`11. The method of claim 10
`wherein the applying the
`electrical pulse across the weakly-
`ionized plasma excites atoms in
`the weakly-ionized plasma and
`generates secondary electrons, the
`secondary electrons ionizing the
`excited atoms, thereby creating a
`strongly-ionized plasma.
`
`The combination of Mozgrin, Lantsman, and Kudryavtsev
`discloses the applying the electrical pulse across the
`weakly-ionized plasma excites atoms in the weakly-
`ionized plasma and generates secondary electrons, the
`secondary electrons ionizing the excited atoms, thereby
`creating a strongly-ionized plasma.
`
`See evidence cited in claim 10
`
`‘142 Patent at 1:41-43 (“Magnetron sputtering systems
`use magnetic fields that are shaped to trap and to
`concentrate secondary electrons, which are produced by
`ion bombardment of the target surface.”)
`
`‘142 Patent at 1:37-40 (“The plasma is replenished by
`electron-ion pairs formed by the collision of neutral
`molecules with secondary electrons generated at the target
`surface.”)
`
`Mozgrin at Figs. 1, 2, 3
`
`Mozgrin at 402, right col, ¶ 2 (“Part 1 in the voltage
`oscillogram represents the voltage of the stationary
`discharge (pre-ionization stage).”)
`
`Mozgrin at 401, right col, ¶ 1 (“Thus, the supply unit was
`made providing square voltage and current pulses with
`[rise] times (leading edge) of 5 – 60 µs…”)
`
`Mozgrin at 401, ¶ spanning left and right cols
`(“[d]esigning the [pulsed supply] unit, we took into
`account the dependences which had been obtained in
`[Kudryavtsev] of ionization relaxation on pre-ionization
`
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`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`
`parameters, pressure, and pulse voltage amplitude.”)
`
`Mozgrin 403, right col, ¶4 (“Regime 2 was characterized
`by intense cathode sputtering due to both high energy and
`density of ion flow.”)
`
`Kudryavtsev at Figs. 1, 6
`
`Kudryavtsev at 34, right col, ¶ 4 (“[s]ince the effects
`studied in this work are characteristic of ionization
`whenever a field is suddenly applied to a weakly ionized
`gas, they must be allowed for when studying emission
`mechanisms in pulsed gas lasers, gas breakdown, laser
`sparks, etc.”)
`
`Kudryavtsev at 31, right col, ¶ 6 (“For nearly stationary n2
`[excited atom density] values … there is an explosive
`increase in ne [plasma density]. The subsequent increase
`in ne then reaches its maximum value, equal to the rate of
`excitation [equation omitted], which is several orders of
`magnitude greater than the ionization rate during the
`initial stage.”)
`
`Kudryavtsev at 31, right col, ¶ 7 (“The behavior of the
`increase in ne with time thus enables us to arbitrarily
`divide the ionization process into two stages, which we
`will call the slow and fast growth stages. Fig. 1 illustrates
`the relationships between the main electron currents in
`terms of the atomic energy levels during the slow and fast
`stages.”)
`
`Kudryavtsev at Abstract (“in a pulsed inert-gas discharge
`plasma at moderate pressures… [i]t is shown that the
`electron density increases explosively in time due to
`accumulation of atoms in the lowest excited states.”)
`
`Kudryavtsev at Equation 1
`
`Kudryavtsev at 30, right col, last ¶ (“n2, and ne are the
`atomic densities in the … first excited states and the
`electron density, respectively … 2e [is] the rate
`coefficient[]….”)
`
`See evidence cited in limitation [1pre] of claim 1.
`
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`
`EXHIBIT D.04
`U.S. Patent No. 6,853,142
`
`‘142 Claims 2 and 11
`
`Mozgrin in view of Lantsman and Kudryavtsev
`
`
`It would have been obvious to one of ordinary skill to
`combine Mozgrin with Kudryavtsev. Mozgrin itself cites
`Kudryavtsev. Moreover, Mozgrin explicitly notes that it
`was designed in accordance with Kudryavtsev. Mozgrin
`at 401, ¶ spanning left and right columns (“Designing the
`[pulsed supply] unit, we took into account the
`dependences which had been obtained in
`[Kudryavtsev].”). Further, Kudryavtsev states, “[s]ince
`the effects studied in this work are characteristic of
`ionization whenever a field is suddenly applied to a
`weakly ionized gas, they must be allowed for when
`studying emission mechanisms in pulsed gas lasers, gas
`breakdown, laser sparks, etc.” Kudryavtsev at 34, right
`col, ¶ 4. Because Mozgrin applies voltage pulses that
`“suddenly generate an electric field,” one of ordinary skill
`reading Mozgrin would have been motivated to consider
`Kudryavtsev to further appreciate the effects of applying
`Mozgrin’s pulse.
`
`Background:
`Ohring at 104 (“Microscopically, positive gas ions in the
`discharge strike the cathode plate and eject neutral target
`atoms…. In addition, other particles (secondary electrons,
`desorbed gases, and negative ions) … are emitted from
`the target.”)
`
`
`
`
`
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