EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`References cited herein:
`
`(cid:120) U.S. Patent No. 7,147,759 (“‘759 Patent”)
`
`(cid:120) U.S. Pat. No. 6,413,382 (“Wang”)
`
`(cid:120) 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”)
`
`(cid:120) D.V. Mozgrin, High-Current Low-Pressure Quasi-Stationary Discharge in a Magnetic
`Field: Experimental Research, Thesis at Moscow Engineering Physics Institute, 1994
`(“Mozgrin Thesis”)
`
`Claims 44 and 49
`
`[1pre.] A magnetically
`enhanced sputtering
`source comprising:
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`The combination of Wang with Kudryavtsev discloses a magnetically
`enhanced sputtering source.
`
`Wang at Title (“Pulsed sputtering with a small rotating magnetron.”).
`
`[1a.] an anode;
`
`The combination of Wang with Kudryavtsev discloses an anode.
`
`‘759 Patent at Fig. 1
`
`
`‘759 Patent at Fig. 1 (“FIG. 1 illustrates a cross-sectional view of a
`known magnetron sputtering apparatus having a pulsed power
`source.”)
`
`‘759 Patent at 3:40-41 (“an anode 130 is positioned in the vacuum
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`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`chamber 104 proximate to the cathode assembly.”)
`
`Wang at Fig. 1
`
`Wang at 3:66-4:1 (“A grounded shield 24 protects the chamber walls
`from sputter deposition and also acts as a grounded anode for the
`cathode of the negatively biased target 14.”)
`
`The combination of Wang with Kudryavtsev discloses a cathode
`assembly that is positioned adjacent to the anode, the cathode
`assembly including a sputtering target.
`
`‘759 Patent at Fig. 1
`
`[1b.] a cathode
`assembly that is
`positioned adjacent to
`the anode, the cathode
`assembly including a
`sputtering target;
`
`
`‘759 Patent at Fig. 1 (“FIG. 1 illustrates a cross-sectional view of a
`known magnetron sputtering apparatus having a pulsed power
`source.”)
`
`‘759 Patent at 3:40-41 (“an anode 130 is positioned in the vacuum
`chamber 104 proximate to the cathode assembly.”)
`
`Wang at Fig. 1
`
`Wang at 3:66-4:1 (“A grounded shield 24 protects the chamber walls
`from sputter deposition and also acts as a grounded anode for the
`cathode of the negatively biased target 14.”)
`
`[1c.] an ionization
`
`The combination of Wang with Kudryavtsev discloses an ionization
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`
`
`Claims 44 and 49
`
`source that generates a
`weakly-ionized
`plasma proximate to
`the anode and the
`cathode assembly;
`
`[1d.] a magnet that is
`positioned to generate
`a magnetic field
`proximate to the
`weakly-ionized
`plasma, the magnetic
`field substantially
`trapping electrons in
`the weakly-ionized
`plasma proximate to
`the sputtering target;
`and
`
`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`source that generates a weakly-ionized plasma proximate to the
`anode and the cathode assembly.
`
`Wang at Fig. 1.
`
`Wang at 7:17-31 (“The background power level PB is chosen to
`exceed the minimum power necessary to support a plasma... [T]he
`application of the high peak power PP quickly causes the already
`existing plasma to spread and increases the density of the plasma.”)
`
`Wang at 7:19-25 (“Preferably, the peak power PP is at least 10 times
`the background power PB … and most preferably 1000 times to
`achieve the greatest effect of the invention. A background power PB
`of 1 kW [causes] little if any actual sputter deposition.”)
`
`Wang at 4:23-31 (“A small rotatable magnetron 40 is thus creating a
`region 42 of a high-density plasma (HDP)…”)
`
`Wang at 7:47-49 (“The initial plasma ignition needs to be performed
`only once and at much lower power levels so that particulates
`produced by arcing are much reduced.”).
`
`The combination of Wang with Kudryavtsev discloses a magnet that
`is positioned to generate a magnetic field proximate to the weakly-
`ionized plasma, the magnetic field substantially trapping electrons in
`the weakly-ionized plasma proximate to the sputtering target.
`
`‘759 Patent at 3:10-12 (“FIG. 1 shows a cross-sectional view of a
`known magnetron sputtering apparatus 100…” that has a magnet
`126.”)
`
`‘759 Patent at 4:4-10 [describing the prior art Fig. 1] (“The
`electrons, which cause ionization, are generally confined by the
`magnetic fields produced by the magnet 126. The magnetic
`confinement is strongest in a confinement region 142….”)
`
`Wang at Fig. 1.
`
`Wang at 4:23-27 (“A small rotatable magnetron 40 is disposed in the
`back of the target 14 to create a magnetic field near the face of the
`target 14 which traps electrons from the plasma to increase the
`electron density.”)
`
`[1e.] a power supply
`
`The combination of Wang with Kudryavtsev discloses a power
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`
`
`Claims 44 and 49
`
`generating a voltage
`pulse that produces an
`electric field between
`the cathode assembly
`and the anode, the
`power supply being
`configured to generate
`the voltage pulse with
`an amplitude and a
`rise time that increases
`an excitation rate of
`ground state atoms
`that are present in the
`weakly-ionized
`plasma to create a
`multi-step ionization
`process that generates
`a strongly-ionized
`plasma, which
`comprises ions that
`sputter target material,
`from the weakly-
`ionized plasma, the
`multi-step ionization
`process comprising
`exciting the ground
`state atoms to generate
`excited atoms, and
`then ionizing the
`excited atoms within
`the weakly-ionized
`plasma without
`forming an arc
`discharge.
`
`
`
`
`
`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`supply generating a voltage pulse that produces an electric field
`between the cathode assembly and the anode, the power supply being
`configured to generate the voltage pulse with an amplitude and a rise
`time that increases an excitation rate of ground state atoms that are
`present in the weakly-ionized plasma to create a multi-step ionization
`process that generates a strongly-ionized plasma, which comprises
`ions that sputter target material, from the weakly-ionized plasma, the
`multi-step ionization process comprising exciting the ground state
`atoms to generate excited atoms, and then ionizing the excited atoms
`within the weakly-ionized plasma without forming an arc discharge.
`
`‘759 Patent at Fig. 5
`
`Wang at Figs. 6, 7.
`
`Wang at 7:61-62 (“The pulsed DC power supply 80 produces a train
`of negative voltage pulses.”).
`
`Wang at 5:23-27 (“[The pulse’s] exact shape depends on the design
`of the pulsed DC power supply 80, and significant rise times and fall
`times are expected.”).
`
`Wang at 4:29-31 (“increases the sputtering rate...”).
`
`Wang at 7:19-25 (“Preferably, the peak power level PP is at least 10
`times the background power level PB, … most preferably 1000 times
`to achieve the greatest effects of the invention. A background power
`PB of 1 kW will typically be sufficient…”)
`
`Wang at 7:31-39 (“The SIP reactor is advantageous for a low-power,
`low-pressure background period since the small rotating SIP
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`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`magnetron can maintain a plasma at a lower power and lower
`pressure than can a larger stationary magnetron. However, it is
`possible to combine highly ionized sputtering during the pulses With
`significant neutral sputtering during the back ground period.”).
`
`Wang at 7:3-6 (“Plasma ignition, particularly in plasma sputter
`reactors, has a tendency to generate particles during the initial arcing,
`which may dislodge large particles from the target or chamber.”)
`
`Wang at 7:47-49 (“The initial plasma ignition needs be performed
`only once and at much lower power levels so that particulates
`produced by arcing are much reduced.”).
`
`Wang at 7:13-28 (“Accordingly, it is advantageous to use a target
`power waveform illustrated in FIG. 6… As a result, once the plasma
`has been ignited at the beginning of sputtering prior to the illustrated
`waveform…”).
`
`Kudryavtsev at 34, right col, ¶ 4 (“Since 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 Fig. 1
`
`Kudryavtsev at Fig. 6
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`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`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 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 Abstract (“[I]n 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.”)
`
`If one of ordinary skill, applying Wang’s power levels did not
`experience Kudryavtsev’s “explosive increase” in plasma density, it
`would have been obvious to adjust the operating parameters, e.g.,
`increase the pulse length and/or pressure, so as to trigger
`Kudryavtsev’s fast stage of ionization. One of ordinary skill would
`have been motivated to use Kudryavtsev’s fast stage of ionization in
`Wang so as to increase plasma density and thereby increase the
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`

`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`sputtering rate. Further, use of Kudryavtsev’s fast stage in Wang
`would have been a combination of old elements that yielded
`predictable results of increasing plasma density and multi-step
`ionization.
`
`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 (Ex. 1004). Because
`Wang applies voltage pulses that “suddenly generate an electric
`field,” one of ordinary skill reading Wang would have been
`motivated to consider Kudryavtsev and to use Kudryavtsev’s fast
`stage in Wang.
`
`The combination of Wang and Kudryavtsev discloses ionizing a feed
`gas to generate a weakly-ionized plasma proximate to a sputtering
`target.
`
`Wang at Fig. 1
`
`Wang at 4:5-6 (“A sputter working gas such as argon is supplied
`from a gas source 32….”).
`
`Wang at 4:20-21 (“… a reactive gas, for example nitrogen is supplied
`to the processing space 22….”).
`
`Wang at 7:17-31 (“The background power level PB is chosen to
`exceed the minimum power necessary to support a plasma... [T]he
`application of the high peak power PP quickly causes the already
`existing plasma to spread and increases the density of the plasma.”)
`
`Wang at 7:19-25 (“Preferably, the peak power PP is at least 10 times
`the background power PB … and most preferably 1000 times to
`achieve the greatest effect of the invention. A background power PB
`of 1 kW [causes] little if any actual sputter deposition.”)
`
`Wang at 4:23-31 (“A small rotatable magnetron 40 is thus creating a
`region 42 of a high-density plasma (HDP)…”)
`
`The combination of Wang and Kudryavtsev discloses generating a
`magnetic field proximate to the weakly-ionized plasma, the magnetic
`field substantially trapping electrons in the weakly-ionized plasma
`
`7
`
`[20a.] ionizing a feed
`gas to generate a
`weakly-ionized
`plasma proximate to a
`sputtering target;
`
`[20b.] generating a
`magnetic field
`proximate to the
`weakly-ionized
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`
`
`Claims 44 and 49
`
`plasma, the magnetic
`field substantially
`trapping electrons in
`the weakly-ionized
`plasma proximate to
`the sputtering target;
`and
`
`[20c.] applying a
`voltage pulse to the
`weakly-ionized
`plasma, an amplitude
`and a rise time of the
`voltage pulse being
`chosen to increase an
`excitation rate of
`ground state atoms
`that are present in the
`weakly-ionized
`plasma to create a
`multi-step ionization
`process that generates
`a strongly-ionized
`plasma, which
`comprises ions that
`sputter target material,
`from the weakly-
`ionized plasma, the
`multi-step ionization
`process comprising
`exciting the ground
`state atoms to generate
`excited atoms, and
`then ionizing the
`
`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`proximate to the sputtering target.
`
`‘759 Patent at 3:10-12 (“FIG. 1 shows a cross-sectional view of a
`known magnetron sputtering apparatus 100…” that has a magnet
`126.”)
`
`‘759 Patent at 4:4-10 [describing the prior art Fig. 1] (“The
`electrons, which cause ionization, are generally confined by the
`magnetic fields produced by the magnet 126. The magnetic
`confinement is strongest in a confinement region 142….”)
`
`Wang at Fig. 1.
`
`Wang at 4:23-27 (“A small rotatable magnetron 40 is disposed in the
`back of the target 14 to create a magnetic field near the face of the
`target 14 which traps electrons from the plasma to increase the
`electron density.”)
`The combination of Wang and Kudryavtsev discloses applying a
`voltage pulse to the weakly-ionized plasma, an amplitude and a rise
`time of the voltage pulse being chosen to increase an excitation rate
`of ground state atoms that are present in the weakly-ionized plasma
`to create a multi-step ionization process that generates a strongly-
`ionized plasma, which comprises ions that sputter target material,
`from the weakly-ionized plasma, the multi-step ionization process
`comprising exciting the ground state atoms to generate excited atoms,
`and then ionizing the excited atoms within the weakly-ionized plasma
`without forming an arc discharge.
`
`‘759 Patent at Fig. 5
`Wang at Figs. 6, 7.
`
`Wang at 7:61-62 (“The pulsed DC power supply 80 produces a train
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`
`
`Claims 44 and 49
`
`excited atoms within
`the weakly-ionized
`plasma without
`forming an arc
`discharge.
`
`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`of negative voltage pulses.”).
`
`Wang at 5:23-27 (“[The pulse’s] exact shape depends on the design
`of the pulsed DC power supply 80, and significant rise times and fall
`times are expected.”).
`
`Wang at 4:29-31 (“increases the sputtering rate...”).
`
`Wang at 7:19-25 (“Preferably, the peak power level PP is at least 10
`times the background power level PB, … most preferably 1000 times
`to achieve the greatest effects of the invention. A background power
`PB of 1 kW will typically be sufficient…”)
`
`Wang at 7:31-39 (“The SIP reactor is advantageous for a low-power,
`low-pressure background period since the small rotating SIP
`magnetron can maintain a plasma at a lower power and lower
`pressure than can a larger stationary magnetron. However, it is
`possible to combine highly ionized sputtering during the pulses With
`significant neutral sputtering during the back ground period.”).
`
`Wang at 7:3-6 (“Plasma ignition, particularly in plasma sputter
`reactors, has a tendency to generate particles during the initial arcing,
`which may dislodge large particles from the target or chamber.”)
`
`Wang at 7:47-49 (“The initial plasma ignition needs be performed
`only once and at much lower power levels so that particulates
`produced by arcing are much reduced.”).
`
`Wang at 7:13-28 (“Accordingly, it is advantageous to use a target
`power waveform illustrated in FIG. 6… As a result, once the plasma
`has been ignited at the beginning of sputtering prior to the illustrated
`waveform…”).
`
`Kudryavtsev at 34, right col, ¶ 4 (“Since 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 Fig. 1
`
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`

`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`
`Kudryavtsev at Fig. 6
`
`
`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 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 Abstract (“[I]n 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
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`

`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`excited states.”)
`
`If one of ordinary skill, applying Wang’s power levels did not
`experience Kudryavtsev’s “explosive increase” in plasma density, it
`would have been obvious to adjust the operating parameters, e.g.,
`increase the pulse length and/or pressure, so as to trigger
`Kudryavtsev’s fast stage of ionization. One of ordinary skill would
`have been motivated to use Kudryavtsev’s fast stage of ionization in
`Wang so as to increase plasma density and thereby increase the
`sputtering rate. Further, use of Kudryavtsev’s fast stage in Wang
`would have been a combination of old elements that yielded
`predictable results of increasing plasma density and multi-step
`ionization.
`
`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 (Ex. 1004). Because
`Wang applies voltage pulses that “suddenly generate an electric
`field,” one of ordinary skill reading Wang would have been
`motivated to consider Kudryavtsev and to use Kudryavtsev’s fast
`stage in Wang.
`
`The combination of Wang with Kudryavtsev, Mozgrin, and the
`Mozgrin Thesis discloses the rise time of the voltage pulse is
`approximately between 0.01 and 100V/(cid:541)sec.
`
`See evidence cited in claim 1
`
`Wang at Fig. 6
`
`Wang at 7:56-62 (“The background and pulsed power [of Fig. 6] may
`be generated by distinctly different circuitry, as illustrated in Fig. 7…
`The pulsed DC power supply 80 produces a train of negative voltage
`pulses…”)
`
`Mozgrin Thesis at Fig. 3.2
`
`44. The sputtering
`source of claim 1
`wherein the rise time
`of the voltage pulse is
`approximately
`between 0.01 and
`100V/(cid:541)sec.
`
`
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`

`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`
`
`The peak voltage in region 2 is about 720 V ((cid:35) 4 div x 180 V/div)
`and the voltage in region 1 is about 360 V ((cid:35) 2 div x 180 V/div).
`This difference is about 360 V.
`
`Mozgrin Thesis at 42, ¶ 1 (“a power supply was selected which
`produces square current and voltage pulses with a rise time (leading
`edge of the pulse of 5-60 μs…”).
`
`Mozgrin Thesis at 100, ¶ 2 (“The implementation of the high-current
`magnetron discharge (regime 2) in sputtering and layer deposition
`technologies provides an enhancement in the flux of deposited
`materials or the discharge plasma density (above 2 × 1013 cm-3) if the
`deposition is made from the plasma.”).
`
`One of ordinary skill in the art would have been motivated to
`combine Wang, Kudryavtsev and Mozgrin Thesis. Wang, Mozgrin
`and Mozgrin Thesis are all pulsed magnetron sputtering systems. If
`Wang’s densities were different than those identified in Mozgrin
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`EXHIBIT A.10
`U.S. Patent No. 7,147,759
`
`Claims 44 and 49
`
`Wang in view of Kudryavtsev and Mozgrin Thesis
`
`Thesis, one of ordinary skill would have been motivated to adjust
`Wang’s power levels and pulse characteristics so as to use Mozgrin
`Thesis’s plasma densities, e.g., so as to achieve desired sputtering.
`Further, as explained above with respect to claim 1, it would have
`been obvious to one of ordinary skill to combine Wang with
`Kudryavtsev.
`
`The combination of Wang with Kudryavtsev, Mozgrin, and the
`Mozgrin Thesis discloses the rise time of the voltage pulse is
`approximately between 0.01 and 100V(cid:541)sec.
`
`See evidence cited in claim 20.
`
`See evidence cited in claim 44.
`
`49. The method of
`claim 20 wherein the
`rise time of the voltage
`pulse is approximately
`between 0.01 and
`100V(cid:541)sec.
`
`
`
`
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