`Samsung Electronic's Exhibit 1042 (Vol 3 of 3)
`
`APPLIED MATERIALS EXHIBIT 1042 (Part 3 of 3)
`
`Page 7 of 16
`Appendix 1039-A
`
`Page 245 of 304
`
`Ex. 1042, Page 245
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`
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`APPLIED MATERIALS EXHIBIT 1042 (Part 3 of 3)
`
`Page 8 of 16
`Appendix 1039-A
`
`Page 246 of 304
`
`Ex. 1042, Page 246
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`52
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`I. Safi / Surface and Coatings Technology 135 (2000) 48-59
`
`2.2. Plasma emission monitoring (PEM)
`
`This method of control has been described in detail
`in a previous paper[6]. In the course of this work, the
`plasma contained mainly the emission lines corre-
`sponding to argon, oxygen and the target material.
`Therefore, to control the emission line/s of one of
`these elements, the optical filter had to be chosen so as
`either the wavelength/s of light
`it
`transmitted was
`unique to this element, or the emissionintensity at the
`selected wavelength/s wassufficiently higher than the
`corresponding onesof the other two elements.
`For example, for the reactive sputter-deposition of In
`oxide, a band pass filter had been used for controlling
`on In emission line at 451.1 nm. Sufficient signals up to
`approximately 150 mV were obtained at applied powers
`of the order of 300 W. At this wavelength, there is
`neither an argon nor an oxygenline, sufficiently in-
`tense, to interfere with the In one. A more universal
`technique was required for the large numberof materi-
`als investigated in this work. A high-pass filter, with a
`cut-off wavelength at approximately 620 nm, was suc-
`cessfully used to control the reactive sputter-deposition
`of W, V, Mo andTioxide. At wavelengths greater than
`approximately 620 nm,the intensities of the emission
`lines of these metals are very weak. Thus, the transmit-
`ted signal by this filter
`is either due to argon or
`oxygen-lines. The signal fell as oxygen was admitted
`and it is concluded that the strong signal was due to
`argon, and the control was carried out on the argon
`lines, the fall in intensity being attributed to changesin
`the discharge current and coupling to the components
`of the atmosphere as the oxygen was added. Signals up
`to approximately 1.5-2 V were obtained at applied
`powers of the order of 300 W.
`
`2.3. Voltage control
`
`in a
`Voltage control has been described in detail
`previous paper [6]. This method of control has been
`used in this work in the cases of Al, Zn, Cu and Pb
`whenthey were sputtered in an Ar/O, atmosphere.
`Fig. 3 shows a schematic of the voltage control loop.
`A user connector, located on the rear panel of the
`Advanced Energy™ power supplies which was used in
`this work, provides a 0-5-V DCanaloguesignal repre-
`senting the cathode voltage (i.e. the output voltage of
`the power supply). The DC signal was 0 V when the
`output voltage of the supply wasalso 0 V andit was 5
`V at the full-scale output voltage of the supply. This
`0-5-V DC signal was used as an input to a voltage
`controller. The signal was taken through two controls;
`one of which backs it off against another potential to
`provide a zero reference. The difference from this zero
`signal was then amplified by a variable gain amplifier to
`give an output ranged from 0 to 1 V. The output signal
`
`Vacuum chamber
`
`> Electrical signal
`
`> Gas pipe
`
`Fig. 3. Voltage control (VC) system used in controlling the reactive
`magnetron sputtering processes.
`
`from the voltage controller was then applied to a
`standard pressure controller (process controller) which
`was connected to a piezoelectric control valve of a very
`fast response. The ‘zero reference’ was the signal cor-
`responding to the voltage seen when the target was
`fully poisoned, the ‘1’ was that for metal sputtering.
`Any intermediate degree of target poisoning (i.e. an
`intermediate value of cathode voltage) can be repre-
`sented, in this technique, by a value of input voltage to
`the controller in the range 0-5 V, and a value of
`output voltage in the range 0-1 V. The input to the
`voltage controller was taken from the DC power sup-
`ply, whenit was used, as it represented the dominating
`power applied to the main magnetronrelative to the
`floating power applied by the AC power supply. This
`arrangementprovided better control.
`
`2.4. Substrate condition probe
`
`The information that was required was the ion cur-
`rent density to the substrate andits floating potential.
`In other words, the number and energy of ions that
`bombardedthe growingfilmsrelative to the number of
`atoms deposited. To obtain this information, we used
`what we termed a ‘substrate condition probe’. Fig. 4
`shows a cross-sectional and a bottom view (i.e.
`the
`surface with a direct contact with the plasma) of this
`probe. It essentially consisted of a central cylindrical
`head, whose diameter was 6 mm, surrounded by a
`25 x37 mm guard. The guard, which was entirely
`isolated from the head, was utilised to minimise the
`plasma edge-effect from the probe head. The probe
`was placed in the plane of the substrate following the
`same procedureof placing a substrate; it was mounted
`in the jig, which was in turn inserted into the platen.
`The I-V characteristics were then obtained by bias-
`ing the probe head. The current
`to the guard was
`excluded. Probe measurements were performed using
`
`Page 9 of 16
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`Page 247 of 304
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`Ex. 1042, Page 247
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`Page 9 of 16
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`Ex. 1042, Page 247
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`vr
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`I. Safi / Surface and Coatings Technology 135 (2000) 48-59
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`53
`
`(a) Cross-sectional view.
`
`Copper cylinder
`(probe head)
`
`a
`3.Benen,
`
`(b) Bottom views: Surface with
`contact with plasma
`
`(probe guard)
`Copper probe head
`
`Copper nut
`Screw
`Washer
`~
`‘Ceramic insulator
`
`Aluminium body
`
`Aluminium guard
`
`Fig. 4. A cross-sectional and a bottom view of the probe.
`
`In and Sn targets attached to the main and secondary
`magnetrons, respectively. Keeping the working pres-
`sure at 2X 10~* torr,
`two sets of experiments were
`carried out. The first was when the probe was held
`opposite to the centre of the In magnetron using dif-
`ferent DC powers (i.e. at 100, 200 and 300 W). In
`addition, the characteristics of the probe when it was
`facing the erosion zone of the In magnetron, when the
`applied power was 300 W,wasalso plotted for compar-
`ison. The results are shown in Figs. 5 and 6. In the
`second set of experiments, the probe was held opposite
`to the centre of the In magnetron throughout. The
`applied powers were 50 W and 100 W ACfloating
`between the two magnetrons, and 300 W DC combined
`with 100 W AC. Theresults are shown in Fig. 7. The
`following remarks can be deduced from these figures:
`
`&
`
`.
`
`ten,
`
`10
`
`“120
`
`100
`
`oO
`
`100
`y
`
`~
`+0
`Vottage (V)
`
`2
`
`°
`
`2»
`
`“
`
`a
`
`Fig. 5. The I-V characteristics of the probe when an In magnetron
`was held at 300 W DCandthe probe washeld opposite to the centre
`of the magnetron.
`
`Page 10 of 16
`Appendix 1039-A
`
`Page 248 of 304
`
`Voltage(V)
`100 190 140 -100 120 -110 100 90 40-04
`
`Aysuapyeaa 4
`eeeeeeee(reayyw)
`
`Fig. 6. The negative part of the I-V characteristics of the probe, at
`different DC powers to an In magnetron, whenit was held opposite
`the centre of the magnetron. The curve when the probe was held
`opposite the erosion zoneis also plotted.
`
`to the probe increased with the
`1. The ion-current
`applied DC powerto the magnetron. On the other
`hand, at a fixed DC power(e.g. 300 W), such a
`current was higher when the probe was held oppo-
`site the centre of the magnetron than whenit was
`opposite the erosion zone. Similarly, the ion-cur-
`rent to the probe also increased with the applied
`floating AC power.
`2. At a fixed magnitude of power(e.g. 100 W), the
`ion-current to the probe was lower in the DC case
`than in the floating AC one. Furthermore,
`the
`ion-current to the probe in the case of the 100-W
`AC combined with 300-W DCwasthe highest(Fig.
`7).
`3. The floating potential of the probe was almost
`independent of the applied AC powerandslightly
`dependent on the DC power. However, the order
`of magnitudeof these floating potentials wasslightly
`lower when DCpowers wereapplied.
`
`The above conclusions are in very good agreement
`with the results obtained by Window and Sawvides[12]
`and the results of Glocker[8]. In addition, the ion-cur-
`rent and floating potential, when the probe was oppo-
`site to the erosion zone, are less than the correspond-
`ing values when the probe was opposite to the centre of
`
` — i —e—_—o-—_____0- 0-00
`
`
`
`
`
`(rmayye)Aipeapyawn)
`
`eeemehowe
`
`Fig. 7. The negative part of the I-V characteristics of the probe at
`different AC powers to a non-biased and biased floating In mag-
`netron when the probe was held opposite the centre of the mag-
`netron.
`
`Ex. 1042, Page 248
`
`© Fioatingof300ACa Pioatingat1000AC —o- Pioatingof1000ACandMasedwith3008DC
`Veltage (V)
`“1 ASD 140 130 -120 110 100 0 0-8
`
`
`
`
`
`Currentdensity(mA/em2)
`
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`Appendix 1039-A
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`Page 248 of 304
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`Ex. 1042, Page 248
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`54
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`I. Safi / Surface and Coatings Technology 135 (2000) 48-59
`
`the magnetron under the same conditions (i.e. applied
`power). This result
`is also in good agreement with
`those of Howsonetal. [13] and Spenceretal. [14].
`It is informative to compute the arrival ratio of Ar
`ions to metal atomsat the substrate. It was found that
`this was 0.7 and the energy delivered to the substrate
`by ions per In atom was approximately 21 eV [1-6].
`On the other hand,
`in the case when the applied
`powerto the magnetron was 300 W DC combined with
`100 W AC, J’ =7.1 mA/cm’, V;= —17 V andV, =0
`V (Fig. 7), where J’, V; and V, are the ion current
`density to the substrate, the floating potential of the
`substrate and the plasmapotential, respectively. Con-
`sidering the case of indium oxide, which had a thick-
`ness of 152 nm, it was found that N°/N,, = 5.7, where
`Nj and Nj are the numberof ions bombarding 1 cm?
`of the substrate per second and the number of de-
`posited metal atoms on 1 cm? of the substrate per
`second, respectively. Consequently,
`the energy deliv-
`ered to the substrate by ions per In atom was approxi-
`mately 100 eV.
`Although the two magnetrons were unbalanced in
`the system used in this work, the measured floating
`potentials of the substrate were relatively low, whereas,
`the measured ion current densities were moderate.
`This could be due to the fact that target-to-substrate
`distance is less than the null-point of the magnetrons,
`which meansthat, at such low distance,
`ions cannot
`acquire high kinetic energies when they impinge on the
`substrate, with the lower floating potential
`that
`the
`substrates have. The small target-to-substrate distance
`also affects, but less severely, the ion current density,
`as the substrate can not collect all ions available be-
`cause it is not in the way of the focused beam leaking
`from the cathode,ratherit is in the base of that beam.
`The average ion densities in the AC plasma are approx-
`imately four times that of the DC plasma. This last
`difference, between the AC and the DC plasmas is
`significant. According to optical emission measure-
`ments, the plasma extinguishes on each half-cycle and
`has to be reignited. The increase in ion densities in the
`AC plasmawasattributed to target voltage spikes dur-
`ing the reignition of the plasma on eachhalf-cycle, asit
`is evident on the negative-going part of each cycle.
`Such spikes cause rapid electron acceleration in the
`pre-sheath region leadingto significantly more efficient
`ionisation of gas and hence much higher plasma bom-
`bardment.
`
`3. Experimental details
`
`3.1. The sputtering system
`
`The chamber comprised a 42-cm diameter stainless
`steel chamber, 12-cm deep internally, giving a short
`
`pumpdowntime with the turbomolecular pump, backed
`by a two-stage rotary pump, compared with conventio-
`nal bell-jar systems [3]. The chamber base accommo-
`dated two identical magnetrons. The magnetron, which
`had both the oxygen inlet
`to the chamber and the
`optical fibre input tip of PEM control loop attached to
`its pod will be, henceforth, called the ‘main magnetron’.
`The other magnetron was connected to the argon inlet
`to the chamber.
`An axially mounted aluminium platen was located
`above the magnetron cathode surfaces, and it was onto
`this platen, which waselectrically isolated,
`the sub-
`strates were loaded from the airlock allowing a target-
`to-substrate distance of approximately 40 mm. The
`centrally oriented metal shaft was attachedto the platen
`so that it could be rotated around this axis with a DC
`motorat a rotation speed of up to 60 rev. /min.
`Thepartial pressure of the sputtering gas, argon, was
`produced through a mass flow controller balanced by
`the vacuum pumping and measured with the system
`pirani.
`For the admission of reactive gas a solenoid valve
`was replaced by a piezoelectric valve, having a faster
`response in order to cope with much faster changesin
`the desired supply of reactive gas required to maintain
`a certain cathode status, compared with that of inert
`gas. This was controlled to produce a pre-determined
`optical emission signal or cathode potential in much
`the same wayas is used to control pressure. In addi-
`tion, the total distance between the reactive gas pipe
`exit
`in the chamber and the piezoelectric valve was
`minimised to help reducing the time constant of the
`pipe. These modifications, allied with the pipe outlet
`being very close to the target
`in the very confined
`volumeprovided by the gettering enabled very efficient
`control of the reactive deposition processes to be ob-
`tained.
`
`3.2. The airlock system
`
`the magnetrons
`The system was designed so that
`could be operated continuously during the. changing of
`substrates. We have found this to be of prime impor-
`tance for iterative reactive processing,
`in which the
`partial pressure of the reactive gas is varied gradually
`until the desired film properties are attained. In order
`that this could be done the system was airlocked, that
`is, the main deposition chamber always remained in
`operation whilst
`the samples could be loaded/un-
`loaded via a separately pumped airlock. The airlock
`was 10 cm in diameter and 4.6 cm deep, had a 0.361 |
`volume, and could typically be evacuated from atmo-
`sphere to approximately 40 mtorr in approximately 2
`min, via two-stage rotary pump.
`Samples were mountedsingly in a jig, which was then
`attached to the end of a loading arm, which was moved
`
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`Ex. 1042, Page 249
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`¥
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`L. Safi / Surface and Coatings Technology 135 (2000) 48-59
`
`55
`
`linearly through double Wilson-type vacuum seals,
`mounted off axis (2.2 cm from the centre) in the
`perspex window plate, which allow visual
`location of
`the substrate.
`
`4. Optical measurements
`
`4.1. Calculations of refractive indices from reflectance
`spectra
`
`In this section, the case of transparent non-absorbing
`films deposited on transparent substrates will be con-
`sidered. It should be mentioned first that
`the wave-
`length
`of the incident
`light
`is chosen so that it
`is
`comparableto the film thickness d,),, to allow interfer-
`ence effects to occur [15].
`The maximum and minimum reflectance of a thin
`film on an infinitely thick substrate are given by:
`9
`2
`Niitm — “amb!subs
`a (1)
`"fim + Namb!subs
`
`ca Neus —Mamb
`
`Rain uf ( Neuds FE Namb
`
`2
`\~
`
`(2)
`
`where R,,,,, Rmin> "fim> “subs ANd Mapp are a re-
`flectance maximum,reflectance minimum,the refrac-
`tive index of the thin film, the refractive index of the
`substrate and the refractive index of the ambient
`medium,respectively. By solving Eq. (1) for nam, we
`get:
`
`ioeN Reis,
`
`a Pe a
`film
`amb’
`*subs Ie VRinax
`
`Therelative precision of mq,,
`
`is given by
`
`ARmax
`Rinax
`Angin ye
`Mam 20 —Ryax) Rmax
`
`we
`
`(4)
`
`For example, if R,,,, = 36%, it is then sufficient to
`measure R,,,,, to an accuracy of approximately 2% (i.e.
`AR,,ax = 0.7%)so that the relative error for ng), is not
`larger than 1%.
`In this work,films were deposited on glass substrates
`with m,,,,= 1.525 and the spectrophotometric mea-
`surements werecarried outin air(i.e. 1,,,, = 1).
`Transmittance and reflectance spectra of transparent
`films, produced in this work, were measured using a
`Hitachi U-2000 double-beam spectrophotometerwith a
`simple reflection attachment, which allowed compar-
`ison of the sample with freshly prepared aluminium
`
`
`
`Page 12 of 16
`Appendix 1039-A
`
`Page 250 of 304
`
`+ Ordinaryglassmibrase—o- Topmacface(anrewsed) + Beammrfact(resid) © Matbacpaper © Bact mface
`
`Hl
`
`soo
`
`$80
`‘Wavelength (am)
`
`0
`
`“
`
`7
`
`70
`
`mo
`
`
`
`Reflectance(%)
`
`
`
`beenuveauanreKeo
`
`380
`
`“
`
`a
`
`Fig. 8. Reference spectra of uncoated glass substrates in different
`cases. The reflectance spectrum of matt black paper is included for
`comparison.
`
`coating. In spectrophotometric measurements carried
`out in this work, both transmittance and reflectance
`spectra were measured in the spectral range 350-750
`nm with a scanning speed of 400 nm/min.
`In order to obtain values for the absolute reflection
`coefficients that were required,
`it was necessary to
`make corrections of the measured reflectance spectra
`of the deposited films. The corrections involved:
`
`1. Measuring the reflectance spectrum of the bottom
`surface of an uncoated glass substrate in order to
`subtract it from the measured valuesofreflectance.
`This was achieved by treating the bottom surface of
`an uncoated glass substrate with emery paper so
`virtually eliminating reflection from it (Fig. 8). The
`reflectance spectra of the untreated (or top) sur-
`face and that of an ordinary glass substrate were
`then measured. The reflectance spectrum of the
`back surface was obtained by subtracting the re-
`flectance values of the top surface from those of
`the ordinary substrate, and was averaged to be 5%.
`2. Measuring the reflectance spectrum of a single
`crystal silicon wafer and comparingit with a calcu-
`lated one [16] to derive a correction curve of the
`measuredreflectance in order to obtain the abso-
`lute reflectance of the coatings (Fig. 9). The correc-
`tion ratio was, on average, 0.76.
`
`Thus, the relation between the measuredreflectance,
`R™*"" and the actual one, R,is
`
`R =0.76(R™*"" — 5%)
`
`or
`
`R=0.76R™*"* — 4%
`
`(5)
`
`(6)
`
`if R°"" is the measured value of a
`As a result,
`reflectance maximum, the corresponding actual value,
`Rinax> iS given by
`
`Ex. 1042, Page 250
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`Appendix 1039-A
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`Ex. 1042, Page 250
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`
`
`I. Safi / Surface and Coatings Technology 135 (2000) 48-59
`max,
`
`déim rs
`
`Amax,
`»
`2M Gmmaxs hd Aimax,)
`
`(9)
`
`56
`
`
`
`Reflectance(%)
`
`sesaneenesagaa
`
`woprause,) 30
`
`oes
`
`so o “ 7 = ~
`“= — cd
`Wavelength (2m)
`
`Eq.(9) is also valid in the case of two consecutive
`minima. The problem of this equationis that it ignores
`changesof ry), with wavelength. However, it was con-
`sidered to besufficiently accurate for the estimation of
`dsm for the purpose of this work, especially in the
`relatively narrow range of wavelength studied where
`variations in ng, Were not expected to be so signifi-
`cant.
`Finally, it should be indicated that the results of the
`thickness measurements were satisfactorily consistent
`in the course of this work.
`
`5. Results
`
`5.1. Aluminium oxides
`
`The system was established using aluminium cath-
`odes in both magnetrons. Aluminium oxide is a very
`insulating oxide with a high secondary electron emis-
`sion coefficient, which leads to extreme arcing if DC
`reactive sputtering is attempted.
`In this work, Al,O, films were prepared using the
`mid-frequency AC powered magnetrons technique. The
`main and secondary targets were both Al and the two
`magnetrons were operated in the floating mode at
`PAS, 4, =1 kW. Substrates were held static over the
`main magnetron. In this case, no incorporation of an
`alloying material was required. Voltage control on the
`main Al magnetron was used. The percentage of
`aluminium magnetronvoltageset point, Al®, was grad-
`ually decreased and a film was deposited and charac-
`terised at each value of Al®. The deposition time was3
`min. Fig. 10 shows the dependence of transmittance at
`550 nm, Tsso, of the visibly transparent Al,O,
`films,
`and the corresponding deposition rate, on Al%.. Obvi-
`ously, films of higher Ts59 are deposited at lowerrates.
`The percentage of Al magnetron voltage set point, and
`the corresponding O,
`flow rate, at which the best
`Al,O,film occurred(i.e. the one of the highest trans-
`mittance and deposition rate) were 73.7% and 3.6
`sccm,respectively. The transmittance at 550 nm, re-
`fractive index and deposition rate of this film were
`89.5%, 1.67 and 2.02 nm/s,respectively. Clearly, such a
`result
`is comparable with the best reported results
`[9,17,18], taking into account that the applied powerin
`this work was only 1 kW. Fig. 11 shows the transmit-
`tance and reflectance spectra of the best Al,O; film.
`Finally,it is worth mentioning that, in addition to glass,
`aluminium oxide films have also been deposited, using
`this technique, on stainless steel and single crystal
`silicon substrates for extended periods of time (up to 45
`min) and at high rates without any sign of arcing.
`
`Fig. 9. Calculated and experimental reflectance spectra of a single
`crystal silicon wafer. Also shown is the correction ratio as a function
`of wavelength. Dataof the calculated curve are from [16].
`
`Rapax ¥ 0-76R™25"" — 4%
`
`Thus, by substituting the value of Rinax:
`
`1+ (O7ERES™— 0.04
`Pe1— J0.76Res"" — 0.04
`
`|"
`
`(7)
`
`(8)
`
`Instead ofellipsometry, Eq. (8) was usedto calculate
`refractive indicesoffilms producedin the course ofthis
`work, for the following reasons:
`
`1.
`
`is independent of optical thickness of coatings
`It
`and consequently gives consistent results for vari-
`able optical thickness.
`2. The possibility of obtaining refractive indices over
`many wavelengths rather than at 632.8 nm using
`the ellipsometer that was available.
`3. The ratio of the area oflight beam of the spec-
`trophotometer (~ 10.8 mm’) andthat of the laser
`beam ofthe ellipsometer (~ 0.8 mm?) is approxi-
`mately 14. This gives better integration over the
`coated area of the substrate.
`
`4.2. Calculations of thickness from reflectance spectra
`using interference methods
`
`After calculating mg, using Eq. (8) the film thick-
`ness could be calculated using equations 1sjm4s1m =
`
`(Qk + jdm and Mgimdfim =K—~Z~» Where Xmax is a
`wavelength at which a reflectance maximum occurs and
`Amin is a wavelength at which a reflectance minimum
`occurs. The calculation procedure depended on the
`shape ofthe reflectance spectrum of interest.
`If there were two consecutive maximain the scanned
`spectral range, then forthe first maximum 471 ¢1m4gm =
`(2k+UAmax,
`and that for the second maximum is
`4ngim4aim = {2k -—1) + 1Ajax.- By solving these two
`equations,it is found that
`’
`
`Page 13 of 16
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`
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`L. Safi / Surface and Coatings Technology 135 (2000) 48-59
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`57
`
`5.2. Mixedinsulating oxides
`
`(Typesfimo Rp 5 Bim) Wavelength(am)
`
`Fig. 11. Transmittance and reflectance spectra of the best transpar-
`ent Al oxide film which occurred at 73.7% of Al magnetron voltage
`set-point. The floating AC power was 1 kW. The relevant spectra of
`an uncoated glass substrate are also plotted.
`
`the deposition
`According to the above discussion,
`technique, employed in the course of this work, enjoys
`the following major advantages
`
`1. Substrate rotation enhances atomiclevel mixing of
`the film constituents. The stoichiometry of the film
`is controlled by PEM or voltage control, on one
`magnetron, and dopants are added by sputtering
`from the other magnetron. This means that
`the
`former magnetron serves two purposes; thefirst is
`to sputter metal and oxidise it, and the second
`purpose is to oxidise the metal sputtered from the
`other magnetron.
`2. The combination of DC and mid-frequency AC
`
`Finally, a large numberof oxide films of Mo, W,V,
`Pb, Ti, Sn and Cu doped with dopants such as Zn, Sn,
`Ti, Nb, Ta, Mo or Bi have been deposited, at different
`combinations of powers and at different stoichiome-
`tries, and characterised. Theywereinitially investigated
`for conductivity. Although the transparent films were
`insulating under the deposition conditions and proce-
`dures followed (i.e. unintentional heating or biasing of
`substrates and no post-deposition heat treatment), their
`optical properties (e.g. a very wide range of refractive
`indices) are of great interest in optical applications.
`Table 1 summarises the preparation conditions and
`the optical properties of some of the transparent insu-
`lating oxide films prepared in this work, where PRS.
`powerin a novel way, usingafilter to protect the
`PRC, POC, PEC and Pp are the DC biasing powers
`DC powersupply from the AC one (or the inde-
`applied to the floating Cu, W, V, Mo and Pb mag-
`pendently DC powered magnetrons method),
`_ netrons, respectively, and Cu%. and Pb% are the per-
`permits the composition of the produced films to
`centages of metallic Cu and Pb magnetrons voltages
`be easily and independently manipulated by varying
`set-points (i.e. the occurrence), respectively. The float-
`the magnitude of power applied to each mag-
`ing AC powerand deposition time were 100 W and 6
`netron. As a result, this system is able to obtain a
`min, respectively, throughout.
`sputter-deposited coating of an alloy or multi-ele-
`ment compound whichis either difficult or impossi-
`ble to be formed fromasingle target.
`6. Conclusion
`3. Depending on the materials involved, the use of
`very fast feedback methods, to automatically con-
`trol
`the admission rate of the reactive gas (e.g.
`oxygen)into the sputtering chamber(i.e. PEM and
`voltage control), allows the stoichiometry of the
`deposited films to be independently controlled. The
`very efficient control of the admission rate of oxy-
`gen also allows the deposition rate of reactively
`sputteredfilms to be high.
`4. The use of an airlocked system allows the imple-
`mentation ofan iterative deposition process to vary
`coating stoichiometry and composition. Hence, in-
`formation regarding different composition andstoi-
`chiometry can be attained rapidly without cathode
`acquisition or preparation.
`5. The system, described in this work, is superior to
`[a=Treneminance © Depestionrate
`the dual magnetron technique described by Lewin
`and Howson [19] where two concentric cathode
`annuli of different materials (with separate mag-
`netic fields) comprise one magnetron device in that
`the two sources sputter independently of each
`other. This permits variable compositions to be
`selected only to a limited extent
`in a reactive
`environment, the limit being reached when differ-
`ential poisoning of the two cathode materials domi-
`nates. Clearly, precise stoichiometry control also
`suffers from this problem asa direct result of the
`close proximity of the cathode.
`6. The use of mid-frequency (i.e. 40 kHz) AC power
`in the floating mode secures periodical effective
`
`(esexeaseeress
`
`§
`
`ona
`
`a
`
`”
`
`n
`%
`s
`“
`Percentage ofaleminivm magnetron voltage set-point (%)
`
`”
`
`”
`
`10. Transmittance at 550 nm and the corresponding deposition
`vs. the percentage of aluminium magnetronvoltage set-point of
`ly transparent films of aluminium oxide. The floating AC power
`en the two Al magnetrons was 1 kW.
`
`
`
`Page 14 of 16
`Appendix 1039-A
`
`Page 252 of 304
`
`Ex. 1042, Page 252
`
`Page 14 of 16
`Appendix 1039-A
`
`Page 252 of 304
`
`Ex. 1042, Page 252
`
`
`
`
`
`I. Safi /Surface and Coatings Technology 135 (2000) 48-59
`
`58
`Table 1
`A summary ofthe preparation conditions and optical properties of some of the transparent insulating oxide films prepared in this work*
`Oxide
`DC bias (W)
`Occurrence (%)
`Nem
`Ts (%)
`Deposition
`rate (nm/s)
`
`
`0.80
`67.7
`1.92
`Cux = 30.8
`PRE = 300
`Cu-Sn
`0.36
`72.3
`2.24
`Arjen = 53.9
`PRG = 150
`Mo-Nb
`0.41
`91.9
`1.96
`Atom = 49.3
`PX = 300
`Mo-Nb
`0.44
`91.9
`1.93
`Atjem = 46.3
`PR = 450
`Mo-Nb
`0.30
`814
`2.00
`Atjem = 54.0
`PRC = 100
`Mo-Sn
`0.37
`90.8
`2.17
`Afjem = 51.4
`PRS = 300
`Mo-Sn
`0.42
`90.9
`2.09
`Atom = 45.9
`Pris = 450
`Mo-Ta
`1.25
`74.2
`2.46
`Pox = 54.0
`PRE = 400
`Pb
`0.84
`80.9
`2.44
`Pb. = 52.0
`PRE = 100
`Pb-Bi
`1.28
`88.4
`2.40
`Pb, = 42.8
`Pre = 300
`Pb-Bi
`1.55
`84.0
`2.39
`Pox = 41.4
`PRE = 400
`Pb-Bi
`0.05
`80.1
`2.63
`Atjem = 65.1
`PRE = 400
`Ti
`0.09
`67.1
`2.60
`Atjem = 69-1
`Pre = 400
`Ti-Nb
`0.17
`69.9
`2.28
`Afjem = 67.7
`PC = 400
`Ti-Ta
`0.52
`719
`1.80
`Atjom = 68.9
`PRS = 200
`V-Mo
`0.48
`81.4
`1.79
`Atjem = 65.6
`PRE = 300
`V-Mo
`0.76
`76.4
`2.23
`Atom = 51.6
`PY = 400
`Ww
`0.34
`91.2
`2.29
`Atom = 53.8
`PRE = 150
`W-Mo
`0.71
`87.0
`2.20
`Atpem = 50.0
`PRE = 450
`W-Mo
`0.38
`90.8
`2.29
`Atjem = 621
`PY = 200
`W-Nb
`0.70
`84.8
`2.21
`Atpem = 51.9
`PY= 350
`W-Nb
`1.37
`74.0
`2.14
`Aten = 55.1
`PRE = 400
`W-Nb
`0.36
`91.5
`2.14
`Afjem = 51.9
`PY= 100
`W-Sn
`0.59
`78.1
`2.29
`Atjom = 60.6
`PRE = 200
`W-Ta
`0.83
`70.7
`2.21
`Aven = 56.8
`PRE = 400
`W-Ta
`1.05
`86.3
`2.12
`Agen = 56.3
`PRE = 600
`W-Ta
`W-Ti
`PRE = 150
`Atnem = 55.6
`231
`91.1
`0.35
`
`W-Ti
`PRE = 450
`Atvem = 52.0
`2.24
`87.9
`0.64
`“The floating AC power was 100 W throughout.
`
`J
`
`>
`
`"
`
`>
`
`>
`
`»
`
`;
`"
`,
`
`»
`
`>
`
`>
`
`”
`i
`
`A
`
`>
`
`s
`
`>
`
`”>
`
`>
`
`>
`
`>
`
`>
`
`>
`
`>
`
`»>
`
`7
`
`Ex. 1042, Page 253
`
`sequently, the AC technique can be easily adopted
`for sputtering from larger area cathodes[9]. On the
`other hand,
`the AC plasma used with an un-
`balanced magnetronleads to higher density plasma
`and increased bombardmentof the growing insulat-
`ing films with ions.
`9. This technique opens the door wide for investigat-
`ing virtually all potentially promising thin films(e.g.
`hard coatings, semiconducting films, superconduct-
`ing films,etc.).
`
`References
`
`>
`_—‘1!_N.Danson,I. Safi,G.W. Hall, RP: Howson, Surf: Coat. Techy
`[2] R.P. Howson, N. Danson, I. Safi, Thin Solid Films 351 (1999)
`32-36.
`
`discharging of the insulating layer, due to the sym-
`metrical operation of the electrodes. This allows
`the reactive sputtering process to be arc-free [9],
`and hence, eliminating the undesired effects of
`arcing in reactive sputtering such as driving the
`process to becomeunstable, creating defects in the
`films and reducing the target
`lifetime. Conse-
`quently,
`the defect density in insulating films is
`reduced by orders of magnitude [11] in comparison
`with the DC technique.
`7. The well-defined DC conducting anode allows the
`sputtering process to have long-term stability, at a
`given set point. In addition, the high deposition
`rates obtained are comparable with those of the
`DCtechnique[7,9].
`8. Unlike the additional complexity of the RF tech-
`nique, the coupling of the AC power to the cath-
`odes, in the frequency range used,is simple. Con-
`
`Page 15 of 16
`Appendix 1039-A
`
`Page 253 of 304
`
`Page 15 of 16
`Appendix 1039-A
`
`Page 253 of 304
`
`Ex. 1042, Page 253
`
`
`
`[EE
`
`
`
`L. Safi / Surface and Coatings Technology 135 (2000) 48-59
`
`59
`
`(3)
`
`(4)
`
`(5)
`(6)
`a)
`(8)
`(9)
`
`{10}
`
`11]
`
`R.P. Howson,I. Safi, G.W. Hall, N. Danson, Nucl. Instrum.
`MethodsPhys. Res. B 121 (1997) 96-101.
`I. Safi, N. Danson, R.P. Howson,Surf. Coat. Technol. 99 (1998)
`33-41.
`I.Safi, R.P. Howson, Thin Solid Films 343-44 (1999) 115-118.
`I. Safi, Surf. Coat. Technol. 127 (2-3) (2000) 203-219.
`J. Szezyrbowski, C. Braatz, SPIE 1727 (1992) 122-136.
`D.A. Glocker, J. Vac. Sci. Technol. A 11 (6) (1993) 2989-2993.
`M.Scherer, J. Schmitt, R. Latz, M. Schanz, J. Vac. Sci. Tech-
`nol. A 10 (4) (1992) 1772-1776.
`G. Este, W.D. Westwood, J. Vac. Sci. Technol. A 6 (3) (1988)
`1845-1848.
`S. Schiller, K. Goedicke, J. Reschke, V. Kirchhoff, S. Schneider,
`F. Milde, Surf. Coat. Technol. 61 (1993) 331-337.
`
`(12]
`
`(13)
`
`(14)
`
`[15]
`
`[16]
`
`[17]
`{18}
`[19]
`
`B. Window, N. Sawides, J. Vac. Sci. Technol. A 4 (3) (1986)
`453-456.
`R.P. Howson, H.A. Ja’Fer, A.G. Spencer, Thin Solid Films
`193-94 (1990) 127-137.
`A.G. Spencer, K. Oka, R.P. Howson, R.W. Lewin, Vacuum 38
`(1988) 857-859.
`F. Abeles, in: E. Wolf (Ed.), Progress in Optics, II, North-Hol-
`land Publishing Company, Amsterdam, 1963, pp. 249-288.
`D.E. Gray, American Institute of Physics Handbook, McGraw-
`Hill Book Company, New York, 1972.
`M.Scherer, P. Wirz, Thin Solid Films 119 (1984) 203-209.
`P.J. Clarke, J. Vac. Sci. Technol. A 12 (2) (1994) 594-597.
`R.W. Lewin, R.P. Howson, Proc. 6th Int. Conf. on Ion and
`Plasma Assisted Techniques, Brighton, UK, (1987) pp. 464-469.
`
`eeeeI
`SeRapeSes
`
`Page 16 of 16
`Appendix 1039-A
`
`Page 254 of 304
`
`Ex. 1042, Page 254
`
`Page 16 of 16
`Appendix 1039-A
`
`Page 254 of 304
`
`Ex. 1042, Page 254
`
`
`
`Appendix 1039-B
`Appendix 1039-B
`
`Page 255 of 304
`
`Ex. 1042, Page 255
`
`Page 255 of 304
`
`Ex. 1042, Page 255
`
`
`
`
`
`.
`
`JRNAL
`
`Surface & coatings technology.
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`Available at Linda Hall Library Closed Stacks - Serials (Surface and coatings technology.) and other locations
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`v.228 Suppl.1 (2013:Aug.15)
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