APPLIED MATERIALS EXHIBIT 1042 (Part 3 of 3)
`
`Page 8 of 16
`Appendix 1039-A
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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/5 of light
`it
`transmitted was
`unique to this element, or the emission intensity at the
`selected wavelength/s was sufficiently higher than the
`corresponding ones of 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 oxygen line, sufficiently in-
`tense, to interfere with the In one. A more universal
`technique was required for the large number of 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 and Ti oxide. 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 changes in
`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
`when they were sputtered in an Ar/O2 atmosphere.
`Fig. 3 shows a schematic of the voltage control loop.
`A user connector, located on the rear panel of the
`Advanced EnergyTM power supplies which was used in
`this work, provides a 0—5-V DC analogue signal 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 was also 0 V and it 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 l V. The output signal
`
`Vet-In chm-her
`
`
`
`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, when it was used, as it represented the dominating
`power applied to the main magnetron relative to the
`floating power applied by the AC power supply. This
`arrangement provided better control.
`
`2.4. Substrate condition probe
`
`The information that was required was the ion cur-
`rent density to the substrate and its floating potential.
`In other words, the number and energy of ions that
`bombarded the growing films relative to the number of
`atoms deposited. To obtain this information, we used
`what we termed a ‘substrate condition probe’. Fig. 4
`shows a crossosectional and a bottom view (i.e.
`the
`surface with a direct contact with the plasma) of this
`probe. lt essentially consisted of a central cylindrical
`head, whose diameter was 6 mm, surrounded by a
`25x37 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 procedure of placing a substrate; it was mounted
`in the jig, which was in turn inserted into the platen.
`The l-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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`T
`
`I. Sufi / Surface and Coatings Technology 135 (20m) 48-59
`
`53
`
`d“ 4!. -I. 4' Al” ‘III
`
`whom
`rlfl M * J! 0 fl
`
`~40 J.
`
`-I
`
`-I.
`
`U
`
`4.!
`
`:52 #0
`t2tt("MID-ovum)
`
`Fig. 6. The negative part of the l—V characteristics of the probe. at
`different DC powers to an In magnetron. when it was held opposite
`the centre of the magnetron. The curve when the probe was held
`opposite the erosion zone is also plotted.
`
`to the probe increased with the
`l. The ion-current
`applied DC power to 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 when it 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 DC was the highest (Fig.
`7).
`3. The floating potential of the probe was almost
`independent of the applied AC power and slightly
`dependent on the DC power. However, the order
`of magnitude of these floating potentials was slightly
`lower when DC powers were applied.
`
`The above conclusions are in very good agreement
`with the results obtained by Window and Sawides [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
`
`o wig—[c-r fall-CK 1- Q:fiivxgyr-jr-nmir
`VM'IV)
`4“ 4. VI” 4” J” 'H.
`'I.
`r” '1’
`‘7‘ “ e” ‘ - e'
`
`-I'
`
`.
`
`nun.) hLostao;
`(rum-tutu»
`
`Fig. 7. The negative pan 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.
`
`(a) Crose-sectional View.
`
`Copper Cyllndfl
`[probe Mall
`
`O
`a”
`
`('opper nut
`Screw
`“'axhev
`.
`( {timid Mullah)!
`
`Alumlntum bod)
`
`lprohe git-rd:
`
`(b) Bottom views: Surface with
`contact with plasma
`
`Aluminium guard
`
`Copper probe ma
`
`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 2><10'3 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, was also 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 AC floating
`between the two magnetrons, and 300 W DC combined
`with 100 W AC. The results are shown in Fig. 7. The
`following remarks can be deduced from these figures:
`
`I:
`
`.
`
`....
`
`CIIIMM(IM-2)
`
`4“
`
`4”
`
`~II ‘
`
`4“
`'
`
`4.
`4.
`Valle-(V)
`
`~H
`
`I
`
`I
`
`C
`
`a
`
`Fig. 5. The l—V characteristics of the probe when an In magnetron
`was held at 300 W DC and the probe was held opposite to the centre
`of the magnetron.
`
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`

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`54
`
`l. Sufi / Surface and Coming: 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 Howson et al. [13] and Spencer et al. [14].
`It is informative to compute the arrival ratio of Ar
`ions to metal atoms at 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
`power to the magnetron was 300 W DC combined with
`100 W AC, J,‘ = 7.1 mA/cmz, V,= —17 V and VP=0
`V (Fig. 7), where 1,-‘, V, and V,, are the ion current
`density to the substrate, the floating potential of the
`substrate and the plasma potential, respectively. Con-
`sidering the case of indium oxide, which had a thick-
`ness of 152 nm, it was found that Alf/N;l - 5.7, where
`M’ and N; are the number of ions bombarding 1 cm:
`of the substrate per second and the number of de-
`posited metal atoms on 1 cm2 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 means that, 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, rather it 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 plasma was attributed to target voltage spikes dur-
`ing the reignition of the plasma on each half-cycle, as it
`is evident on the negative-going part of each cycle.
`Such spikes cause rapid electron acceleration in the
`pre-sheath region leading to significantly more efficient
`ionisation of gas and hence much higher plasma bom-
`bardment.
`
`3. Experimental details
`
`3.]. The sputtering system
`
`The chamber comprised a 424m diameter stainless
`steel chamber, 12-cm deep internally, giving a short
`
`pump down time 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 was electrically 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 attached to the platen
`so that it could be rotated around this axis with a DC
`motor at a rotation speed of up to 60 rev. /min.
`The partial 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 changes in
`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 way as 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
`volume provided 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 I
`volume, and could typically be evacuated from atmo-
`sphere to approximately 40 mtorr in approximately 2
`min, via two-stage rotary pump.
`Samples were mounted singly in a jig, which was then
`attached to the end of a loading arm, which was moved
`
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`l. Sufi / Surface and Coatings Technology 135 (2000) 48—59
`
`55
`
`
`. «gm-my; hurt-934 ‘A—y-r—nn'i-e—h- - I-e-r-v
`
`I
`
`fifhum-nos)
`;.-..-.—.a-no
`
`”I
`
`l
`
`no
`
`”I
`
`”O
`Wan-‘01..)
`
`u.
`
`a.
`
`7.
`
`m
`
`I.
`
`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 values of reflectance.
`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 comparing it with a calcu-
`lated one [16] to derive a correction curve of the
`measured reflectance 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 measured reflectance,
`Rmca‘“, and the actual one, R, is
`
`R = 0.76(R""““"r - 5%)
`
`or
`
`R = 0.76R’"““’“' — 4%
`
`(5)
`
`(6)
`
`if Rflfii’“ is the measured value of a
`As a result,
`reflectance maximum, the corresponding actual value,
`Rm“, is given by
`
`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 refmcrive 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 x of the incident
`light
`is chosen so that it
`is
`comparable to the film thickness dm," 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:
`,
`.,
`-
`"film _ "ambnsubs
`Rm, = —,——
`"film + namhnsuhs
`
`(1)
`
`R ‘ = (
`In"
`
`h
`— n
`n
`subs
`am )
`n\uh\ + namb
`
`1
`"
`
`(2)
`
`where Rum, Rm, nmm, um,“ and nflmh 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 nfilm, we
`get:
`
`n
`
`= n
`
`film
`
`1+ Rm,
`n —
`subs 1 _ m
`
`
`
`”2
`
`amh
`
`The relative precision of "mm is given by
`
`ARmux
`Rm“
`A"film _
`nmm ' 2(1—Rm,,) 7?...
`
`(3)
`
`(4)
`
`For example, if Rm, = 36%, it is then sufficient to
`measure Rm, to an accuracy of approximately 2% (i.e.
`ARM“ = 0.7%) so that the relative error for rim," is not
`larger than 1%.
`In this work, films were deposited on glass substrates
`with nwh, = 1.525 and the spectrophotometric mea-
`surements were carried out in air (i.e. rim,h = l).
`Transmittance and reflectance spectra of transparent
`films, produced in this work, were measured using a
`Hitachi U-2000 double-beam spectrophotometer with a
`simple reflection attachment, which allowed compar-
`ison of the sample with freshly prepared aluminium
`
`
`
`Page 12 of 16
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`

`
`
`I. Safi / Surface and Coatings Technology 135 (2000) 48-59
`X ax)‘ an
`m | m _
`d. = ’—
`znfilm()‘max: _ xmax.)
`flm
`
`
`
`(9)
`
`56
`
`WP”
`
`UKUGIISSII
`
`d.
`”0 ~ I. ~ 90
`"mama:
`
`u-
`
`no
`
`7!.
`
`fl
`
`Eq. (9) is also valid in the case of two consecutive
`minima. The problem of this equation is that it ignores
`changes of nm with wavelength. However, it was con—
`sidered to be sufficiently accurate for the estimation of
`dfilm for the purpose of this work, especially in the
`relatively narrow range of wavelength studied where
`variations in "mm 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.
`
`Fig. 9. Calculated and experimental reflectance spectra of a single
`crystal silicon wafer. Also shown is the correction ratio as a function
`of wavelength. Data of the calculated curve are from [16].
`
`R"m z 0.7mm?“ — 4%
`
`(7)
`
`5. Results
`
`Thus, by substituting the value of Rm“:
`
`5.1. Aluminium oxides
`
`nmm = 1.525
`
`
`1+ 0.76R:‘,§§‘“'—0.04
`1— 0.76R::;w'—0.04
`
`”3
`
`(8)
`
`Instead of ellipsometry, Eq. (8) was used to calculate
`refractive indices of films produced in the course of this
`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 of light beam of the spec-
`trophotometer (~ 10.8 mmz) and that of the laser
`beam of the ellipsometer (~ 0.8 mmz) 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 am, using Eq. (8) the film thick-
`ness could be calculated using equations "filmdfilm =
`
`(2k + DMZ“ and "filmdfilm =kL33, where km“ is a
`wavelength at which a reflectance maximum occurs and
`km is a wavelength at which a reflectance minimum
`occurs. The calculation procedure depended on the
`shape of the reflectance spectrum of interest.
`If there were two consecutive maxima in the scanned
`spectral range, then for the first maximum 4nmmdmm =
`(2k + mm“ and that for the second maximum is
`4:15,,"de = [2(k — l) + 11km“, By solving these two
`equations, it is found that
`'
`
`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, A120} films were prepared using the
`mid-frequency AC powered magnetrons technique. The
`main and secondary targets were both A] and the two
`magnetrons were operated in the floating mode at
`113.2,.“ =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 magnetron voltage set point, Alf}, was grad-
`ually decreased and a film was deposited and charac-
`terised at each value of Alf}. The deposition time was 3
`min. Fig. 10 shows the dependence of transmittance at
`550 nm, T550, of the visibly transparent Al203 films.
`and the corresponding deposition rate, on All. Obvi-
`ously, films of higher T550 are deposited at lower rates.
`The percentage of Al magnetron voltage set point, and
`the corresponding 02 flow rate, at which the best
`A1303 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 reponed results
`[9,17,18], taking into account that the applied power in
`this work was only 1 kW. Fig. 11 shows the transmit-
`tance and reflectance spectra of the best A130J 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.
`
`Page 13 of 16
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`

`7——————~—
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`l. Safi / Surface and Coating Technology 135 (2000) 48-59
`
`57
`
`5.2. Mixed insulating oxides
`
`Finally, a large number of oxide films of Mo, W, V,
`Pb, Ti, Sn and Cu doped with dopants such as Zn, Sn,
`Ti, Nb, Ta, M0 or Bi have been deposited, at different
`combinations of powers and at different stoichiome-
`tries, and characterised. They were initially 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 P8,“,
`P‘BC, PLX, FEE and P3? are the DC biasing powers
`applied to the floating Cu, W, V, Mo and Pb mag-
`netrons. respectively, and Cu"?c and Pb?c are the per-
`oentages of metallic Cu and Pb magnetrons voltages
`set-points (i.e. the occurrence), respectively. The float-
`ing AC power and deposition time were 100 W and 6
`min, respectively, throughout.
`
`‘99‘
`
`6. Conclusion
`
`the deposition
`According to the above discussion,
`technique, employed in the course of this work, enjoys
`the following major advantages
`
`1. Substrate rotation enhances atomic level 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; the first 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
`
`”W711i . up
`
` vim-mon)
`
`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 unooated glass substrate are also plotted.
`
`power in a novel way, using a filter to protect the
`DC power supply from the AC one (or the inde-
`pendently DC powered magnetrons method),
`permits the composition of the produced films to
`be easily and independently manipulated by varying
`the magnitude of power applied to each mag-
`netron. As a result, this system is able to obtain a
`sputter-deposited coating of an alloy or multi-ele-
`ment compound which is either difficult or impossi-
`ble to be formed from a single target.
`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
`sputtered films to be high.
`4. The use of an airlocked system allows the imple-
`mentation of an iterative deposition process to vary
`coating stoichiometry and composition. Hence, in-
`formation regarding different composition and stoi-
`chiometry can be attained rapidly without cathode
`acquisition or preparation.
`5. The system, described in this work, is superior to
`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 as a direct result of the
`close proximity of the cathode.
`The use of mid-frequency (i.e. 40 kHz) AC power
`in the floating mode secures periodical effective
`
` ‘Iifltllllllllfl:1
`
`n
`
`n
`
`71
`a
`vs
`14
`mamm—wmm)
`
`a
`
`10. Transmittance at 550 nm and the corresponding deposition
`vs. the percentage of aluminium magnetron voltage 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
`
`Page 14 of 16
`Appendix 1039-A
`
`Page 252 of 304
`
`

`

`
`
`58
`
`l. Sufi /Surfnce and Coatings Technology 135 (2000) 48-59
`
`Table l
`A summary of the preparation conditions and optical properties of some of the transparent insulating oxide films prepared in this work‘
`
`Oxide
`DC bias (W)
`Occurrence (%)
`um,“
`T55" (‘71:)
`Deposition
`rate (nm/s)
`
`
`0.80
`07.7
`1.92
`Cu: - 30.8
`P2,? - 300
`Cu-Sn
`0.30
`72.3
`2.24
`mg,” - 53.9
`PB; - 150
`Mo-Nb
`0.41
`91.9
`1.90
`mg,“ - 49.3
`P35 - 300
`Mo—Nb
`0.44
`91.9
`1.93
`ML, - 40.3
`ME - 450
`Mo-Nb
`0.30
`81.4
`2.00
`mg", - 54.0
`MS - 100
`Mo-Sn
`0.37
`90.8
`2.17
`70;, - 51.4
`ng - 300
`Mo-Sn
`0.42
`90.9
`2.09
`A1,?“ - 45.9
`[fig - 450
`Mo-Ta
`1.25
`74.2
`2.40
`Pb: - 54.0
`PE,“ - 400
`Pb
`0.84
`80.9
`2.44
`Pb: - 52.0
`Raf - 100
`Pb-Bi
`1.28
`88.4
`2.40
`80;: - 42.8
`PE," - 300
`Pb-Bi
`1.55
`84.0
`2.39
`1,0,”; - 41.4
`P9: - 400
`Pb-Bi
`0.05
`80.1
`2.03
`141;, - 05.1
`P‘T’f - 400
`Ti
`0.09
`07.1
`2.00
`A13“, - 09.1
`T,“ — 400
`Ti-Nb
`0.17
`09.9
`2.28
`411",“ - 07.7
`T,“ - 400
`Ti-Ta
`0.52
`77.9
`1.80
`Ar?” - 08.9
`P?" - 200
`V-Mo
`0.48
`81.4
`1.79
`4.3., - 05.0
`1"," = 300
`V-Mo
`0.70
`70.4
`2.23
`A521,, - 51.0
`93." = 400
`w
`0.34
`91.2
`2.29
`mg... = 53.8
`Pa.“ - 150
`W-Mo
`0.71
`87.0
`2.20
`411;, = 50.0
`PR.“ - 450
`W—Mo
`0.38
`90.8
`2.29
`A1,?“ - 02.1
`P3? = 200
`W—Nb
`0.70
`84.8
`2.21
`411;,“ - 51.9
`pa“ = 350
`W—Nb
`1.37
`74.0
`2.14
`mg,“ = 55.1
`PP,“ - 400
`W—Nb
`0.30
`91.5
`2.14
`,1... =- 51.9
`H3," - 100
`W-Sn
`0.59
`78.1
`2.29
`Ar;'m - 00.0
`P‘Jf - 200
`W-Ta
`0.83
`70.7
`2.21
`A13“, - 56.8
`p3“ - 400
`W-Ta
`1.05
`80.3
`2.12
`Ant, - 50.3
`P9f - 000
`W-Ta
`0.35
`91.1
`2.31
`Art?” - 55.0
`9?," - 150
`w—ri
`
`W-Ti 0.04 pa.‘ - 450 AIS“, - 52.0 2.24 87.9
`
`
`
`
`'The floating AC power was 100 W throughout.
`
`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 become unstable, 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.
`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
`DC technique [7,9].
`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-
`
`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 magnetron leads to higher density plasma
`and increased bombardment of 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
`
`[l] N. Danson. l. Safi. G.W. Hall, R.P. Howson, Surf. Coat. Tech-
`nol. 99 (1998) 147-160.
`[2] R.P. Howson, N. Danson, l. Safi, Thin Solid Films 351 (1999)
`32-36.
`
`Page 15 of 16
`Appendix 1039-A
`
`Page 253 of 304
`
`Page 15 of 16
`Appendix 1039-A
`
`Page 253 of 304
`
`

`

`
`
`r—_—_—_
`
`l. Sufi / Surface and Coatings Technology 135 (2000) 48-59
`
`59
`
`[3]
`
`[4]
`
`[5]
`[6]
`l7]
`[8}
`[9]
`
`[10]
`
`[11]
`
`l. Safi. G.W. Hall. N. Danson. Nucl. Instrum.
`R.P. Howson.
`Methods Phys. Res. B 121 (I997) 96-101.
`1. Safi. N. Danson. R.P. Howson. Surf. Coat. Technol. 99 (1998)
`33-41.
`I. Sufi. R.P. Howson. Thin Solid Films 343-44 (1999) 115-118.
`I. Safi. Surf. Coat. Technol. 127 (2-3) (2000) 203-219.
`J. Szczyrbowski. C. Braatz. SPlE 1727(1992) 122—136.
`DA. Glocker. J. Vac. Sci. Technol. A ll (6) (1993) 2989-2993.
`M. Schcrer. 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) 0988)
`1845-1848.
`S. Schiller. K. Goedickc. J. Reschke. V. Kirchhoff. S. Schneider.
`F. Milde. Surf. Coat. Technol. 61 (1993) 331-337.
`
`[l2]
`
`[13]
`
`[14]
`
`[IS]
`
`[16]
`
`[17]
`[18]
`[19]
`
`B. Window. N. Sawides. J. Vac. Sci. Technol. A 4 (3) (1986)
`453—456.
`R.P. Howson. H.A. Ja'Fcr. AG. Spencer. “tin Solid Films
`[93-94(1990) 127—137.
`A.G. Spencer. K. Oka. R.P. Howson. R.W. Lewin. Vacuum 38
`(I988) 857—859.
`F. Abeles, in: E. Wolf (Ed). Progress in Optics. ll. 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. Win. Thin Solid Films 119 (1984) 203—209.
`PJ. Clarke. J. Vac. Sci. Technol. A 12 (2) (1994) 594—597.
`R.W. Lewin. R.P. Howson. Proc. 6th Int. Cont. on lon and
`Plasma Assisted Techniques. Brighton. UK. (1987) pp. 464—469.
`
`m.4am
`
`mwuy.
`
`Page 16 of 16
`Appendix 1039-A
`
`Page 254 of 304
`
`Page 16 of 16
`Appendix 1039-A
`
`Page 254 of 304
`
`

`

`Appendix 1039-B
`Appendix 103 9-B
`
`Page 255 of 304
`
`

`

`
`
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`Surface & coatings technology.
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`
`Page 256 of 304
`
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`

`Deta I [S
`
`Title
`Subjects
`
`Identifier
`
`Surface & coatings technology.
`Electroplating -- Periodicals
`Metals -- Finishing -- Periodicals
`Surface preparation -- Periodicals
`
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`
`LC : 86642343
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`Surface and coatings technology
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`Vol. 27, no. 1 (Jan. 1986)-
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