US20210254209A1 - Atomic layer deposition of fluoride thin films - Google Patents
Atomic layer deposition of fluoride thin films Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/26—Electron or ion microscopes; Electron or ion diffraction tubes
- H01J37/285—Emission microscopes, e.g. field-emission microscopes
Definitions
- the present disclosure relates to atomic layer deposition, specifically deposition of fluoride thin films.
- Thin layer deposition of material provides the ability to modify substrates or templates to have specific desired properties.
- the alkaline earth metal fluorides MgF 2 , CaF 2 , BaF 2 , and SrF 2 share the spectacular property of exhibiting high transparency, ranging from wavelengths in vacuum ultraviolet (“VUV”) to the long infrared spectrum, covering wavelengths from 150 nm to 11 ⁇ m.
- VUV vacuum ultraviolet
- these materials have found uses in a range of optical applications.
- Calcium fluoride is of particular interest for optical applications because of its low refractive index (n ⁇ 1.46).
- alkaline earth metal fluorides including CaF 2 , (e.g., molecular-beam epitaxy (“MBE”), electron beam evaporation (“EBE”), thermal evaporation, pulsed laser deposition (“PLD”), and chemical vapor deposition (“CVD”)), the use of atomic layer deposition (“ALD”) has proved difficult for these materials.
- MBE molecular-beam epitaxy
- EBE electron beam evaporation
- PLD pulsed laser deposition
- CVD chemical vapor deposition
- the temperature of the deposition process is considered.
- Prior reports regarding ALD of alkaline earth metal fluorides have been above 200° C., such as 200-450° C. There remains a need for a lower temperature, such as sub-225° C. or sub-200° C.
- ALD deposition process for alkaline earth metal fluorides e.g., atomic layer deposition
- At least one embodiment relates to a method of forming a secondary electron emissive (“SEE”) coating.
- a substrate is provided within an ALD reactor.
- a coating of CaF 2 is deposited by atomic layer deposition process including at least one cycle of: pulsing a first metal precursor comprising an alkaline metal amidinate into the reactor for a first metal precursor pulse time; purging the reactor of the first metal precursor; pulsing a second precursor comprising a fluorinated compound into the reactor for a second precursor pulse time; and purging the reactor of the co-reactant precursor.
- the depositing occurs at a reaction temperature greater than a highest sublimation temperature of the first metal precursor and the second metal precursor and less than 50° C. above the highest sublimation temperature.
- Another embodiment relates to method of forming an electron amplifier.
- An electron amplifier substrate having an emissive layer and a resistive layer is provided within an ALD reactor.
- a coating of CaF 2 is deposited by atomic layer deposition process including at least one cycle of: pulsing a first metal precursor comprising [Ca(amd) 2 ] 2 into the reactor for a first metal precursor pulse time; purging the reactor of the first metal precursor; pulsing a second precursor selected from the group consisting of hydrogen fluoride (“HF”), HF-pyridine (“HF-Py”), WF 6 , TaF 5 , MoF 6 , and NbF 5 into the reactor for a second precursor pulse time; and purging the reactor of the second precursor.
- HF hydrogen fluoride
- HF-Py HF-pyridine
- Another embodiment relates to an electron detector device comprising a microchannel plate having a plurality of channels extending therethrough.
- a resistive coating is deposited on the microchannel plate.
- the device further includes an emissive coating deposited on the resistive coating; the emissive coating comprising CaF 2 .
- FIG. 1 shows one embodiment of an ALD process for deposition of CaF 2 employing [Ca(amd) 2 ] 2 and HF precursors.
- FIGS. 2A-2D show quartz crystal microbalance (“QCM”) studies on the [Ca(amd) 2 ] 2 -HF ALD process.
- FIGS. 2A-2B show mass change per cycle (“MCPC”) (or mass grown per cycle (“MGPC”)) for saturation studies of the two precursors Ca and HF, respectively.
- FIG. 2C is a plot of MCPC vs. growth temperature.
- FIG. 2D shows thin film thickness vs. applied number of cycles. The linear fit (dashed line) serves to guide the eye.
- FIGS. 3A-3B show QCM studies during nucleation phase of CaF 2 ALD on an Al 2 O 3 -coated QCM crystal.
- a feeding sequence of 3.0 sec-15.0 sec-1.0 sec-10 sec was applied at 225° C.
- FIGS. 4A-4B show enlarged areas of QCM nucleation studies (from FIG. 3A ) for the ALD of CaF 2 on Al 2 O 3 .
- FIG. 4A shows initial three cycles;
- FIG. 4B shows steady-state regime (from FIG. 3B ).
- Blue and green rectangles indicate the dose times of the two precursors.
- FIG. 5 shows root-mean-squared (“RMS”) roughness obtained from atomic force microscopy (“AFM”) images.
- RMS root-mean-squared
- FIGS. 6A-6G are AFM images of CaF 2 thin films deposited on 18 nm ALD Al 2 O 3 .
- FIG. 7 is a XRD of the CaF 2 layer.
- FIGS. 8A-8F are high-angle annular dark-field (“HAADF”) spectra from scanning transmission electron microscope (“STEM”) experiments on ALD CaF 2 thin film deposited at 225° C. on Si(100).
- HAADF high-angle annular dark-field
- FIG. 9 shows the refractive index of ALD CaF 2 in the ultraviolet (“UV”) and visible range. Data points in the UV range were obtained from reflectivity measurements while values for n in the visible range were obtained from ellipsometry.
- FIG. 10 shows electron signal gain of CaF 2 -coated micro-channel plates (“MCPs”).
- FIG. 11 is a plot of X-ray reflectivity (“XRR”) data and the corresponding fit for an as-deposited CaF 2 ALD thin film, deposited at 225° C. on Si using [Ca] and HF-PY applying 2250 cycles.
- XRR X-ray reflectivity
- FIGS. 12A-12B show repeated QCM studies during nucleation of CaF 2 ALD on an Al 2 O 3 coated QCM crystal.
- a feeding sequence of 3.0 sec-15.0 sec-1.0 sec-10 sec was applied at 225° C. in both cases.
- FIG. 13 is a representative X-ray photoelectron spectroscopy (“XPS”) depth profile of ALD CaF 2 grown on Si(100) at 225° C.
- XPS X-ray photoelectron spectroscopy
- FIGS. 14A-14F are HAADF overlaid images for the elements Ca, F, O, and Si.
- ALD is utilized.
- ALD is a half-reaction or half-cycle, two-step process where, in a first half-cycle, a first precursor binds to the surface of the material to be etched (adsorption), the first precursor is purged, and then, in a second half-cycle, a second precursor (or co-reactant) is added to react with the adsorbed/bound intermediate entity formed by the first precursor.
- the reaction of the second precursor with the first adsorbed entity forms a deposited material.
- the general ALD process includes a substrate that is reacted with an alkaline metal precursor in the first half reaction to form a first intermediate entity having the alkaline metal from the alkaline metal precursor.
- second precursor such as a fluorine containing reducing agent
- FIG. 1 illustrates one embodiment of such a process, where the alkaline metal fluoride form is CaF 2 .
- the ALD occurs with a substrate serving as the initial deposition surface.
- the substrate may be an aluminum compound.
- the substrate surface should be considered.
- F-terminated surfaces to react Ca precursor (e.g., AlF 3 surface).
- surface nature can define the nucleation delay (few-to-many initial ALD cycles) for the process until the process achieves steady state growth of the ALD layer. Note that the Al 2 O 3 or silicon surface is mostly OH terminated and favors fluoride growth due to strong interaction with subsequent fluorine-based precursor dose.
- the ALD process includes a first metal precursor.
- the first metal precursor comprises an amidinate, such as calcium amidinate ([Ca(amd) 2 ] 2 ).
- the ALD process further includes a second precursor.
- the second precursor is reactive with the intermediate entity formed by the first metal precursor.
- the second precursor may be a fluorinated precursor.
- the second precursor is selected from the group consisting of HF, HF-pyridine, WF 6 , TaF 5 , MoF 6 , and NbF 5 .
- each ALD process consists of a cycle, which may be repeated to form a supercycle, with a first metal precursor vapor pulse, such as calcium amidinate ([Ca(amd) 2 ] 2 ) (e.g., for 3 seconds), for a first precursor exposure (e.g., for 3 seconds); followed by a first metal precursor purge (e.g., for 15 seconds), such as where the reactor is pumped to a vacuum; followed by a second precursor pulse, such as hydrogen fluoride (e.g., for 1 second), with a second precursor exposure (e.g., for 1 second); followed by a second precursor purge (e.g., for 10 seconds).
- a first metal precursor vapor pulse such as calcium amidinate ([Ca(amd) 2 ] 2 ) (e.g., for 3 seconds)
- a first precursor exposure e.g., for 3 seconds
- a first metal precursor purge e.g., for 15 seconds
- a second precursor pulse such as hydrogen fluoride (
- the precursor dose and purge time is based on the self-limiting behavior of the precursors. This can be varied in wide range from a few milliseconds to 10s of seconds. Further if a longer dose then purge time is utilized, the times may need to increase to avoid a CVD type reaction, which can results in non-uniformity and particles formation.
- ALD schemes can be constructed as a super-cycle comprising various sub-cycles for depositing a material as described or for depositing multiple different materials for multiple dopants or formation of bi- (tri-, etc.) metallic materials, such as varying the parameters for any of the individual steps within a cycle.
- the deposition may be a doped layer or a mixed metal composite.
- the respective pulse and exposures may be the same time or pulse may be for a shorter time than the overall exposure.
- the first precursor is a vapor and the first precursor pulse comprises input to the reactor of a first precursor vapor for a first metal precursor pulse time of a few milliseconds to 10s of seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 3 seconds.
- the first partial pressure of the first precursor pulse can be in the range of 0.01-1000 Torr (e.g., 10, 25, 50, 75, 100, 500, or 1000 Torr, inclusive of all ranges and values therebetween), such as, in one embodiment, at least 0.5-100 Torr, such as 0.88 Torr.
- the time length, pressure, and amount of precursor for the pulse are all factors in determining the overall amount for each of those operation parameters.
- the pressure and amount may follow from the duration of the pulse but depend on the size of the chamber and the type of valve as would be understood from general knowledge regarding ALD.
- the process is described with regard to the pulse duration, but it should be understood that the precursor partial pressure is what dictates the diffusion boundary conditions.
- a carrier gas such as argon or other non-reactive (with the substrate or the precursors) gas, may be used.
- the first precursor exposure comprises exposing the substrate to the first precursor for a first exposure time and a first partial pressure of the first metal precursor so that the first precursor binds with the substrate or coating from prior ALD cycles on the substrate.
- the pulse given the short time for the pulse/exposure for this ALD process the pulse lasts the entire exposure until the purge starts with the pulse time and exposure time being the same.
- the first metal precursor pulse time may be less than the first exposure time, or they may be equal such that the exposure is the same as the pulse.
- the first exposure time can be in the range of 0.5-500 seconds (e.g., 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween).
- the first predetermined time is in the range of 1-10 seconds (e.g., about 3 seconds).
- the first partial pressure of the first metal precursor can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween).
- the first partial pressure of the first metal precursor is in the range of 0.1-1 Torr (e.g., about 0.88 Torr). A longer dose is needed for high surface area powder/catalysis coatings.
- the first precursor purge evacuates unreacted precursor from the reactor.
- the first precursor purge may be for a first precursor purge time of 0.5-30 seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 15 seconds.
- the first precursor purge reduces the pressure in the reactor to within the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween), such as substantially to vacuum.
- the base material can be heated to a predetermined temperature during the ALD process.
- the first predetermined temperature can be in the range of 50-200° C. (e.g., 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200° C., inclusive of all ranges and values therebetween).
- the first predetermined temperature is in the range of 100-300° C. (e.g., 225° C.). Temperature also impacts the overall energy in the system and the performance for diffusion and/or reaction.
- the deposition temperature range where more or less same growth as function of growth occurs is referred to as the “ALD window.”
- the ALD reaction should occur at a temperature of the of the precursor sufficient to give constant precursors evaporation rate (i.e., vapor pressure). If vapor pressure is not enough, there may still be layer growth, but the surface coverage will be poor. If vapor pressure is too much, it will waste precursor, and there may be CVD growth if there is not sufficient purge time due to mixing of precursors.
- the temperature of the layer growth can be as low as subliming temperature of the ALD precursors. For example if precursor sublimes at 150° C. films can also grow around that temperature. But generally layer growth temperature is 25-50° C. higher than precursor sublimation temperature.
- the substrate after reaction with the first metal precursor, is then exposed to a second precursor by a second precursor pulse introducing the second precursor to the reactor and then exposing for the second precursor exposure such that the second precursor reacts with the first metal precursor or, more particularly, with intermediate entity formed by the first metal precursor and the substrate (or ALD coating on the substrate).
- the second precursor pulse comprises input to the reactor of the second precursor vapor for a second precursor pulse time of 0.5-30 seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 1 second.
- the first partial pressure of the second precursor pulse can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween) such as 0.88 Torr.
- the second precursor exposure time can be in the range of 0.5-500 seconds (e.g., 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween), such as about 1 second.
- the second partial pressure of the second precursor can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween). In some embodiments, the second partial pressure of the second precursor is in the range of 0.1-1 Torr (e.g., about 0.5 Torr) such as 0.88 Torr.
- the second precursor purge evacuates unreacted precursor from the reactor.
- the second precursor purge may be for a second precursor purge time of 0.5-500 seconds (0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween), such as 10 seconds.
- the second precursor purge reduces the pressure in the reactor to within the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween), such as substantially to vacuum.
- the second precursor may include one or more of HF, WF 6 , TaF 5 , MoF 6 , NbF 5 , and hexafluoroacetylacetonate (“hfacac”).
- any number of cycles of exposing the base material to the first metal precursor and the second precursor can be performed to reach a thickness of coating or to provide a desired alteration of the substrate properties.
- the number of cycles of the ALD process can be in the range of 1-50 (e.g., 1 cycle, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 cycles, inclusive of all ranges and values therebetween).
- CaF 2 is an ionic crystal with the fluorite structure.
- the lattice is a face centered cubic (“FCC”) structure with three sub-lattices.
- the unit cell of the material is most easily described as a simple cubic lattice formed by the F ⁇ ions where a Ca 2+ ion is contained in every second cube.
- the remaining empty cubes called as interstitial or hollow sites are important for defect formation and diffusion, but also for the accommodation of unwanted impurities like rare earth ions and dopants.
- the natural cleavage plane of the crystal is the (111) surface. It is build up from F ⁇ —Ca 2+ —F ⁇ triple layers of 3.14 ⁇ distance and is terminated by fluorine ions.
- the mass per steady state CaF 2 ALD cycle is 12 ng/cm 2 (F ⁇ —Ca 2+ —F ⁇ ) or growth rate is 0.3 A/cycle ( FIG. 2D ); therefore, in one embodiment, the process is depositing a partial layer in each cycle of CaF 2 .
- CaF 2 films can be utilized as a SEE material.
- the CaF 2 film may be deposited on (and within) MCP materials.
- the MCP may include the CaF 2 emissive layer over a resistive layer and in communication with electrodes.
- the ALD of CaF 2 was carried out in a hot-wall viscous flow reactor described elsewhere, using ultrahigh purity Argon (UHP, 99.999%) carrier gas at a mass flow rate of 45 sccm and a background pressure of 0.87 Torr.
- ALD was performed in the temperature range 75-300° C. while standard depositions were carried out at 225° C.
- the reactor was equipped with a quartz crystal microbalance (Maxtek BSH-150 sensor head, housing a single-side polished 6 MHz RC-cut quartz crystal sensor (Phillip Technologies), backside purged). If not stated otherwise, QCM experiments were carried out on CaF 2 surface.
- the QCM surface was coated with ⁇ 5 nm ALD Al 2 O 3 using 50 cycles of trimethylaluminum (“TMA”) and H 2 O with the timing sequence 1.0 sec-10.0 sec-1.0 sec-10.0 sec for precursor dose and purge length, respectively.
- TMA trimethylaluminum
- the ALD reactor also housed a quadrupole mass spectrometer (“QMS”) (Stanford Research Systems, RGA300, differentially pumped and located downstream from the sample/QCM position, separated from the reactor by a 35 ⁇ m orifice).
- QMS quadrupole mass spectrometer
- Transmittance absorbance Fourier-transform infrared (“FT-IR”) spectroscopy was carried out in a similarly equipped, smaller ALD reactor connected to a Nicolet 6700 FTIR (Thermo Scientific) spectrometer.
- the FTIR sample substrate was a steel mesh loaded with ZrO 2 nanoparticles heated to 225° C.
- the Ca precursor bis(N,N′-di-i-propylformamidinato)calcium(II) dimer, (Strem Chemicals, 99.99%-Ca, [Ca(amd) 2 ] 2 ) was maintained at 131° C. in a stainless steel bubbler, which was connected via stainless steel tubing and a manifold (heated to 145° C.
- HF-Py Sigma Aldrich, 98%), TMA, and H 2 O were kept at room temperature.
- ALD of CaF 2 thin films was accomplished by sequential feeding of [Ca(amd) 2 ] 2 and HF-Py, separated by purge steps using Ar.
- the optimized recipe for [Ca(amd) 2 ] 2 -purge-HF-Py-purge was as follows: 3.0 sec-10.0 sec1.0 sec15.0 sec.
- As substrates n-type Si(100), Si(111), fused silica, GCA plates (Incom Inc.), sapphire (Al 2 O 3 ), MgF 2 (111) and TiN were used. Sample size was in the range of 2 cm 2 -3 cm 2 .
- CaF 2 thin films were analyzed ex situ using XRR, spectroscopic ellipsometry (“SE”), X-ray diffractometry (“XRD”), XPS, and transmission electron microscopy (“TEM”). Thickness values were obtained from SE (J. A. Woollam Co. Alpha SE).
- SE spectroscopic ellipsometry
- XRD X-ray diffractometry
- TEM transmission electron microscopy
- Thickness values were obtained from SE (J. A. Woollam Co. Alpha SE).
- XRR measurements were performed on a Bruker D8 Discovery in the range 0.1-2° (Cu K ⁇ source).
- Raw data from the XRR measurements were fitted using the software GenX and using stoichiometries obtained from XPS measurements.
- XPS measurements were carried on a Thermo Fisher k-Alpha+. The XPS spectra were analyzed using the Thermo Fisher Avantage software and were referenced to the C 1s peak at 284.8 e
- the spin-orbit split doublet areas and full width at half maximum (“FWHM”) values were constrained for the respective core level spectra applying a mixed Lorentzian-Gaussian peak shape (mixing factor was 0.3, where 1.0 is a pure Lorentzian and 0.0 is a pure Gaussian fitting).
- Lift-out TEM lamellae were prepared using a Zeiss 1540XB FIB-SEM and imaged on a 200 keV FEI Tecnai F20ST (S)TEM.
- MCP Gain measurements FIG. 10 ) were carried out in a vacuum chamber using a Keithley picoammeter voltage sources under UV light irradiation (Hg-lamp).
- a non-steady-state regime with changing slope i.e., MCPC
- MCPC non-steady-state regime with changing slope
- Regime I is characterized by a decreasing MCPC, indicating the loss of reactive surface sites.
- the above described behavior can be seen in detail in FIG. 3B , where a decreasing MCPC for the HF exposure is identified.
- ⁇ m HF approaches 0.0 ng cm ⁇ 2 cycle ⁇ 1 , indicating that the mass gain from AlF 3 formation and mass loss from CaF 2 formation are of the same value and balance each other out.
- FIGS. 12A-12B The growth of CaF 2 was investigated using the here presented process several times and found identical values for different runs ( FIGS. 12A-12B ). The nucleation was further examined using AFM and FIGS. 6B-6G show AFM images of the different growth Regimes.
- AFM imaging CaF 2 ALD was carried out on ALD grown Al 2 O 3 (18 nm) on silicon to provide a similar surface as during QCM experiments. The RMS roughness increases slightly from 0.12 nm (Al 2 O 3 surface reference) to 0.44 nm for the 100 cycle sample.
- Granular shapes are of 20-30 nm in diameter, indicating that island-like growth took place and a closed layer of CaF 2 is formed.
- the roughness (0.27 nm) is similar compared to the 35 cycle deposition.
- Lee also provided a good approach to calculate the amount of adsorbed HF molecules in dependence of the ratio of ⁇ M [Ca(amd) 2 ] 2 and the respective molecular masses of involved species.
- the ratio of ⁇ M [Ca(amd) 2 ] 2 can be described as:
- ALD CaF 2 The structure and texture of ALD CaF 2 was evaluated on different substrates, including sapphire, MgF 2 , Si(111), and Si(100).
- the composition of ALD-grown CaF 2 thin films was obtained from XPS.
- the ideal ratio of F/Ca was found to be 2.0 for films deposited at between 175-225° C. and the films were free of carbon after sputtering, while oxygen concentrations were around 4.7 at. %. Annealing the films at 400° C. decreased the oxygen concentration to 4.4 at. %. Details of XPS results are listed in Table 1 below. The composition stayed constant throughout the bulk of the thin films (see XPS depth profile, FIG. 13 ). The homogeneity of the deposition with respect to composition was mapped using HAADF imaging in a STEM FIG. 14 .
- FIG. 8A shows the HAADF image of a representative, enlarged interface region of a cross-cut sample of 77 nm thickness.
- FIGS. 8B-8E show the images obtained from scattered electrons with respect to the elements of interest (i.e., Si, O, Ca, and F, respectively), and FIG. 8F is a hypermap of the three elements Si, Ca, and O.
- the HAADF experiments reveal the formation of a sharp interface with the native silicone oxide and a highly homogenous distribution of Ca and F. Matching XPS results, minor oxygen impurities are seen in FIG. 8B .
- the structure of the ALD grown CaF 2 was investigated using X-ray diffraction, which revealed polycrystalline thin films with a predominant orientation in the CaF 2 (111) direction ( FIG.
- FIG. 8A shows a TEM image of as deposited CaF 2 , and the material was found to be crystalline throughout the whole film. Interestingly, large single-crystalline domains were identified, indicating the growth of high-quality CaF 2 thin films.
- FIGS. 2A-2D show the MGPC for saturation studies of the two precursors ( FIGS. 2A and 2B for [Ca(amd) 2 ] 2 and HF, respectively), the MGPC vs. temperature ( FIG. 2C ) and the overall thickness of CaF 2 films vs. number of ALD cycles ( FIG. 2D ).
- FIGS. 2A and 2B show self-limiting MGPC values of (11.03 ⁇ 0.76) ng cm ⁇ 2 cycle ⁇ 1 and (10.08 ⁇ 0.11) ng cm ⁇ 2 cycle ⁇ 1 for the Ca and HF precursor, respectively, with a dose time of 1.0 second for [Ca(amd) 2 ] 2 and HF being sufficient to achieve ALD-like growth.
- a broad ALD window i.e., the MGPC being independent of the substrate temperature
- FIG. 2C shows self-limiting MGPC values of (11.03 ⁇ 0.76) ng cm ⁇ 2 cycle ⁇ 1 and (10.08 ⁇ 0.11) ng cm ⁇ 2 cycle ⁇ 1 for the Ca and HF precursor, respectively, with a dose time of 1.0 second for [Ca(amd) 2 ] 2 and HF being sufficient to achieve ALD-like growth.
- a broad ALD window i.e., the MGPC being independent of the substrate temperature
- FIG. 2C shows self-limiting MGPC values of (11.03 ⁇ 0.7
- 2D shows a clear linear trend of film thickness vs. the applied number of ALD cycles (3 sec. -15 sec.-1 sec.-10 sec.) and the slope of the linear fit yields a growth rate per cycle (GPC) of 0.034 nm cycle ⁇ 1 .
- GPC growth rate per cycle
- ⁇ is the density of the deposited material
- the density of was calculated to be (3.04 ⁇ 0.18) g cm ⁇ 3 .
- the density was also calculated from XRR data, shown in FIG. 11 . From this, a density of 3.14 g cm ⁇ 3 was obtained, matching literature values (3.18 g cm ⁇ 3 ) for cubic, crystalline CaF 2 closely.
- FIG. 9 shows the refractive index n for ALD CaF 2 in the UV (selected values) and visible range.
- the two different measurements demonstrate the same trend, with the refractive index decreasing monotonically with increasing wavelength.
- the overall low refractive index makes this material promising for optical applications (e.g., such as VUV reflecting coatings, if combined with a material of higher refractive index (e.g., LaF 3 ).
- the CaF 2 ALD process was further applied to MCP structures, which were readily coated with a resistive coating of W:Al 2 O 3 , which is described in detail elsewhere. Results for four CaF 2 coatings with varying thickness and respective signal gains are shown in FIG. 10 . While all coatings show and increased signal gain increased voltage, the CaF 2 coating of 6.4 nm shows the best performance with a total gain>106 at 1300 V bias voltage. This value is close/higher than those reported for established SEE materials such as MgO and Al 2 O 3 .
- Coupled means the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent or fixed) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members coupled directly to each other, with the two members coupled to each other using a separate intervening member and any additional intermediate members coupled with one another, or with the two members coupled to each other using an intervening member that is integrally formed as a single unitary body with one of the two members.
- circuit A communicably “coupled” to circuit B may signify that the circuit A communicates directly with circuit B (i.e., no intermediary) or communicates indirectly with circuit B (e.g., through one or more intermediaries).
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Abstract
Description
- This invention was made with government support under Contract No. DE-AC02-06CH11357 awarded by the United States Department of Energy to UChicago Argonne, LLC, operator of Argonne National Laboratory. The government has certain rights in the invention.
- The present disclosure relates to atomic layer deposition, specifically deposition of fluoride thin films.
- Thin layer deposition of material provides the ability to modify substrates or templates to have specific desired properties. For example, the alkaline earth metal fluorides MgF2, CaF2, BaF2, and SrF2 share the fascinating property of exhibiting high transparency, ranging from wavelengths in vacuum ultraviolet (“VUV”) to the long infrared spectrum, covering wavelengths from 150 nm to 11 μm. As a result, these materials have found uses in a range of optical applications. Calcium fluoride is of particular interest for optical applications because of its low refractive index (n<1.46).
- While various deposition techniques have been used with alkaline earth metal fluorides, including CaF2, (e.g., molecular-beam epitaxy (“MBE”), electron beam evaporation (“EBE”), thermal evaporation, pulsed laser deposition (“PLD”), and chemical vapor deposition (“CVD”)), the use of atomic layer deposition (“ALD”) has proved difficult for these materials. Further, in order to accommodate a range of underlying substrates and avoid altering of the overall properties, particularly optical properties, the temperature of the deposition process is considered. Prior reports regarding ALD of alkaline earth metal fluorides have been above 200° C., such as 200-450° C. There remains a need for a lower temperature, such as sub-225° C. or sub-200° C. ALD deposition process for alkaline earth metal fluorides.
- At least one embodiment relates to a method of forming a secondary electron emissive (“SEE”) coating. A substrate is provided within an ALD reactor. A coating of CaF2 is deposited by atomic layer deposition process including at least one cycle of: pulsing a first metal precursor comprising an alkaline metal amidinate into the reactor for a first metal precursor pulse time; purging the reactor of the first metal precursor; pulsing a second precursor comprising a fluorinated compound into the reactor for a second precursor pulse time; and purging the reactor of the co-reactant precursor. The depositing occurs at a reaction temperature greater than a highest sublimation temperature of the first metal precursor and the second metal precursor and less than 50° C. above the highest sublimation temperature.
- Another embodiment relates to method of forming an electron amplifier. An electron amplifier substrate having an emissive layer and a resistive layer is provided within an ALD reactor. A coating of CaF2 is deposited by atomic layer deposition process including at least one cycle of: pulsing a first metal precursor comprising [Ca(amd)2]2 into the reactor for a first metal precursor pulse time; purging the reactor of the first metal precursor; pulsing a second precursor selected from the group consisting of hydrogen fluoride (“HF”), HF-pyridine (“HF-Py”), WF6, TaF5, MoF6, and NbF5 into the reactor for a second precursor pulse time; and purging the reactor of the second precursor.
- Another embodiment relates to an electron detector device comprising a microchannel plate having a plurality of channels extending therethrough. A resistive coating is deposited on the microchannel plate. The device further includes an emissive coating deposited on the resistive coating; the emissive coating comprising CaF2.
- This summary is illustrative only and is not intended to be in any way limiting. Other aspects, inventive features, and advantages of the devices or processes described herein will become apparent in the detailed description set forth herein, taken in conjunction with the accompanying figures, wherein like reference numerals refer to like elements.
- Before turning to the figures, which illustrate certain exemplary embodiments in detail, it should be understood that the present disclosure is not limited to the details or methodology set forth in the description or illustrated in the figures. It should also be understood that the terminology used herein is for the purpose of description only and should not be regarded as limiting.
-
FIG. 1 shows one embodiment of an ALD process for deposition of CaF2 employing [Ca(amd)2]2 and HF precursors. -
FIGS. 2A-2D show quartz crystal microbalance (“QCM”) studies on the [Ca(amd)2]2-HF ALD process.FIGS. 2A-2B show mass change per cycle (“MCPC”) (or mass grown per cycle (“MGPC”)) for saturation studies of the two precursors Ca and HF, respectively.FIG. 2C is a plot of MCPC vs. growth temperature.FIG. 2D shows thin film thickness vs. applied number of cycles. The linear fit (dashed line) serves to guide the eye. -
FIGS. 3A-3B show QCM studies during nucleation phase of CaF2 ALD on an Al2O3-coated QCM crystal. A feeding sequence of 3.0 sec-15.0 sec-1.0 sec-10 sec was applied at 225° C. -
FIGS. 4A-4B show enlarged areas of QCM nucleation studies (fromFIG. 3A ) for the ALD of CaF2 on Al2O3.FIG. 4A shows initial three cycles;FIG. 4B shows steady-state regime (fromFIG. 3B ). Blue and green rectangles indicate the dose times of the two precursors. -
FIG. 5 shows root-mean-squared (“RMS”) roughness obtained from atomic force microscopy (“AFM”) images. -
FIGS. 6A-6G are AFM images of CaF2 thin films deposited on 18 nm ALD Al2O3. -
FIG. 7 is a XRD of the CaF2 layer. -
FIGS. 8A-8F are high-angle annular dark-field (“HAADF”) spectra from scanning transmission electron microscope (“STEM”) experiments on ALD CaF2 thin film deposited at 225° C. on Si(100). -
FIG. 9 shows the refractive index of ALD CaF2 in the ultraviolet (“UV”) and visible range. Data points in the UV range were obtained from reflectivity measurements while values for n in the visible range were obtained from ellipsometry. -
FIG. 10 shows electron signal gain of CaF2-coated micro-channel plates (“MCPs”). -
FIG. 11 is a plot of X-ray reflectivity (“XRR”) data and the corresponding fit for an as-deposited CaF2 ALD thin film, deposited at 225° C. on Si using [Ca] and HF-PY applying 2250 cycles. -
FIGS. 12A-12B show repeated QCM studies during nucleation of CaF2 ALD on an Al2O3 coated QCM crystal. A feeding sequence of 3.0 sec-15.0 sec-1.0 sec-10 sec was applied at 225° C. in both cases. -
FIG. 13 is a representative X-ray photoelectron spectroscopy (“XPS”) depth profile of ALD CaF2 grown on Si(100) at 225° C. -
FIGS. 14A-14F are HAADF overlaid images for the elements Ca, F, O, and Si. - In one embodiment, ALD is utilized. In its simplest form, ALD is a half-reaction or half-cycle, two-step process where, in a first half-cycle, a first precursor binds to the surface of the material to be etched (adsorption), the first precursor is purged, and then, in a second half-cycle, a second precursor (or co-reactant) is added to react with the adsorbed/bound intermediate entity formed by the first precursor. The reaction of the second precursor with the first adsorbed entity forms a deposited material.
- In one embodiment, the general ALD process includes a substrate that is reacted with an alkaline metal precursor in the first half reaction to form a first intermediate entity having the alkaline metal from the alkaline metal precursor. In a second half reaction, second precursor, such as a fluorine containing reducing agent, is exposed to the first intermediate entity and reacted to form the alkaline metal fluoride.
FIG. 1 illustrates one embodiment of such a process, where the alkaline metal fluoride form is CaF2. - The ALD occurs with a substrate serving as the initial deposition surface. The substrate may be an aluminum compound. As starting surface is key point for many ALD deposition, the substrate surface should be considered. For example, embodiments relating to fluoride layer growth will benefit from F-terminated surfaces to react Ca precursor (e.g., AlF3 surface). Secondly, surface nature can define the nucleation delay (few-to-many initial ALD cycles) for the process until the process achieves steady state growth of the ALD layer. Note that the Al2O3 or silicon surface is mostly OH terminated and favors fluoride growth due to strong interaction with subsequent fluorine-based precursor dose.
- The ALD process includes a first metal precursor. In one embodiment, the first metal precursor comprises an amidinate, such as calcium amidinate ([Ca(amd)2]2).
- The ALD process further includes a second precursor. The second precursor is reactive with the intermediate entity formed by the first metal precursor. The second precursor may be a fluorinated precursor. In some embodiments, the second precursor is selected from the group consisting of HF, HF-pyridine, WF6, TaF5, MoF6, and NbF5.
- In one embodiment, each ALD process consists of a cycle, which may be repeated to form a supercycle, with a first metal precursor vapor pulse, such as calcium amidinate ([Ca(amd)2]2) (e.g., for 3 seconds), for a first precursor exposure (e.g., for 3 seconds); followed by a first metal precursor purge (e.g., for 15 seconds), such as where the reactor is pumped to a vacuum; followed by a second precursor pulse, such as hydrogen fluoride (e.g., for 1 second), with a second precursor exposure (e.g., for 1 second); followed by a second precursor purge (e.g., for 10 seconds). It should be appreciated that the precursor dose and purge time is based on the self-limiting behavior of the precursors. This can be varied in wide range from a few milliseconds to 10s of seconds. Further if a longer dose then purge time is utilized, the times may need to increase to avoid a CVD type reaction, which can results in non-uniformity and particles formation.
- It should be appreciated that more complicated ALD schemes can be constructed as a super-cycle comprising various sub-cycles for depositing a material as described or for depositing multiple different materials for multiple dopants or formation of bi- (tri-, etc.) metallic materials, such as varying the parameters for any of the individual steps within a cycle. In one embodiment, the deposition may be a doped layer or a mixed metal composite.
- The respective pulse and exposures may be the same time or pulse may be for a shorter time than the overall exposure.
- In some embodiments, the first precursor is a vapor and the first precursor pulse comprises input to the reactor of a first precursor vapor for a first metal precursor pulse time of a few milliseconds to 10s of seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 3 seconds. The first partial pressure of the first precursor pulse can be in the range of 0.01-1000 Torr (e.g., 10, 25, 50, 75, 100, 500, or 1000 Torr, inclusive of all ranges and values therebetween), such as, in one embodiment, at least 0.5-100 Torr, such as 0.88 Torr. One of skill in the art will appreciate that the time length, pressure, and amount of precursor for the pulse are all factors in determining the overall amount for each of those operation parameters. For example, the pressure and amount may follow from the duration of the pulse but depend on the size of the chamber and the type of valve as would be understood from general knowledge regarding ALD. Note, for ease of reference herein, the process is described with regard to the pulse duration, but it should be understood that the precursor partial pressure is what dictates the diffusion boundary conditions. A carrier gas, such as argon or other non-reactive (with the substrate or the precursors) gas, may be used.
- In some embodiments, the first precursor exposure comprises exposing the substrate to the first precursor for a first exposure time and a first partial pressure of the first metal precursor so that the first precursor binds with the substrate or coating from prior ALD cycles on the substrate. In some embodiments, given the short time for the pulse/exposure for this ALD process the pulse lasts the entire exposure until the purge starts with the pulse time and exposure time being the same. The first metal precursor pulse time may be less than the first exposure time, or they may be equal such that the exposure is the same as the pulse. The first exposure time can be in the range of 0.5-500 seconds (e.g., 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween). In some embodiments, the first predetermined time is in the range of 1-10 seconds (e.g., about 3 seconds). The first partial pressure of the first metal precursor can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween). In some embodiments, the first partial pressure of the first metal precursor is in the range of 0.1-1 Torr (e.g., about 0.88 Torr). A longer dose is needed for high surface area powder/catalysis coatings.
- The first precursor purge evacuates unreacted precursor from the reactor. The first precursor purge may be for a first precursor purge time of 0.5-30 seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 15 seconds. The first precursor purge reduces the pressure in the reactor to within the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween), such as substantially to vacuum.
- In some embodiments, the base material can be heated to a predetermined temperature during the ALD process. For example, the first predetermined temperature can be in the range of 50-200° C. (e.g., 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200° C., inclusive of all ranges and values therebetween). In some embodiments, the first predetermined temperature is in the range of 100-300° C. (e.g., 225° C.). Temperature also impacts the overall energy in the system and the performance for diffusion and/or reaction. In an ALD process, the deposition temperature range where more or less same growth as function of growth occurs is referred to as the “ALD window.” The ALD reaction should occur at a temperature of the of the precursor sufficient to give constant precursors evaporation rate (i.e., vapor pressure). If vapor pressure is not enough, there may still be layer growth, but the surface coverage will be poor. If vapor pressure is too much, it will waste precursor, and there may be CVD growth if there is not sufficient purge time due to mixing of precursors. The temperature of the layer growth can be as low as subliming temperature of the ALD precursors. For example if precursor sublimes at 150° C. films can also grow around that temperature. But generally layer growth temperature is 25-50° C. higher than precursor sublimation temperature.
- The substrate, after reaction with the first metal precursor, is then exposed to a second precursor by a second precursor pulse introducing the second precursor to the reactor and then exposing for the second precursor exposure such that the second precursor reacts with the first metal precursor or, more particularly, with intermediate entity formed by the first metal precursor and the substrate (or ALD coating on the substrate).
- In some embodiments, the second precursor pulse comprises input to the reactor of the second precursor vapor for a second precursor pulse time of 0.5-30 seconds (e.g., 0.5, 1, 5, 10, 20, or 30 seconds, inclusive of all ranges and values therebetween), such as 1 second. The first partial pressure of the second precursor pulse can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween) such as 0.88 Torr.
- In some embodiments, exposing the electrode to second precursor for a second precursor exposure time and a second partial pressure of the second precursor so that second precursor reacts with the entity formed by the first metal precursor reacting with the substrate (or previous ALD deposited coatings). The second precursor exposure time can be in the range of 0.5-500 seconds (e.g., 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween), such as about 1 second. The second partial pressure of the second precursor can be in the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween). In some embodiments, the second partial pressure of the second precursor is in the range of 0.1-1 Torr (e.g., about 0.5 Torr) such as 0.88 Torr.
- The second precursor purge evacuates unreacted precursor from the reactor. The second precursor purge may be for a second precursor purge time of 0.5-500 seconds (0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450 or 500 seconds, inclusive of all ranges and values therebetween), such as 10 seconds. The second precursor purge reduces the pressure in the reactor to within the range of 0.01-10 Torr (e.g., 0.01, 0.05, 0.1, 0.5, 1.0, 5.0, or 10 Torr, inclusive of all ranges and values therebetween), such as substantially to vacuum. In some embodiments, the second precursor may include one or more of HF, WF6, TaF5, MoF6, NbF5, and hexafluoroacetylacetonate (“hfacac”).
- Any number of cycles of exposing the base material to the first metal precursor and the second precursor can be performed to reach a thickness of coating or to provide a desired alteration of the substrate properties. In some embodiments, the number of cycles of the ALD process can be in the range of 1-50 (e.g., 1 cycle, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 cycles, inclusive of all ranges and values therebetween). CaF2 is an ionic crystal with the fluorite structure. The lattice is a face centered cubic (“FCC”) structure with three sub-lattices. The unit cell of the material is most easily described as a simple cubic lattice formed by the F− ions where a Ca2+ ion is contained in every second cube. The remaining empty cubes called as interstitial or hollow sites are important for defect formation and diffusion, but also for the accommodation of unwanted impurities like rare earth ions and dopants. The lattice constant is a=5.451 Å. The natural cleavage plane of the crystal is the (111) surface. It is build up from F−—Ca2+—F− triple layers of 3.14 Å distance and is terminated by fluorine ions. Consider the mass per steady state CaF2 ALD cycle is 12 ng/cm2 (F−—Ca2+—F−) or growth rate is 0.3 A/cycle (
FIG. 2D ); therefore, in one embodiment, the process is depositing a partial layer in each cycle of CaF2. This can be tuned based on available reaction sites on the depositing surface and precursor's structure. In one embodiment, CaF2 films can be utilized as a SEE material. For example, the CaF2 film may be deposited on (and within) MCP materials. The MCP may include the CaF2 emissive layer over a resistive layer and in communication with electrodes. - Experiments investigated the nucleation of ALD CaF2 thin films on ALD alumina by depositing a defined Al2O3 thin film on QCM crystals prior to CaF2 ALD.
FIG. 3A shows the QCM trace for such an experiment, andFIG. 3B shows the MCPC for both precursors (blue and green for [Ca(amd)2]2 and HF, respectively) and the overall mass gain for each cycle (black). In addition,FIGS. 4A-4B show enlarged areas of the QCM trace inFIG. 3A , showing the initial three cycles and a cut-out of the steady-state regime (cycle 55-57). - The ALD of CaF2 was carried out in a hot-wall viscous flow reactor described elsewhere, using ultrahigh purity Argon (UHP, 99.999%) carrier gas at a mass flow rate of 45 sccm and a background pressure of 0.87 Torr. ALD was performed in the temperature range 75-300° C. while standard depositions were carried out at 225° C. To monitor the growth mechanisms in situ, the reactor was equipped with a quartz crystal microbalance (Maxtek BSH-150 sensor head, housing a single-side polished 6 MHz RC-cut quartz crystal sensor (Phillip Technologies), backside purged). If not stated otherwise, QCM experiments were carried out on CaF2 surface. Prior to the QCM experiments, the QCM surface was coated with ˜5 nm ALD Al2O3 using 50 cycles of trimethylaluminum (“TMA”) and H2O with the timing sequence 1.0 sec-10.0 sec-1.0 sec-10.0 sec for precursor dose and purge length, respectively. The ALD reactor also housed a quadrupole mass spectrometer (“QMS”) (Stanford Research Systems, RGA300, differentially pumped and located downstream from the sample/QCM position, separated from the reactor by a 35 μm orifice). Transmittance absorbance Fourier-transform infrared (“FT-IR”) spectroscopy was carried out in a similarly equipped, smaller ALD reactor connected to a Nicolet 6700 FTIR (Thermo Scientific) spectrometer. The FTIR sample substrate was a steel mesh loaded with ZrO2 nanoparticles heated to 225° C. The Ca precursor bis(N,N′-di-i-propylformamidinato)calcium(II) dimer, (Strem Chemicals, 99.99%-Ca, [Ca(amd)2]2) was maintained at 131° C. in a stainless steel bubbler, which was connected via stainless steel tubing and a manifold (heated to 145° C. to avoid condensation) to the reactor. The HF-Py (Sigma Aldrich, 98%), TMA, and H2O were kept at room temperature. ALD of CaF2 thin films was accomplished by sequential feeding of [Ca(amd)2]2 and HF-Py, separated by purge steps using Ar. The optimized recipe for [Ca(amd)2]2-purge-HF-Py-purge was as follows: 3.0 sec-10.0 sec1.0 sec15.0 sec. As substrates, n-type Si(100), Si(111), fused silica, GCA plates (Incom Inc.), sapphire (Al2O3), MgF2(111) and TiN were used. Sample size was in the range of 2 cm2-3 cm2.
- CaF2 thin films were analyzed ex situ using XRR, spectroscopic ellipsometry (“SE”), X-ray diffractometry (“XRD”), XPS, and transmission electron microscopy (“TEM”). Thickness values were obtained from SE (J. A. Woollam Co. Alpha SE). XRR measurements were performed on a Bruker D8 Discovery in the range 0.1-2° (Cu Kα source). Raw data from the XRR measurements were fitted using the software GenX and using stoichiometries obtained from XPS measurements. XPS measurements were carried on a Thermo Fisher k-Alpha+. The XPS spectra were analyzed using the Thermo Fisher Avantage software and were referenced to the C 1s peak at 284.8 eV. For fitting the 2p peaks, the spin-orbit split doublet areas and full width at half maximum (“FWHM”) values were constrained for the respective core level spectra applying a mixed Lorentzian-Gaussian peak shape (mixing factor was 0.3, where 1.0 is a pure Lorentzian and 0.0 is a pure Gaussian fitting). Lift-out TEM lamellae were prepared using a Zeiss 1540XB FIB-SEM and imaged on a 200 keV FEI Tecnai F20ST (S)TEM. MCP Gain measurements (
FIG. 10 ) were carried out in a vacuum chamber using a Keithley picoammeter voltage sources under UV light irradiation (Hg-lamp). All measurements were carried out using the same reference electron generating MCP kept at fixed voltage which give define flux of electrons (input current) on the CaF2 monitor MCP, While the potential across the monitor CaF2-coated MCPs was varied from 0-1200 V, the reference MCP was operated with a voltage gap of 200 V across its front and end panels, being 100 V above the CaF2-coated MCP. The gain was calculated as the ratio of the current collected on the anode divided by the dark current. - From
FIG. 3A , a non-steady-state regime with changing slope (i.e., MCPC) can be identified up to ˜33 cycles, followed by a linear regime with constant slope. By separating the individual contributions from the Ca precursor exposure and the HF exposure, these two regimes can be separated into four more discreet regimes exhibiting different trends, overall growth rates and, potentially, different growth modes. - Regime I (1-5 cycles) shows an initial, global maximum for MCPC which is explained by a high vapor pressure for both precursors in this cycle (i.e., an high amount of precursor molecules due to non-equilibrium conditions when the valves are opened the first time). In this Regime, the HF exposure also contributes a positive MCPC, which is explained by the formation of AlF3 from Al2O3 and HF according to the reaction equation given below.
-
Al2O3+6HF→2AlF3+3H2O (1) - As two AlF3 units are formed per Al2O3, this reaction should be identified as a positive mass change in QCM experiments.
- Following this, Regime I is characterized by a decreasing MCPC, indicating the loss of reactive surface sites. The above described behavior can be seen in detail in
FIG. 3B , where a decreasing MCPC for the HF exposure is identified. Between the second and fifth cycle, ΔmHF approaches 0.0 ng cm−2 cycle−1, indicating that the mass gain from AlF3 formation and mass loss from CaF2 formation are of the same value and balance each other out. - Regime II (6th-33rd cycle) is characterized by a gradual increase in MCPC for the Ca-exposure and a gradual decrease in MCPC for the HF exposure, which both stabilize in a plateau. In this Regime, the maximum negative MCPC (mass loss) during the HF exposure was found to be −24.0 ng cm−2 cycle−1, whereas the maximum positive MCPC for the Ca exposure is of 40.0 ng cm−2 cycle−1, yielding a total MCPC of 13.0 ng cm−2 cycle−1. Both trends support each other and suggest that with an increased amount of Ca-precursor chemisorbed to the surface, more HF can transform Ca-amd species to CaF2. Vice versa, the more CaF2 is growing, the more Ca-amd can chemisorb on the surface. This can already be seen during the first three cycles (
FIG. 3B ). - Regime III resembles a transition phase with decreased mass loss (HF exposure) and mass gain (Ca exposure) and a total mass gain of 10.0 ng cm−2 cycle−1, which is pursued in Regime IV, the steady-state growth regime. That the previous reached plateau of Regime II is not the final steady-state MCPC indicates that the film is agglomerating during these initial 40 cycles. It is assumed that this CaF2-ALD process exhibits an island-growth mode before a closed layer is formed. Assuming island-growth explains the increasing negative MCPC for HF exposures in Regime II. Until a closed layer is formed, the formation of AlF3 (mass gain) and CaF2 (mass loss) compete with each other. Once a dense layer of CaF2 is formed, no further mass gain from AlF3 should contribute to the QCM measurement and only mass loss from CaF2 formation should be observed. The formation of a closed CaF2 can be seen in the transient Regime III. Enlarged details of the steady-state growth are shown in
FIG. 4B . With the HF exposure, an immediate mass loss is accompanied, suggested the removal of the heavy amidinate ligands from the Ca-precursor fragments on the surface ad replacement with fluorine anions. - A higher, overall MCPC in Regime II can be explained with a rougher surface (islands), having a higher active surface area than the finally closed layer, and thereby providing more reactive surface sites. The growth of CaF2 was investigated using the here presented process several times and found identical values for different runs (
FIGS. 12A-12B ). The nucleation was further examined using AFM andFIGS. 6B-6G show AFM images of the different growth Regimes. For AFM imaging, CaF2 ALD was carried out on ALD grown Al2O3 (18 nm) on silicon to provide a similar surface as during QCM experiments. The RMS roughness increases slightly from 0.12 nm (Al2O3 surface reference) to 0.44 nm for the 100 cycle sample. Already for 5 cycles, granular shapes can be observed on the surface, making it distinct from the reference sample (FIG. 12A ). With the MGPC being rather low for this process, it is likely that this image shows contribution from CaF2 growth and Al2O3/AlF3 etching. For 10 and 25 cycles (Regime II), the roughness is virtually identical but higher as for 5 cycles. Also, the grain diameter is of about 10-20 nm. For all these three samples, dark regions, corresponding to open voids, are identified, indicating a not completely closed layer of CaF2. For 35 cycles (Regime III), these voids do not contribute significantly to the surface appearance and the roughness increased to 0.3 nm. Granular shapes are of 20-30 nm in diameter, indicating that island-like growth took place and a closed layer of CaF2 is formed. For 50 cycles, the roughness (0.27 nm) is similar compared to the 35 cycle deposition. These findings match perfectly with the above discussed results and mechanisms from in situ QCM studies and corroborate our interpretation. After 50 and 100 cycles, the ALD CaF2 film shows an RMS-roughness of 0.44 nm and grains sizes increased to 20-50 nm, suggesting increases nucleation and fast growth.FIG. 5 shows the RMS-roughness plotted against ALD cycles. - By subtracting this linear component, the RMS-roughness from island-growth is obtained (
FIG. 5 , black dots). Matching the assumption of island-growth, the RMS-roughness increases initially, then decreases back to zero. The trend in RMS-roughness from island-growth correlates perfectly with the trend of MCPC values from QCM studies. A similar behaviour was observed for the nucleation of amorphous tungsten on Al2O3, indicating that the subtraction of a linear component for the ALD CaF2 thin films helps to correlate the respective data. - Lee, et al., have described a convincing mechanism for the ALD of metal fluorides employing HF as fluorine source together with various metalorganic precursors. (See LEE, et al., “Atomic Layer Deposition of Metal Fluorides Using HF-Pyridine as the Fluorine Precursor,” Chemistry of Materials 28(7), pp. 2022-2032 (2016)). In their studies, the adsorption of HF molecules on the previously formed MFx(M=Mg, Mn, Zn, Zr, and Hf; x=2 or 4) surface is suggested, acting as fluorine reservoir for the next metal precursor exposure. This prevailing HF than allows the partial removal and substitution of alkylamido, alkyl or alkyl-substituted cyclopentadienyl ligands. It is believed that this mechanism is valid for the recited process as well, although amidinate ligands are removed and substituted by fluorine.
- Lee also provided a good approach to calculate the amount of adsorbed HF molecules in dependence of the ratio of ΔM[Ca(amd)
2 ]2 and the respective molecular masses of involved species. The ratio of ΔM[Ca(amd)2 ]2 can be described as: -
- with M[Ca], M(CaF
2 ), and M(Hamd) being the molar masses of the respective compounds. The amount of released Hamd during the Ca-precursor exposure x is calculated by: -
- Using values obtained from QCM studies (
FIGS. 3A-3B and 4A-4B ) and the ratio for -
- of 2.7, x=0.7. This means there are roughly 0.7 HF molecules adsorbed per previously formed CaF2 unit in each ALD cycle. Lee, et al., correlated the amount of adsorbed HF molecules to the Lewis-acidity of the deposited metal fluorides. In agreement with the definition of Lewis-acidity, metal fluorides such as ZrF4 and HfF4 tend to adsorb more HF (x=2.2-2.4 and 2.2, respectively) than weak Lewis acids like MgF2 and MnF2 (x=0.0). Our results regarding adsorbed HF molecules place the deposited CaF2 thin films close to that from depositing AlF3, which was reported to adsorb 0.8 HF molecules per AlF3 unit. This is contradicting the assumption of CaF2, comprising a metal with low electronegativity, acting as weak Lewis acid. Lee also found that the amount of adsorbed HF varies depending on the ligands within a given class of metal precursors. For ZrF4, x was 2.0 when using tetra-tert-butoxyzirconium (“ZTB”) and 2.4 if tetrakis-(diethylamido)-zirconium(IV) was employed.
- Based on our results, it is believed that that the organic ligand of metalorganic precursors might influence the affinity of a given metal fluoride surface to accumulate HF molecules. Apart from the concept of Lewis-acidity, the size, charge and bonding situation of the ligand might increase the tendency to adsorb HF molecules.
Scheme 1 shows the mechanism of CaF2 ALD using [Ca(amd)2]2 and HF and the above discussed assumption of adsorbed HF molecules after the formation of CaF2. - The structure and texture of ALD CaF2 was evaluated on different substrates, including sapphire, MgF2, Si(111), and Si(100).
- The composition of ALD-grown CaF2 thin films was obtained from XPS. The ideal ratio of F/Ca was found to be 2.0 for films deposited at between 175-225° C. and the films were free of carbon after sputtering, while oxygen concentrations were around 4.7 at. %. Annealing the films at 400° C. decreased the oxygen concentration to 4.4 at. %. Details of XPS results are listed in Table 1 below. The composition stayed constant throughout the bulk of the thin films (see XPS depth profile,
FIG. 13 ). The homogeneity of the deposition with respect to composition was mapped using HAADF imaging in a STEMFIG. 14 . -
TABLE 1 Composition of CaF2 thin films for as-deposited and annealed (N2, 400° C.) samples. Concentration (at. %) Ca F O C N F/Ca As deposited Surface 27.9 57.6 4.6 9.9 n.d. 2.1 (175° C.) Sputtered 32.0 62.2 8.5 n.d. n.d. 1.9 As deposited Surface 29.2 61.3 3.2 6.3 n.d. 2.1 (200° C.) Sputtered 31.4 62.6 6.0 n.d. n.d. 2.0 Annealed Surface 24.0 45.2 5.3 24.0 1.5 1.9 Sputtered 31.2 64.5 4.4 n.d. n.d. 2.1 n.d. = not detected. -
FIG. 8A shows the HAADF image of a representative, enlarged interface region of a cross-cut sample of 77 nm thickness.FIGS. 8B-8E show the images obtained from scattered electrons with respect to the elements of interest (i.e., Si, O, Ca, and F, respectively), andFIG. 8F is a hypermap of the three elements Si, Ca, and O. The HAADF experiments reveal the formation of a sharp interface with the native silicone oxide and a highly homogenous distribution of Ca and F. Matching XPS results, minor oxygen impurities are seen inFIG. 8B . The structure of the ALD grown CaF2 was investigated using X-ray diffraction, which revealed polycrystalline thin films with a predominant orientation in the CaF2 (111) direction (FIG. 7 ). These findings were corroborated by TEM.FIG. 8A shows a TEM image of as deposited CaF2, and the material was found to be crystalline throughout the whole film. Interestingly, large single-crystalline domains were identified, indicating the growth of high-quality CaF2 thin films. -
FIGS. 2A-2D show the MGPC for saturation studies of the two precursors (FIGS. 2A and 2B for [Ca(amd)2]2 and HF, respectively), the MGPC vs. temperature (FIG. 2C ) and the overall thickness of CaF2 films vs. number of ALD cycles (FIG. 2D ). -
FIGS. 2A and 2B show self-limiting MGPC values of (11.03±0.76) ng cm−2 cycle−1 and (10.08±0.11) ng cm−2 cycle−1 for the Ca and HF precursor, respectively, with a dose time of 1.0 second for [Ca(amd)2]2 and HF being sufficient to achieve ALD-like growth. FromFIG. 2C , a broad ALD window (i.e., the MGPC being independent of the substrate temperature) can be seen, ranging from 175-275° C. with an average value of (9.9±0.2) ng cm−2 cycle−1. It should be noted that other ALD processes for CaF2 thin films are usually operated at temperatures around/between 225-400° C.FIG. 2D shows a clear linear trend of film thickness vs. the applied number of ALD cycles (3 sec. -15 sec.-1 sec.-10 sec.) and the slope of the linear fit yields a growth rate per cycle (GPC) of 0.034 nm cycle−1. Taking into account the MGPC from saturation studies and the ALD window investigation, an average MGPC of (10.34±0.61) ng cm−2 cycle−1 was obtained. According to: -
- where ρ is the density of the deposited material, the density of was calculated to be (3.04±0.18) g cm−3. The density was also calculated from XRR data, shown in
FIG. 11 . From this, a density of 3.14 g cm−3 was obtained, matching literature values (3.18 g cm−3) for cubic, crystalline CaF2 closely. - With respect to a potential application of the ALD CaF2 as SEE layer for MCP-detectors, optical window for deep UV filters for space application. Passivation layer for Ca-ion batteries, or other uses, CaF2 thin films were evaluated regarding their refractive index and extinction coefficient in the UV range (150-250 nm) using a VUV optics system at TRIUMF particle accelerator. The reflectivity was measured as a function of angle for wavelengths. Details of the calculations are described above in Eqs. 2 and 3. The obtained refractive index values for different wavelengths are summarized in Table 2 below.
-
TABLE 2 Refractive index and extinction coefficient for CaF2 (77 nm on Si) at different wavelengths in the UV range. As-deposited Annealed λ (nm) n k n K 150 1.56 ± 0.02 0.011 ± 0.002 1.56 ± 0.02 0.011 ± 0.002 160 1.58 ± 0.02 0.0027 ± 0.001 1.58 ± 0.02 165 1.58 ± 0.02 0.010 ± 0.002 1.58 ± 0.02 170 1.58 ± 0.02 0.0073 ± 0.002 1.58 ± 0.02 175 1.60 ± 0.02 0.0043 ± 0.002 1.60 ± 0.02 180 1.41 ± 0.05 0.028 ± 0.005 1.41 ± 0.05 193 1.45 ± 0.02 0.020 ± 0.005 1.45 ± 0.02 200 1.45 ± 0.02 0.016 ± 0.05 1.45 ± 0.02 250 1.32 ± 0.05 failed 1.32 ± 0.05 -
FIG. 9 shows the refractive index n for ALD CaF2 in the UV (selected values) and visible range. The two different measurements demonstrate the same trend, with the refractive index decreasing monotonically with increasing wavelength. The overall low refractive index makes this material promising for optical applications (e.g., such as VUV reflecting coatings, if combined with a material of higher refractive index (e.g., LaF3). - The CaF2 ALD process was further applied to MCP structures, which were readily coated with a resistive coating of W:Al2O3, which is described in detail elsewhere. Results for four CaF2 coatings with varying thickness and respective signal gains are shown in
FIG. 10 . While all coatings show and increased signal gain increased voltage, the CaF2 coating of 6.4 nm shows the best performance with a total gain>106 at 1300 V bias voltage. This value is close/higher than those reported for established SEE materials such as MgO and Al2O3. - No claim element herein is to be construed under the provisions of 35 U.S.C. § 112(f), unless the element is expressly recited using the phrase “means for.”
- As utilized herein, the terms “approximately,” “about,” “substantially,” and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the disclosure as recited in the appended claims.
- It should be noted that the term “exemplary” and variations thereof, as used herein to describe various embodiments, are intended to indicate that such embodiments are possible examples, representations, or illustrations of possible embodiments (and such terms are not intended to connote that such embodiments are necessarily extraordinary or superlative examples).
- The term “coupled” and variations thereof, as used herein, means the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent or fixed) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members coupled directly to each other, with the two members coupled to each other using a separate intervening member and any additional intermediate members coupled with one another, or with the two members coupled to each other using an intervening member that is integrally formed as a single unitary body with one of the two members. If “coupled” or variations thereof are modified by an additional term (e.g., directly coupled), the generic definition of “coupled” provided above is modified by the plain language meaning of the additional term (e.g., “directly coupled” means the joining of two members without any separate intervening member), resulting in a narrower definition than the generic definition of “coupled” provided above. Such coupling may be mechanical, electrical, or fluidic. For example, circuit A communicably “coupled” to circuit B may signify that the circuit A communicates directly with circuit B (i.e., no intermediary) or communicates indirectly with circuit B (e.g., through one or more intermediaries).
- The term “or,” as used herein, is used in its inclusive sense (and not in its exclusive sense) so that when used to connect a list of elements, the term “or” means one, some, or all of the elements in the list. Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is understood to convey that an element may be either X, Y, Z; X and Y; X and Z; Y and Z; or X, Y, and Z (i.e., any combination of X, Y, and Z). Thus, such conjunctive language is not generally intended to imply that certain embodiments require at least one of X, at least one of Y, and at least one of Z to each be present, unless otherwise indicated.
- References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below”) are merely used to describe the orientation of various elements in the figures. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure.
- Although the figures and description may illustrate a specific order of method steps, the order of such steps may differ from what is depicted and described, unless specified differently above. Also, two or more steps may be performed concurrently or with partial concurrence, unless specified differently above.
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