DEPOSITION SYSTEM WITH INTEGRATED COOLING ON A ROTATING DRUM
20190214234 ยท 2019-07-11
Inventors
Cpc classification
C23C14/0078
CHEMISTRY; METALLURGY
C23C14/0063
CHEMISTRY; METALLURGY
H01J37/321
ELECTRICITY
C23C14/0047
CHEMISTRY; METALLURGY
International classification
C23C14/00
CHEMISTRY; METALLURGY
Abstract
In one aspect, a system of depositing a film on a substrate is disclosed, which includes at least one metallization source for generating metal atoms, and at least one reactive source for generating at least one reactive ionic species. The system further includes a pair of inner and outer concentric cylinders, where the outer cylinder has first and second openings positioned relative to the metallization source and the reactive source to allow entry of the metal atoms and the reactive ionic species into a metallization region and a reaction region, respectively, between the two cylinders. At least one mount is coupled to the inner cylinder for mounting the substrate thereto such that said substrate is in radiative thermal communication with the inner surface of the outer cylinder, said inner cylinder being rotatable for moving the substrate between the two regions so as to expose the substrate alternatingly to said metal atoms and said reactive ionic species. Further, the outer cylinder includes at least one cooling channel through which a cooling fluid can flow for maintaining the inner surface of the outer cylinder at a temperature suitable for radiative cooling of the substrate.
Claims
1. A system of depositing a film on a substrate, comprising: at least one metallization source for generating metal atoms, at least one reactive source for generating at least one reactive ionic species, a pair of inner and outer concentric cylinders, said outer cylinder having first and second openings positioned relative to the metallization source and the reactive source to allow entry of the metal atoms and the reactive ionic species into a metallization region and a reaction region, respectively, between the two cylinders, at least one mount coupled to said inner cylinder for mounting the substrate thereto such that said substrate is in radiative thermal communication with inner surface of the outer cylinder, said inner cylinder being rotatable for moving the substrate between the two regions so as to expose the substrate alternatingly to said metal atoms and said reactive ionic species, wherein said outer cylinder comprises at least one cooling channel through which a cooling fluid can flow for maintaining said inner surface of the outer cylinder at a temperature suitable for radiative cooling of the substrate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0036] The present disclosure is generally directed to deposition of metal thin films on substrates, e.g., via magnetron sputter deposition, and their subsequent reaction and in some cases densification by exposure to a reactive species generated, for example, by a plasma or ion source, as well as temperature control, e.g., during deposition.
[0037] As used herein, the term reaction refers to a chemical reaction, such as oxidation, nitriding or carburization of a film by one or more active ionic species, such as for example O.sub.2, N.sub.2 or some form of carbon-containing ionic species. As discussed in more detail below, such ionic species can be introduced onto a deposited metallic film as a gas. Although various embodiments discussed below employ oxidation reactions, it should be understood that the present teachings are not limited to oxidation and can employ other reactions, such as those noted above. The term about as used herein denotes a variation of less than 5% around a numerical value.
[0038] In many embodiments, the film sputtering and the subsequent oxidation take place sequentially in separate metallization and reaction zones. This is in contrast to many prior art systems that use a batch chamber in which a sputter source and an ion source are placed in close proximity to one another, resulting in cross talk between their respective plasmas, and where oxidation is simultaneous with film deposition. By contrast, in various embodiments disclosed herein, both film deposition and film exposure to reactive species are shielded from one another by one or more conductance limiting shield.
[0039] By way of example, in one embodiment, a sputtered film, for example, represented as metal M, can be deposited as a thin layer on a substrate mounted onto a rotating drum that moves the substrate past a sputter source. The thin metal layer can be subsequently oxidized as the drum rotates the substrate past a plasma source, which bombards the film with activated and ionized O.sub.2 and argon ions. These ions possess sufficient energy and density, e.g., an average energy in a range of about 30 eV about 300 eV and a beam current equal to or greater than 1 ampere for typical metal deposition rate of equal to or less than 5 A/rev (angstroms per revoluation), such that when they impinge on the film they can oxidize and densify the metal film M into an oxidized film of the form M.sub.yO.sub.x. For example, if M is aluminum, then one would obtain Al.sub.2O.sub.3 upon oxidation with a plasma source. In some embodiments, each film deposition stage can result in the deposition of a film having a thickness, e.g., equal to or less than 5 A/rev. Multiple stages of metal deposition and exposure to reactive ionic species, e.g., as a substrate mounted on a rotating drum makes multiple passes through a metallization region and a reaction region, can result in a total film thickness, e.g., up to about 7 A/rev when fully reacted.
[0040] Embodiments disclosed herein allow for the deposition of a metal on a substrate using reactive magnetron sputtering in an open loop mode using a standard DC sputtering supply such as an MDX or Pinnacle or similar DC sputtering supply with no need for feedback control of the MFC. Further, no pulsing is required since the process of metallization and reaction take place in separate zones with no cross talk between the respective plasmas. Due to this separation, there can be insignificant build-up, and in some cases no build-up, of insulating layers, which could otherwise cause arcing. Additionally, very high effective rates of metal oxide generation can be achieved using this method. An added benefit due to the setup of the conductance limiting shield or baffle is to allow temperature control, and specifically reduction of the deposition temperatures to low temperatures of <100 C. that allow extrinsic stress control of the film, as well as deposition on temperature sensitive substrates such as plastic (e.g. polycarbonate).
[0041] Further, there is no need in embodiments disclosed herein for the use of any aperture over the magnetron to build up a pressure difference between the argon at the magnetron and the much lower O.sub.2 pressure from an ion source. Therefore, target utilization is only limited by magnetron design. Further, embodiments disclosed herein may use a cylindrical structure for substrate mounting. In some such embodiments, no uniformity tuning may be needed across the substrate surface for flat substrates.
[0042] According to aspects disclosed herein, it is desirable to have control over three inputs in the deposition process: substrate temperature, deposition rate and film stress. In many embodiments, the substrate temperature is mainly governed by power input during the metallization and reaction processes. For example, power can be input from heat lamps as heat to the substrate to increase atom mobility and produce more stable and dense films. Power can also come from the deposition and/or reaction processes themselves. If P.sub.1 is the power input to the substrate due to the magnetron, and P.sub.2 is the power input to the substrate due to the ion source, the total power input is P.sub.total=P.sub.1+P.sub.2. Note that P.sub.1 is not the actual power into the magnetron but the power input from the growing film due to the film deposition from the magnetron and other energetic particles. Likewise for the ion source, P.sub.2 contributes to the substrates' temperature during film growth due to the ion energy and flux density (beam current). The temperature of substrates may rise quickly during the initial stages of plasma deposition, and may eventually level off, reaching quasi thermal equilibrium, and proceeding to slowly rise to some final value at the end of the deposition cycle.
[0043] The control of substrate temperature during film growth is important for several reasons. First, the substrate's temperature can affect the film stress, as one aspect of film stress is directly linked to temperature during processing, as discussed further below. Second, for temperature sensitive substrates such as plastics, the substrate's temperature must stay well below the softening point so that they do not deform during the deposition process. This is especially important, for example, in plastic optical components and lenses, since raising their temperatures beyond their softening point can change their optical and/or mechanical tolerances. For example, the temperature of polycarbonate or Lexan should be kept below 115 C. to avoid deformation.
[0044] The deposition temperature can have a significant role in the total film stress. As described in Milton Oring: The Material Science of thin Films Academic Press 1992, the total film stress is given by:
t=.sub.intrinsic+.sub.thermal (1)
[0045] The intrinsic stress component can be caused by many factors such as inclusions, defects, bombarding energy of incoming particles, etc. Total stress, .sub.t in equation (1) can be measured by finding the bow in a substrate and from that calculating the stress using the modified Stoney equation. The effect of the thermal component of the film stress and how it can be controlled by controlling substrate temperature during deposition is of particular interest in various embodiments disclosed herein.
[0046] The temperature or thermal component of the film stress is expressed as:
where T.sub.1 is the final temperature and T.sub.2 is the initial temperature of the substrate, .sub.1 is the coefficient of thermal expansion (CTE) of the substrate over the T range, .sub.2 is the CTE of the growing film over the same temperature range, v.sub.f is Poissons ratio for film, E.sub.f is the Young Modulus for the film, and k is E.sub.f/(1v.sub.f). Depending on the difference between the CTE of the substrate and the growing film (), the final stress component can be either tensile or compressive. Since one does not have control over CTE as it is determined based on fixed properties of the film and substrate, one way to minimize this component of stress is to minimize T in the above equation.
[0047] The cooling of substrate mounted on a rotating drum may be achieved via a coolant flowing through serpentine stainless lines affixed or welded to the drum, which receive the coolant via a rotating Ferrofluidic type feedthrough. However, these feedthroughs can be very expensive and have been known to leak over time. Furthermore, substrates are usually held in place by point contact or flush mounted to a puck to maximize conductive cooling, in which case thermal heat transfer is limited by poor interface coupling. Even for the best cooled drums, cooling for the substrate in a vacuum in this way is extremely inefficient. For insulating substrates such as glass and plastic, which are poor thermal conductors, cooling in this way is even more inefficient.
[0048] According to aspects of the present disclosure, it is shown that the use of radiative cooling can have a significant impact on the reduction of the film temperature during deposition, thus enabling the deposition of relatively thick films on temperature sensitive substrates without their deformation or melting even in cases where substrates/film combination have a large .
[0049] Various embodiments disclosed herein may use radiative cooling, a passive cooling method using the film/substrate emissivity, and the absorptivity of a cooled surface placed in close proximity to the film/substrate, such that the heat generated in the film/substrate by the processes to which the film/substrate is exposed, such as the metal deposition process, is absorbed by the cooled surface. Using a large enough surface area and a low enough temperature of the cold surface, radiative cooling can be an effective method not only for temperature reduction but also for temperature control using a feedback loop to a cooling generator.
[0050] Consider two surfaces in close proximity to one another. Surface 1 is at temperature T.sub.1 with emissivity .sub.1 and surface 2 is at temperature T.sub.2 with emissivity .sub.2, assuming T.sub.2>T.sub.1. The heat transfer rate ({dot over (Q)}.sub.12) from the warm to cool surface is then given by:
where A1 is the area of the surface 2 at the higher temperature and is Boltzmann's constant. By controlling the temperature of the cooling surface and the relative emissivities of the two surfaces, a significant impact on heat removal from surface 2 to surface 1 can be implemented.
[0051] In various embodiments disclosed herein, two concentric cylinders are used instead of flat surfaces, one for mounting one or more substrate(s) and the other for providing a cooled surface for radiative cooling of the substrate(s).
where .sub.1 and .sub.2 denote, respectively, the emissivity of the surfaces of the inner and outer cylinders that are in radiative thermal communication with one another.
[0052] In order to maximize the radiative heat transfer from the hot to the cold cylinder, based on equation (4), one may maximize the temperature difference, which can be expensive, or may optimize the emissivity, or both. As both .sub.1 and .sub.2 approach 1, equation (4) is maximized for fixed temperatures.
[0053] Emissivity can be affected, among other factors, by surface finish. Table I below lists the emissivities for various substrates and surface treatments.
TABLE-US-00001 TABLE I emissivity of various materials Emissivity Coefficient Surface Material -- Alumina, Flame 0.8 sprayed Aluminum 0.09 Commercial sheet Glass smooth 0.92-0.94 Bead blasted SS 0.44 aluminum sand 0.22 blasted
[0054] For example, for glass, which is a popular substrate material, the emissivity is about 0.9. This is true for a wide range of glasses. To maximize the transfer of heat, in many embodiments, the inner surface of the outer cylinder has preferably an emissivity close to 1. Polished aluminum or stainless steel (SS) has an emissivity () of only about 0.1. Even bead blasted SS or aluminum will only have of about 0.22. However, if the SS surface is treated by the plasma flame spray method, that is flame sprayed alumina is deposited over a stainless steel shell, one can obtain an emissivity of about 0.8. This will be shown below (see
[0055]
[0056] Surface treatments such as flat black or Cat-A-Lac Black Paint can also be used to treat metal surfaces to adjust surface emissivity in order to obtain values close to 1. However, in various embodiments disclosed herein, the use of flame spray is more advantageous as it also possesses the ability to reduce particulates during the film deposition process. For example, a film deposited on a metal surface may develop a stress, and after conversion to an oxide that stress may be exacerbated. Eventually, for a smooth surface, the stress build up and the combination of adhesion and stress may cause the film to erupt off. The eruption of these films will cause flaking and particles to be deposited through the chamber and on the substrates. However, a surface treated with flame spray can be about 1000 times rougher than a bead blasted surface. Hence, the amount of film that can be deposited on the flame spray treated surface can be many orders of magnitude greater before the surface loses its ability to grab the film. The reason is that the film will not be a continuous stressed body as in smooth surfaces or even in bead blasted surface, which can become planarized by deposition of growing films once it gets to some critical thickness. Once this critical thickness occurs, the top film layer is continuous again and the stress build up will eventually cause delamination or buckling in these layers. The flame sprayed surface does not suffer from these issues as the surface is very rough and is not planarized, so the film is never continuous over large areas. For example, a properly prepared flame sprayed alumina stainless steel surface can survive the direct deposition of up to of silicon for a sputtering target without producing any buckling.
[0057]
[0058] The outer fixed cylinder 1 is affixed to stand offs 7, which also serve to thermally isolate the cylinder from chamber 8. Chamber 8 has two top mounted lift mechanisms. Flange or mount 9 may be lifted by a hoist (not shown), which may lift both the outer and inner cylinders 1 and 2. Outer cylinder 1 is affixed to flange or mount 9 by attachment mechanism 11. This mechanism may be made of a thermal isolating material such as alumina. Moreover, the top plate or flange 10 may also be lifted by a separate hoist, thereby lifting only the internal cylinder 2 from the vacuum chamber 8 to allow loading of substrates.
[0059] On either side of chamber 8, 180 degrees apart, are a metallization source 12, shown herein as a magnetron sputter cathode, and a reactive source or ion source 13, shown herein as an ion source assembly with electron neutralizer 14. In the embodiment of
[0060] The reactive source or ion source is enclosed in a vestibule 27 below the vacuum pump 17. The purpose of a pump 17 on the ion source vestibule 27 is to provide additional pumping speed, since the conductance of cylinders 1 and 2 limit the pumping speed to the ion source 13 from pump 3. However, the ion source 13 is preferably operated under a gas load at 2-710.sup.4 torr as measured at gauge 29 shown in
[0061] The outer cylinder 1 may have a plurality of openings, such as cutouts or openings 18 and 19 as shown in
[0062]
[0063]
[0064]
[0065] In various embodiments, the number of conductance limiting baffles and the inter-annular distance may be chosen based on the gas load from the ion source 13 and the speed of the cryogenic pump 3. The intra-annular distance 22 is chosen so as to optimize conductance for pump 3 so as to continually remove O.sub.2 gas 25, to prevent the gas from traversing from the ion source 13 to the sputter source 12. Given the diameter of the two cylinders, the conductance of the structure may be calculated as follows. Conductance depends on whether the flow is molecular or viscous. As defined in A. Roth Vacuum Technology 3rd ed. 1990 Elsevier North Holland, if D is the pipe diameter and P.sub.avg is the average pressure:
DP.sub.avg>0.5 cm-torr/viscous flow
DP.sub.avg<0.005 torr-cm/molecular flow
[0066] For example, for a 100 cm diameter cylinder and an average pressure of the ion source at 510.sup.4 torr of O.sub.2 then PD=0.05. Technically this is called transitional flow, but since it is closer to molecular flow, the conductance of two cylinders of diameters D1=2*R1 and D2=2*R2 and length L may be estimated as described in Roth (A. Roth Vacuum Technology 3rd ed. 1990 Elsevier North Holland):
where K is a constant depending on the ratio of the two cylinder diameters, T is the temperature of the gas being modeled, and m is the mass of the gas being modeled. Using this equation, the conductance for a given pump 3 may be optimized such that the O.sub.2 pressure is well below the ability to poison the sputter target.
[0067]
[0068] During operation of the embodiment described in relation with
[0069] The chamber 8 may be pumped down by pump 3 and to some extent pump(s) 17. A base pressure of less than or equal to about 110.sup.6 torr is obtained as measured by a vacuum gauge such as a Bayard-Alpert hot filament gauge or equivalent high vacuum gauge. In this embodiment, the substrates are depicted as being manually loaded in a batch style system. In other embodiments, they may also be loaded in a loaded locked arrangement. In such an arrangement, the main process chamber is not vented to the atmosphere, but only the load locked portion through which substrates are transferred to the process chamber is exposed to the atmosphere.
[0070] When the base vacuum is obtained, a cryogenic coolant is allowed to flow to the cooling channels 6. The inner cylinder 2 may be rotated at a desired speed, for example at 100 revolutions per minute (rev/min), but the speed may vary from about 40 rev/min to about 600 rev/min. At this point, the reactive gas and/or argon gas may be introduced into the ion source(s) 13. The pressure may be set by gauge 29, shown in
[0071] When the ion source 13 is turned on to some predetermined beam voltage and beam current, the inner cylinder 2 may be rotated for a fixed time past the ion beam to pre-clean the substrates 20. The ion bombardment at the substrate may be tuned to remove several atomic layers of contaminant at the substrate surface. This may be estimated based on the voltage of the incoming ion beam, the current of the beam at the substrate, and the density and sputter yield of the substrate at the operating beam voltage. The etch rate ER or removal rate of the substrate can be expressed for normal incident ions in units of angstrom per minute (Ang/min) as:
where S is the sputter yield (atoms/ion) at the beam voltage, J is the current density of the beam (mA/cm.sup.2), A is the area in cm.sup.2 and is the density of the material being removed (gm/cm.sup.3). For a substrate rotating past the beam, the actual time in the beam is proportional to the area subtended by the beam in relation to the total surface area of the cylinder. The sputter yield of various substrate materials is available as a function of incoming ion voltage.
[0072] While the ion beam cleaning is occurring, a movable shutter may be placed over the magnetron. The purpose of the shutter is to shield any target atoms to prevent deposition on the substrate at this time. Argon gas may be fed into the magnetron and controlled by a mass flow controller such that the pressure is in a range of about 0.8 mtorr to about 10 mtorr. The gas pressure at the magnetron may be measured by a vacuum gauge 30, as shown in
[0073] The power to the magnetron may be ramped up to some fixed power P1 for some quantity of time t1, to burn off any residual contaminants at the target surface. After the sputter target cleaning time, the argon is left to continue to flow to the sputter cathode 12, and the ion source 13 now has an amount of O.sub.2 added to the argon gas already flowing in the ion source.
[0074] The ion beam voltage and current may be adjusted for the current process. When the shutter to the magnetron 12 is opened, metal atoms sputtered from magnetron are continuously deposited onto the rotating substrate as it passes by. The substrate subsequently passes by the ion source 13 and is quickly oxidized and densified via exposure to the argon and oxygen ion mix in the source. Depending on the film properties required, pure O.sub.2 in the ion source may also be used. During the oxidation of the metal film, oxygen atoms that are not gettered away by the film will make their way around the cylinder by way of the inter-annular distance 22 as shown in
[0075] In some embodiments, for a fixed rotational speed 51 of the inner cylinder, the power P1 applied to the magnetron is such that less than or equal to about 7 Angstrom/revolution of metal is deposited. If the metal thickness is greater, the incoming average ion energy which is between about 40-350 eV may not be sufficient for the ions to penetrate the metal layer to completely oxidize it. In one embodiment, the incoming ion energy is a mean energy for the gridless end hall ion source used. In other embodiments, gridded DC or RF ion sources may be used, although they have a lower beam current than end hall ion sources.
[0076] If the rotational speed were doubled and the power to the magnetron and ion sources were kept constant, the results may be unchanged as the metal deposition rate per revolution would be halved but the energetics of the end hall source do not produce over stoichiometric films at low beam energies. To increase deposition rate, one may double the magnetron power, which would double the deposition rate. In doing so, one would have to double the rotating speed to about 200 rev/min in addition to doubling the beam current. The beam voltage for this example would also increase slightly, but it is the beam current of the incoming ions of O.sub.2 that must increase to maintain film stoichiometry. The constraints to produce quality films are driven by the ion source design and its operating pressure.
[0077] In one embodiment, the beam voltage cannot go below a minimum threshold, which may be about 30 to about 50 Volts depending on the film, as energetics do not produce stoichiometric films. Also, when the ion beam voltage is too great, such as greater than about 180 to about 250 Volts, then beam ions may begin to break bonds, causing films that are again absorbing. The beam voltage is a main driver in film stress behavior. As beam voltage is increased, films become more compressively stressed. As the beam voltage decreases, films become less compressively stressed.
[0078] In various embodiments, during the entire deposition process, the recirculating cryogenic coolant removes heat from the ion beam and sputter sources through radiative cooling. This cryogenic coolant may be run at a specific temperature, such as about 183 K. Therefore, the temperature of the substrate during the process may settle to some thermal equilibrium very quickly into the run and remain at that temperature thereafter. After the deposition is completed, the cryogenic refrigerant may be stopped, allowing the system to warm up to room temperature so that the system may be vented without thermal shock occurring to the substrates, and to prevent condensation on the cold substrates.
[0079] In some embodiments, the substrate temperature may be actively controlled, as opposed to just letting the substrates come to some arbitrary equilibrium temperature as discussed above. This may be implemented by using an optical pyrometer, such as an optical pyrometer marketed by K-Space Associates, measuring the temperature of the substrate, and using a feedback loop to the cryogenic cooler such that the chiller temperature is set to maintain a specific substrate temperature while balancing some amount of the input heat load. By way of example,
[0080] One aspect of the method of conductively isolating the sputter and ion sources is that for a process using 100% O.sub.2 in the ion beam, there is no argon present in the film down to the detection limits of Rutherford backscattered spectroscopy (RBS). If argon is introduced into the ion beam, then argon may be inserted into the growing film up to about 4-6%.
[0081] As discussed above, in the design of the two concentric cylinders 1 and 2 as disclosed herein, the intra-annular distance 22 between cylinders 1 and 2 may be chosen such that there is sufficient pumping speed for pump 3 to remove O.sub.2 or any reactive gas used in the source that is not consumed in the ion assisted deposition process at the substrate through aperture 19. The O.sub.2 reacts with the metal film M, where M is converted to MO. Any residual O.sub.2 left must now be removed. The goal is to choose the speed of the pump 3 and the conductance such that the reduced O.sub.2 left, if any, that reaches the magnetron, is in a range where arcing will be very unlikely to occur. This threshold limit may be set such that the rate of removal of metal from the target is much greater than the arrival rate of any residual O.sub.2. The threshold limit may be less than about 110.sup.5 torr partial pressure of O.sub.2 at the magnetron.
EXAMPLES
[0082] In one hypothetical example, sputtering can be carried out by affixing substrates on the inner rotating cylinder, lowering the inner cylinder into the outer cylinder and pumping the main chamber to a base of less than or equal to about 110.sup.6 torr. The inner cylinder can be set to rotate from about 10 to about 600 rpm. The ion source can have O.sub.2 flow into it such that a pressure of 510.sup.4 torr is established. The ion source can be ignited with a neutralization source to provide a source of electrons to the plasma. The cylinder can be set to rotate at a speed of about 100 rev/min. The magnetron can have a gas flow provided such that the pressure at the gauge is about 510.sup.3 torr. The magnetron power can then be set such that the combination of power and rotational speed is such that no more than 5-7 Angstrom/revolution is deposited on the inner cylinder and substrates. As the metal is deposited at the magnetron, it can subsequently be oxidized at the ion source and the process can be repeated at a rate determined by the rotational speed of the cylinder to which the substrates are affixed. For example, if the magnetron power is at 2 kW, 5 angstroms of film can deposited per rotation and the rotation is 60 rpm or 1 rev/sec, then the rate is 5 Angstrom/sec. For 4 kW magnetron power and 120 rpm (this would still provide 5 Angstrom/rev of film), the effective rate would be 10 Angstrom/sec. As the rotational speed is increased, the power to the magnetron must also be increased to maintain the 5 Angstrom/rev Likewise, the ion source beam voltage and current may be changed to reflect the increase in the other variables. By proceeding to higher rotational speed and higher magnetron and beam parameters, very high deposition rates may be obtained. Rates higher than the standard bath system may provide for oxide coating.
[0083] Although embodiments described herein have concentrated mainly on oxide coatings, one of ordinary skill in the art would understand that the method may be applied to other types of coatings, such as nitrides and carbide coatings. Moreover, although flat substrate are depicted, other substrates and shapes such as plastic or glass aspheres and blade edges may be used. For non-planer or spherical substrates, various masks may be installed, for example at aperture 18, to give a non-uniform thickness of metal films across the substrate.
[0084] Those having ordinary skill in the art will appreciate that various changes can be made to the above embodiments without departing from the scope of the invention.