Abstract:
Alternative sputter target compositions or configurations for thin-film electrolytes are proposed whereby the sputter target materials system possesses sufficient electrical conductivity to allow the use of (pulsed) DC target power for sputter deposition. The electrolyte film materials adopt their required electrically insulating and lithium-ion conductive properties after reactive sputter deposition from the electrically conducting sputter target materials system.

Description:
RELATED APPLICATIONS 
       [0001]    This application is related to and claims the benefit under 35 U.S.C. § 119 of U.S. provisional application Ser. No. 61/016,038, entitled “METHOD FOR SPUTTER TARGETS FOR ELECTROLYTE FILMS,” filed Dec. 21, 2007, which is incorporated herein by reference in its entirety. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention is related to the fabrication of lithium-ion thin-film electrolytes for use in thin-film electrochemical energy storage and conversion devices. 
       BACKGROUND OF THE INVENTION 
       [0003]    Presently, lithium-ion electrolyte layers are deposited from ceramic, insulating sputter targets using radio-frequency (RF) excitation (1 MHz-1 GHz) on the sputter target together with a RF tuner and a RF matching network. The main reason for this approach lies in the fact that the ceramic target composition or stoichiometry can be fabricated identical, or at least most similar, to the stochiometry of the lithium-ion electrolyte layer to be deposited. However, both the use of the ceramic insulating sputter target and the RF sputter method may be undesirable due to their associated high costs, limitations in deposition area and rate, and hardware sophistication and challenges. 
         [0004]    The electrically insulating type target typically requires the use of RF excitation when sputtering. Otherwise, when not using RF excitation, such as direct current (DC), pulsed DC (e.g. 250 kHz), or alternate current with a lower frequency (AC; e.g. 100 kHz) excitation, the target surface charges up substantially and releases the built-up charges in form of an electric arc to the substrate, the chamber wall, and/or the dark space shield. Electric arcing could be either so severe that electronics in the power supply connected to the sputter target may not prevent this event from occurring, which detrimentally affects the film growth on the substrate, or the sputter process could be interrupted too frequently by the preventive electronics of the power supply that a sputter deposition may not take place. Unfortunately, the entire RF electronics around a sputter target are fairly expensive as well as require the vacuum deposition chamber to be RF compatible. Most large sputter deposition tools used in semi-conductor manufacturing are not RF compatible but are only direct current (DC) or pulse DC compatible. The design and build of new, large vacuum deposition chambers takes substantial amounts of time and money because these chambers are not anticipated to be built and sold in large numbers. 
         [0005]    Another issue in RF sputtering is that, for deposition of oxide dielectric films, ceramic targets are typically formed of multiple smaller tiles due to limitations in fabricating large area ceramic sputter targets in thicknesses (e.g. ¼ inch) that are appropriate for use in sputter processes. Further, the reactors required for RF sputtering tend to be rather complicated. In particular, the engineering of low capacitance efficient RF power distribution to the sputter cathode is difficult in RF systems. Routing of low capacitance forward and return power into a vacuum vessel of the reaction chamber often exposes the power path in such a way that diffuse plasma discharge is allowed under some conditions of impedance tuning of the matching networks. 
         [0006]    Typically, it has been difficult to fabricate large area, insulating, ceramic sputter targets because their constituent tile size, singly-tiled or multi-tiled, is limited by today&#39;s available ceramic processing methods (cold pressing plus subsequent sintering or, instead, hot pressing of appropriate starting powders) in light of the performance requirements for ceramic sputter target tiles when sputtered under the thermal stresses of high rate sputter deposition. However, owing to the inherent brittleness of ceramic tiles and their limited, practical thickness when to be used in magnetron sputter targets (typical thickness is about ½ to ¼ inch for practical usage purposes) wherein the magnetic field of the magnetron has to go well through the sputter target tile thickness, tile manufacturers face the challenging task of making the target tiles as large as possible while being limited in its thickness. Thus, target manufacturers have encountered a loosely defined limit for the area/thickness ratio for every target tile material above which the target tile fabrication yield becomes too low to be economically viable. For practical and well performing Li 3 PO 4  sputter target tiles, the tile size limit today for ¼ inch thick targets is on the order of 10″ in diameter or 7″×7″ for non-disc shapes. 
         [0007]    In addition to the difficult or even impossible fabrication of large area, insulating, ceramic sputter targets that prove to be mechanically sufficiently resilient in high-rate sputter depositions, issues such as local charging/arcing, cross talk with other areas, and severe and variable impedance mismatch between the power supply and deposition environment conspire to limit the nominal practical sputter target area to be below about 1000 cm 2  for well established ceramic sputter materials such as Al 2 O 3  and about 500 cm 2  for less established ceramic materials, such as Li 3 PO 4 . 
         [0008]    In light of the issues involved in ceramic tile fabrication and the associated use of RF target excitation, it is desirable to switch from ceramic to metallic target tiles, if possible with respect to the necessary reactive sputter deposition in the case of metallic tiles, because metallic plates of about ¼ inch in thickness can more easily be fabricated in large areas. Another inherent benefit of using metallic targets over ceramic targets is based on the fact that the far more ductile metallic targets can be sputtered at much higher deposition powers and deposition rates, which creates a stressful temperature gradient inside a sputter target tile with which metallic target tiles can cope much more readily compared to brittle ceramic tiles. 
         [0009]    The economics of mass-producing lithium-ion thin film electrochemical storage and conversion devices strongly depend on the capital expenditures for a given production throughput, which in turn is affected by the deposition rate, deposition area, deposition yield, and equipment up-time. In this regard, the issues of having to use relatively small, brittle ceramic sputter targets or target tiles in conjunction with RF sputter target excitation represents a significant economic barrier in scaling the production processes of lithium-ion thin film electrochemical storage and conversion devices to industrial levels. 
         [0010]    To avoid the cost and tool issues involved in RF sputtering one may seek to sputter deposit said electrolyte or dielectric layers from electrically conducting sputter targets using DC or pulsed DC target excitation power. In that case, the charge-up and electric arcing issues are fewer and typically manageable. Both of these DC sputter methods are less expensive than RF and simpler to implement in vacuum deposition systems. However, in order to attain an electrically insulating but ionically (here: lithium-ion) conducting electrolyte or dielectric layer from an electrically conducting sputter target, one has to sputter deposit the target material in a reactive atmosphere to achieve the electrically insulating film composition of the correct stoichiometry. In some cases one may opt to attain the correct film stoichiometry via co-sputtering from a suitable, second sputter target, which, if electrically insulating, would require RF power excitation whereas if electrically conducting, could be sputtered by DC or pulsed DC excitation as well. 
         [0011]    There is not a substantial track record in the field of creating sputter deposition targets that are amenable to DC or pulse DC deposition while producing insulating/dielectric, lithium containing films with electrolytic properties when deposited. Nor is there a significant amount of published work on the subject of using alternative sputter target compositions or configurations specifically to allow for DC deposition of sputtered materials that turn into electrolytes by becoming electrically insulating and ionically conducting when deposited as well. This scarcity of published information or patents extends to not only lithium-ion but all electrolytes. Most of the published work in this area focuses on how to increase the target area or how to improve the hardware. Whereas, the motivation of the present invention is to fabricate a conductive target composition that allows the use of DC or pulsed DC target sputter power to accomplish a lithium-ion electrolyte thin film cheaper and faster. 
         [0012]    U.S. Patent application No. 2006/0054496 discloses oxide and oxynitride films being presented and deposited by a DC sputter method from a metallic target material. This disclosure focuses, however, on the sputter hardware and does not, for example, address the problem of modifying the composition/structure of the target to facilitate DC powered deposition of sputter materials whose physical vapor deposited films turn into thin-film electrolytes. 
         [0013]    U.S. Pat. No. 5,753,385 (the “&#39;385 patent”) uses metallic sputter targets of zirconium and yttrium to form oxides that are used as high-temperature, oxygen-ion conducting membranes in solid oxide fuel cells. Although these membranes have electrolytic properties, they are only high-temperature electrolytic properties and are exclusively relative to oxygen ions. The present invention, in contrast, focuses, for example, on ambient-temperature lithium-ion electrolytes. The underlying chemistry and physical parameters to form oxygen-ion electrolytes and lithium-ion electrolytes are very different. For example, a high-temperature oxygen-ion electrolyte needs to be crystalline while a lithium-ion electrolyte of the present invention only needs to be glassy or amorphous. In fact, if the lithium-ion electrolyte of the present invention is or becomes crystalline during its fabrication or thereafter at any time during its lifetime, it will severely limit the associated lithium thin-film electrochemical storage and conversion device to the use of only non-metallic lithium-ion anodes because a metallic lithium anode may short-circuit a lithium thin-film electrochemical storage and conversion device by creating an electrochemical short-circuit pathway from the anode to the cathode via grain boundary diffusion inside the crystalline electrolyte. If no (glassy or amorphous lithium-ion electrolyte) or virtually no (nano-crystalline lithium-ion electrolyte) grain boundaries exist, the inadvertent and undesirable formation of an electrochemical short-circuit pathway may not occur. The reason why the &#39;385 patent can afford the use of a (high-temperature oxygen-ion) crystalline electrolyte lies mostly in the fact that the fuel cell device does not possess a creeping, easily diffusing, short-circuit creating, metallic lithium anode. Due to the vast difference of the motivation as well as benefits between the current invention and the &#39;385 patent, one of ordinary skill in the art would not come up, for example, with a way to fabricate a lithium-ion thin-film electrolyte by non-RF sputter deposition techniques based on the &#39;385 patent. 
         [0014]    U.S. Pat. No. 7,179,350 B2 discloses a hybrid approach optimized for reactive sputtering, whereby the magnetron head is driven by both DC and RF controllers at the same time. Its focus, however, is on sputter hardware modification and not on target composition to achieve a lithium electrolyte film. 
         [0015]    While battery and fuel cell thin film electrolytes have been radio-frequency (RF) sputter deposited for more than one decade, the instrumentation used for these growths has been relatively small: research and development or pilot line systems only. As this technology is scaled to the necessary (profitable) full industrial level, there is a need for more economical equipment and less costly consumables. Accordingly, the ability to sputter deposit electrolyte and dielectric layers over very large areas more quickly, and with less expense by using larger metallic targets and less expensive DC type sputter target excitation is very appealing, and the proper solution should result in significant savings of both time and money during high volume production. 
       SUMMARY OF THE INVENTION 
       [0016]    Various aspects and embodiments of the present invention, as described in more detail and by example below, address certain of the shortfalls of the background technology and emerging needs in the relevant industries. Accordingly, the present invention is directed, for example, to a sputter target and a method of forming a sputter target that substantially obviate one or more of the shortcomings or problems due to the limitations and disadvantages of the related art. 
         [0017]    The use herein of the terms “electrically conductive” and “electrically insulating” when describing material shall be interchangeable with the terms “electronically conductive” and “electronically insulating,” respectively. The use of each of these terms when describing a material is neither exclusive nor inclusive of whether that material does or does not also conduct ions. 
         [0018]    Thin film electrochemical storage and conversion devices include electrically insulating but ionically conducting layers, so-called electrolyte or dielectric layers. When sputter depositing these layers, either electrically insulating or conducting sputter targets may be used. The thin-film electrochemical storage and conversion devices of the present invention employ a lithium-ion electrolyte layer (one type of ionically conducting layer) which primarily conducts lithium ions. 
         [0019]    One aspect of an embodiment of the invention involves the sputter deposition of electrically insulating but lithium-ion conducting films (conductive ceramic films) using the less expensive DC or pulsed DC method, both of which can be implemented in any vacuum deposition tool/chamber more simply and reliably compared to the more sophisticated and more expensive RF method. This DC or pulsed DC approach uses the electrically conducting sputter targets and converts their composition into the correct film stoichiometry by reactive sputter deposition. 
         [0020]    Another aspect of an embodiment of the invention pertains to overcoming the practical limitation of the sputter target size, both in surface area and thickness, and/or sputter tile size within a multi-tiled sputter target that can be used to deposit the required electrically insulating, lithium-ion conducting electrolyte or dielectric layers. 
         [0021]    A further aspect of an embodiment of the invention involves the generally higher thermal conductivity of metallic targets compared to their ceramic counterparts. This allows for the use of thicker metallic sputter targets, because for a given sputter target thickness the target cooling from the cooled target backing plate through the entire bulk of the sputter target is more efficient for metallic targets while additionally their thermal gradients are typically much smaller. Associated with the beneficial option of using thicker metallic targets is a less frequent maintenance schedule, reduced down-time of the production equipment, and thus lower fabrication costs of the thin film electrochemical storage and conversion devices because thicker sputter targets can be operated for longer periods before they have to be replaced. A compromise between target thickness and magnetron action at the sputter target surface may need to be made in order to optimize the performance of the production sputter equipment. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0022]    Some features and advantages of the invention are described with reference to the drawings of certain preferred embodiments, which are intended to illustrate and not to limit the invention. 
           [0023]    The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention that together with the description serve to explain the principles of the invention. In the drawings: 
           [0024]      FIG. 1  illustrates a sequence of processing steps that can be used to fabricate lithium-ion thin-film electrolytes for use in thin-film electrochemical energy storage and conversion devices according to an embodiment of the present invention. 
           [0025]      FIG. 2  illustrates an embodiment of the sputter deposition of an electrolyte film from a Li 3 P sputter target in an O 2 /N 2  reactive plasma sputter plume in which the substrate is immersed, thus causing the deposition of the electrolyte film onto the substrate. 
           [0026]      FIG. 3  illustrates an embodiment of the sputter deposition of an electrolyte film from a composited sputter target consisting of a Li x P phase and a Li 2 O phase. 
           [0027]      FIG. 4  illustrates an embodiment of the sputter deposition from  FIG. 3  when the Li 2 O is replaced by Li 3 N. 
           [0028]      FIG. 5  illustrates an embodiment of the sputter deposition of an electrolyte film onto a substrate, which is immersed in two plasmas formed from two different sputter targets. 
           [0029]      FIG. 6  illustrates an embodiment of the deposition of an electrolyte film onto a substrate which is created by directing both the plasma sputter plume of a sputter deposition and the evaporation plume of a resistive evaporation process onto the substrate. 
           [0030]      FIG. 7  illustrates an embodiment of the method of a thick metallic sputter target for the sputter deposition of an electrolyte film. 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0031]    These and other aspects of the invention will now be described in greater detail in connection with exemplary embodiments that are illustrated in the accompanying drawings. 
         [0032]    It is to be understood that the present invention is not limited to the particular methodology, compounds, materials, manufacturing techniques, uses, and applications described herein, as these may vary. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. It must be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to “an element” is a reference to one or more elements and includes equivalents thereof known to those skilled in the art. Similarly, for another example, a reference to “a step” or “a means” is a reference to one or more steps or means and may include sub-steps and subservient means. All conjunctions used are to be understood in the most inclusive sense possible. Thus, the word “or” should be understood as having the definition of a logical “or” rather than that of a logical “exclusive or” unless the context clearly necessitates otherwise. Structures described herein are to be understood also to refer to functional equivalents of such structures. Language that may be construed to express approximation should be so understood unless the context clearly dictates otherwise. 
         [0033]    Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. Preferred methods, techniques, devices, and materials are described, although any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in the practice or testing of the present invention. Structures described herein are to be understood also to refer to functional equivalents of such structures. Unless the context of the disclosure or claims dictate otherwise, for example, the terms “target” and “target title” may be used interchangeably. 
         [0034]    All patents and other publications identified are incorporated herein by reference for the purpose of describing and disclosing, for example, the methodologies described in such publications that might be used in connection with the present invention. These publications are provided solely for their disclosure prior to the filing date of the present application. Nothing in this regard should be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention or for any other reason. 
         [0035]      FIG. 1  illustrates an embodiment of an exemplary process  100  for fabricating lithium-ion thin-film electrolytes for use in thin-film electrochemical energy storage and conversion devices according to some embodiments of the present invention. Process  100  includes fabricating, for example, a mechanically robust and substantially conductive sputter target, step  101 , providing a vacuum deposition chamber, step  103 , sputtering the mechanically robust and substantially conductive sputter target, step  105 , and depositing the lithium-ion thin-film electrolyte in a reactive sputter gas atmosphere, step  107 . 
         [0036]    In step  101 , according to embodiments of the present invention, the sputter target is made from electrically conductive or at least semi-conductive, target materials with a conductivity of greater than about 10 −4  S/cm at room temperature. For the present invention, the conductivity is preferably at least 10 −8  S/cm at room temperature and most preferably 1 S/cm at room temperature. By using appropriate materials for the sputter target and operating it in a reactive gas environment, an electrically insulting but lithium-ion conducting film may be deposited. This effect relies on using a reactive sputter gas environment whereby the ejected target materials react with each other and with some subset of the neutral and/or ionized constituents of the sputter plasma to form a new chemical compound on the substrate. In step  107 , deposition in a reactive sputter gas atmosphere can convert the material sputtered from a lithium-ion conducting sputter target into an electrically insulating and lithium-ion conducting electrolyte film. In step  107 , possible gas constituents include oxygen, nitrogen, fluorine, chlorine, bromine, iodine, sulfur, selenium, tellurium, phosphorus, arsenic, antimony, bismuth, lead, carbon, hydrogen, silicon, lithium, sodium, magnesium, and zirconium that are introduced into the sputter reactor in gaseous form, either as chemical elements or chemical compounds. Possible target constituents include lithium, phosphorus, oxygen, nitrogen, fluorine, chlorine, bromine, iodine, sulfur, selenium, tellurium, arsenic, antimony, bismuth, lead, carbon, hydrogen, silicon, sodium, magnesium, and zirconium, as well as the materials from the group of lithium phosphate (Li 3 PO 4 ), nitrided lithium phosphate, lithium phosphide and sub-phosphide (Li x P for 1≦x≦100), lithium nitride and sub-nitride (Li x N for 3≦x≦100), phosphorus oxide and sub-oxide (PO x  for x≦2.5), phosphorus nitride and sub-nitride (PN x  for x≦1.7), and lithium oxide and sub-oxide (Li x O for 1≦x≦100). The material systems are also selected such that any insulting film that might form on the surface of the target as a result of reaction with the sputter gas does not substantially impede subsequent deposition. The reactions leading to the conversion of the sputtered constituents and gas constituents into the electrolyte film occur on the surface of the film as it is being deposited. 
         [0037]    By making the target electrically conducting, the type of target excitation is no longer limited to RF power. Therefore, in step  103 , the vacuum deposition chamber provided does not have to be RF compatible, which otherwise is difficult for large manufacturing tools. Similarly, the sputtering process in step  105  can be done with cheaper DC or pulsed DC power electronics at higher rates compared to RF. In addition, the depositing process in step  107  can be finished faster and cheaper compared with previous RF methods. 
         [0038]    According to the embodiments of the present invention, steps  103 ,  105 , and  107  may be performed with any combination of RF (ranging from 1 MHz to 1 GHz), AC, pulsed DC, and DC power (alone or together in various combinations) to produce the films of interest. It is also possible that, in step  107 , more than one film constituent is deposited in sequence using a non-sputter technique such as thermal evaporation, chemical vapor deposition, or cathodic arc deposition. This non-sputtered constituent may be deposited from an electrically insulating or conducting source. The latter source material most preferably includes the deposition be performed in a reactive atmosphere with regard to the chemical reactivity of the source material. 
         [0039]    In accordance with the embodiments of the present invention, the sputter target in step  101  may be made of a single compound, a multi-constituent composite, or a collection of target tiles within the confines of the target with significantly different compositions. In all cases, individual tile segments are preferably larger than 300 cm 2 . If more than one different kind of target is needed to create the desired film, one may use a substrate translation in conjunction with optional target switching and/or deposition from multiple sputter cathodes whose sputtered species are simultaneously directed towards the growing film on the substrate. An added benefit of this invention is that the electrically conductive target will necessarily be more thermally conductive than a typical electrically insulating target. This increase in thermal conductivity will allow for the implementation of thicker targets (up to 5 cm) compared with thinner ones before (0.6 cm), thereby reducing the frequency of target replacement (reduces overall cost of fabrication). 
         [0040]    The following examples are included to provide further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention. 
         [0041]    Example 1 ( FIG. 2 ) provides an exemplary embodiment of process  100  in which a LIPON electrolyte film of composition Li 2.9 PO 3.3 N 0.46    205  may be deposited onto a substrate  207  by DC, pulsed DC, AC, or RF reactive sputtering from semi-conducting target of the composition Li 3 P 201 when immersed in a sputter plasma plume  203  including the sputtered material and a reactive gas mixture of oxygen and nitrogen, with or without addition of inert gas such as argon. The O 2 /N 2  ratio is to be adapted to less than 1/100 due to the much higher affinity of the depositing Li and P species to bond with oxygen compared to nitrogen. For a given oxygen/nitrogen ratio (for example, 1/1000) inside the vacuum deposition reactor both kinetic and thermodynamic factors determine the final stoichiometric parameters x, y, and z in the growing Li x PO y N z  film. Among the kinetic parameters are the target sputter power (for example, 2000 W for 10 inch in diameter Li 3 P target), the pulsed duty cycle (for example, periods of 2 μs power on and 2 μs power off), the target-to-substrate distance (for example, 7.5 cm), the deposition rate (for example, 3 μm/h), the substrate temperature (for example, 150° C.), the substrate bias (for example, −70V), the nitrogen flow rate (for example, 300 sccm), and the oxygen flow rate (for example, 0.3 sccm, as may be indirectly established through the N 2  gas supply that contains 0.1 vol % O 2 ). In concert with the kinetic parameters, thermodynamic factors such as the substrate temperature (among other factors, is a function of the sputter target power) and the oxygen/nitrogen ratio at the growing film surface play a role in the stoichiometry of the growing LIPON film. 
         [0042]    Example 2 ( FIG. 3 ) provides an exemplary embodiment of process  100  in which a LIPON electrolyte film of Li 2.9 PO 3.3 N 0.46    205  may be deposited by DC, pulsed DC, AC, or RF reactive sputtering from a composite target  301  composed of lithium rich Li x P (x&gt;&gt;3)  305  and Li 2 O,  307  either composited on a microscopic level or on a centimeter scale by alternatingly placing Li x P tiles and Li 2 O tiles substantially close to each other so that when sputtering such target in a reactive, at least nitrogen containing sputter plasma plume  303 , with or without addition of inert gas such as argon, the concentration ratio of Li/P yields about 2.9, the O/P ratio yields about 3.3, while the N/P ratio amounts to about 0.46. The microscopic composition of Li x P (x&gt;&gt;3)  305  and Li 2 O  307  may be preferred over the centimeter scale composite, because it provides a semi-conducting surface of the sputter target  301  that is useful for operating the target under DC or pulse sputter conditions. 
         [0043]    Example 3 ( FIG. 4 ) provides an exemplary embodiment of process  100  in which the sputter target  401  comprises Li 3 N  407  instead of Li 2 O  307  as illustrated by Example 2 and the so-fabricated sputter target  401  is DC, pulsed DC, AC, or RF sputtered in a plasma plume  403  containing at least nitrogen and oxygen. 
         [0044]    Example 4 provides an exemplary embodiment of process  100  in which the sputter target comprises P 2 O 5  instead of Li x P (x&gt;&gt;3) as provided by Example 3 ( FIG. 4 ) and the so-fabricated sputter target is DC, pulsed DC, AC, or RF sputtered in an atmosphere containing at least nitrogen. 
         [0045]    Example 5 provides an exemplary embodiment of process  100  in which the sputter target comprises PN instead of P 2 O 5  as provided by Example 4 and the so-fabricated sputter target is DC, pulsed DC, AC, or RF sputtered in an atmosphere containing at least nitrogen and oxygen. 
         [0046]    Example 6 provides an exemplary embodiment of process  100  in which the sputter target is fabricated from a microscopic composite of metallic lithium and PN and the so-fabricated sputter target is DC, pulsed DC, AC, or RF sputtered in an atmosphere containing at least nitrogen and oxygen. 
         [0047]    Example 7 ( FIG. 5 ) provides an exemplary embodiment of process  100  in which a LIPON electrolyte film of composition Li 2.9 PO 3.3 N 0.46    205  may be deposited by DC, pulsed DC, AC, or RF reactive sputtering from at least two separated sputter targets  201  and  501  whose sputter plasma plumes  503  and  503 A are both directed towards the substrate  207  where the Li 2.9 PO 3.3 N 0.46  electrolyte film  205  is grown. The first sputter target  201  may be fabricated as provided by Example 1 ( FIG. 2 ) while the second sputter target  501  may be fabricated as provided by Example 5. To improve film uniformity in terms of composition, among other desirable uniformity features such as thickness, one may rotate the substrate  207  around its vertical axis  505  within the slightly differently composed sputter plasma plumes  503  and  503 A. A third sputter target may be added to the vacuum deposition reactor that either has the composition of the first or second target or it may have a different composition, such as the target provided in Example 6. 
         [0048]    Example 8 ( FIG. 6 ) provides an exemplary embodiment of process  100  in which the deposition of the LIPON film  205  provided by Example 3 ( FIG. 4 ) may be supported by a non-sputter deposition process  600 , such as resistive evaporation of metallic lithium from a suitable crucible  601 , such as Ta. The lithium vapor  603  that is directed towards the growing LIPON film  205  not only adjusts the lithium concentration in the film  205  but may also vary the concentrations of oxygen and nitrogen that are co-deposited into the film through the deposition of lithium in the nitrogen and oxygen containing atmosphere  403  and  605 . To improve film uniformity in terms of composition, among other desirable uniformity features such as thickness, one may rotate the substrate  207  around its vertical axis  505 . 
         [0049]    Example 9 provides an exemplary embodiment of process  100  in which the deposition provided by Example 8 may comprise a shutter mechanism that may temporarily interrupt either the sputter deposition or the non-sputter deposition for seconds to minutes so as to create a layered stack of differently electrolytically active layers, which may or may not be diffused into each other by a thermal treatment of the LIPON film, either during deposition or after the deposition. 
         [0050]    Example 10 ( FIG. 7 ) provides an exemplary embodiment of process  100  in which a sputter target  701  is fabricated from a Li 50 Al 50  alloy and DC, pulsed DC, AC, or RF sputtered deposited in a sputter plasma plume  703  consisting of the sputtered material and a reactive gas mixture of F 2 —Ar resulting in the glassy lithium ion electrolyte LiAlF 4    705 . The Li 50 Al 50  alloy is metallically conducting and can be made up to 5 cm thick by standard metallurgical methods inside inert atmosphere such as argon. Sputtering such thick target  701  is still possible because it has a high heat conductivity that allows the cooling  711  of the target backside  707  through the target backing plate  709  to remain feasible. Such a thick target requires less frequent replacement than a thinner target and thus reduces (i) the maintenance intervals of the vacuum deposition reactor and (ii) the operational costs. 
         [0051]    The embodiments and examples described above are exemplary only. One skilled in the art may recognize variations from the embodiments specifically described here, which are intended to be within the scope of this disclosure and invention. As such, the invention is limited only by the following claims. Thus, it is intended that the present invention cover the modifications of this invention provided they come within the scope of the appended claims and their equivalents.