WO2008134053A1

WO2008134053A1 - Thin film battery fabrication using laser shaping

Info

Publication number: WO2008134053A1
Application number: PCT/US2008/005462
Authority: WO
Inventors: Jianchao Li; Kai-Wei Nieh; Sandeep Makhar; Tung-Hsiu Shih
Original assignee: Front Edge Technology, Inc.
Priority date: 2007-04-27
Filing date: 2008-04-28
Publication date: 2008-11-06

Abstract

A method of fabricating a battery comprises selecting a battery substrate having cleavage planes, and shaping the battery with pulsed laser bursts from a pulsed laser beam to control or limit fracture along the cleavage planes. Before or after the shaping step, a plurality of battery component films can be deposited on the battery substrate. The shaping step can be used to cut the battery substrate or to vaporize portions of the films to form shaped battery features, or both. The battery component films include at least a pair of. electrodes about an electrolyte which cooperate to form a battery. Pulsed laser shaping can be used to replace' the use of a mask in the fabrication of shaped battery components. Pulsed laser cutting was also found to work well on thin substrates with a thickness of less than 100 microns.

Description

THIN FILM BATTERY FABRICATION USING LASER SHAPING

BACKGROUND

Embodiments of the present invention relate to methods of fabricating thin film batteries.

Thin film batteries are used in various applications, such as portable electronics, medical devices and space systems. A thin film battery typically comprises a substrate having one or more battery component films that include an electrolyte sandwiched between electrode films such an anode, cathode, and/or current collector films, that cooperate to store electrical charge and generate a voltage. The battery component films that are typically less than 100 microns allowing the thin film batteries to be less than about 1/100^th of the thickness of conventional batteries. The battery component films are formed by processes, such as for example, physical and chemical vapor deposition (PVD or CVD), oxidation, nitridation, and electroplating.

Furthermore, in many applications, thin film batteries having thin or compact dimensions are desirable and the energy density and specific energy of the battery are also important performance measures. The energy density level is the fully charged output energy level per unit volume of the battery. The specific energy level is the fully charged output energy level per unit weight of the battery. However, conventional battery films and substrate materials often constrain the size dimensions, and limit the maximum energy density and specific energy levels that can be obtained from such batteries.

Battery performance can be improved by forming the battery on thin plate-like substrates, such as for example ceramic substrates composed Of AI₂O₃ or SiO₂, which increase the energy to volume/weight ratio of the battery. In such processes, an array of battery cells is formed on the plate-like substrate, and thereafter, individual battery cells are mechanically cut out from the substrate. As one example, the battery cells can be cut out with a diamond or carbide cutting wheel. However, the battery cells are often damaged due to cracking along the edges of the cut. Micro-cracks that originate from the fracture points along the cutting line can also affect the performance of the thin film battery cells and result in cell failure. Increasing the width along the cutting edge to provide a wider gap pr spacing between the battery cells is undesirable because it decreases the energy density of the final battery cells and also reduces substrate yields per unit area. The cutting process can also contaminate the battery cells with the cutting or grinding residue. Further, handling of the thin plate-like substrates with micron sized battery films is difficult during the cutting process because some battery component films, such as for example, lithium or other films, are adversely affected when exposed to air or moisture. Thus, for a number of reasons, conventional battery cutting processes are often inadequate and result in low battery cell yields.

Cutting of the battery cells is even more problematic when the battery cells are built on very crystalline substrates having cleavage places. For example, mica substrates have been used to reduce the total weight and volume of the battery while providing good mechanical strength for the battery cells and dielectric strength. Mica has a flat planar structure with cleavage properties that allow mica to be split into thin foils along its cleavage planes. Thus, the mica substrate can be made very thin with thicknesses of less than about 100 microns or even less than about 25 microns. However, it is difficult to cut a substrate comprising a mica sheet because the substrate can split along the cleavage planes while it is being cut. Thus, cutting of sheet-like substrates with cleavage planes generates special cutting problems.

Thus it is desirable to be able to cut a substrate to form individual battery cells without damaging the cells. It is also desirable to be able to cut a battery substrate composed of mica without causing cleavage faults along the cutting line. It is further desirable not to contaminate the thin films that form the battery cells with grinding or cutting residue. It is also desirable to reduce oxidation of battery cells during processing by their exposure to the external environment.

Conventional thin film fabrication methods, which are used to shape the battery component films on the substrate to form a three-dimensional battery structure, can also have problems. Typically, the battery component films, such as the cathode, electrolyte, etc., are shaped to form particular shapes, using successive masking and deposition process steps. In these methods, a mask comprising patterned apertures is positioned or deposited as a layer on top of a mica substrate. Thereafter, a second layer is deposited onto the underlying substrate surface through the patterned apertures of the mask to form features. Successive masking and deposition steps are used to build up a three-dimensional shaped structure for the thin film battery.

However, conventional masking methods can have undesirable effects when used on a crystalline substrate having cleavage planes. For instance, when the mask is peeled back from the substrate in these processes, it can cause splitting along cleavage planes or fracture across the planes at portions of the substrate adjacent to the interface between the mask aperture and material deposited through the aperture. The edge of the mask can also stick to the underlying substrate material, and when peeled back, remove a portion of a plate-like layer of a substrate at a cleavage plane, or result in a non-uniform or broken edge of the feature being formed through the aperture in the mask.

Thus it is further desirable to form a three-dimensional structure of battery component films on a battery substrate without the excessive use of masks to define the shape of the features. It is further desirable to shape battery component films on the substrate without forming non-uniform or broken edges of the shaped features of the films. It is also desirable to reduce the number of handling steps in the fabrication of a thin film battery to reduce contamination and stress fractures, and increase process throughput.

DRAWINGS

These features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings, which illustrate examples of the invention. However, it is to be understood that each of the features can be used in the invention in general, not merely in the context of the particular drawings, and the invention includes any combination of these features, where:

FIG. 1A is a schematic sectional side view of an embodiment of a thin film battery formed on a planar surface of a substrate;

FIG. 1 B is a schematic sectional side view of another embodiment of a battery showing twin battery cells formed on opposing surfaces of the substrate;

FIG. 2 is a schematic top view of an embodiment of a thin film battery having multiple battery cells on a single surface;

FIG. 3 is a flowchart of an embodiment of a process for forming a set of battery component films on a substrate; FIG. 4 is a schematic sectional side view of a single-sided battery;

FIG. 5 is a flowchart of an embodiment of a process for forming a single-sided battery by depositing battery component films on a substrate and shaping the films with a laser;

FIG. 6A is a schematic sectional side view of a partially fabricated battery preform comprising a stack of unshaped battery component films deposited on the substrate; ■ FIG. 6B is a schematic sectional side view showing the battery preform of FIG. 6A after shaping with pulsed laser beam bursts;

FIG. 7 is a schematic sectional side view of another embodiment of a thin film battery formed which has battery cells on both sides of the substrate; FIG. 8 is a flowchart of an embodiment of a process for forming the thin film battery of

FIG. 7 by depositing battery component films on a substrate and shaping the films with laser; FIG. 9 is a schematic diagram of an embodiment of a pulsed laser cutter for cutting a battery substrate;

FIGS. 10A and 10B are scanning electron micrographs of top views of a hole cut in a battery substrate by a CO₂ laser (FIG. 10A), and by a pulsed femtosecond laser (FIG. 10B);

FIGS. 10C and 10D are optical microscope images of detailed sections of the holes cut in the battery substrate in FIGS. 10A and 10B, respectively;

FIG. 10E is a scanning electron micrograph of a hole cut in a battery substrate by a pulsed femtosecond laser; FIGS. 11A to 11C are flowcharts of different embodiments of processes for cutting a battery substrate with or without battery component films on the substrate;

FIGS. 12A to 12D are schematic sectional side views showing cutting and sealing of the laser cut edge of a battery substrate comprising battery cells having battery component films, electrically conducting barrier layer on contact portions used for the positive and negative terminals, and an overlying protective multilayer coating;

FIG. 13A is a schematic sectional side view showing the battery preform of FIG. 6A after laser shaping according to another embodiment of a shaping method;

FIG. 13B is a schematic sectional side view of the shaped preform of FIG. 13A having insulating adhesive and anode current collector deposited thereon; and FIGS. 14A and 14B are photographs of a top side and bottom side of a battery having films shaped by a laser.

SUMMARY

Methods of fabricating a battery on a battery substrate are provided. In one embodiment, the method comprises selecting a battery substrate having cleavage planes. A plurality of pulsed laser bursts of a pulsed laser beam is applied to the battery substrate to cut through the battery substrate substantially without causing fractions along the cleavage planes of the battery substrate. A plurality of battery component films is deposited on the battery substrate before or after application of the plurality of pulsed laser bursts. The plurality of component films comprises at least a pair of electrodes about an electrolyte that cooperate to form a battery cell. In another embodiment, the method comprises selecting a battery substrate with cleavage planes, cutting the battery substrate by applying a plurality of pulsed laser bursts having a fluence of from about 10 to about 800 J/cm², and, before or after cutting the battery substrate, depositing a plurality of battery component films thereon, the films comprising at least a pair of electrodes about an electrolyte that cooperate to form a battery cell.

In a further embodiment, the method comprises providing a battery substrate having cleavage planes; depositing one or more battery component films on the battery substrate, the battery component films comprising electrode films at least partially surrounding an electrolyte film; applying a plurality of pulsed laser beam bursts to the battery component films of the battery preform, the pulsed laser bursts being applied at a sufficiently high power level to vaporize portions of the battery component films to form shaped features substantially without causing fractures along the cleavage planes of the battery substrate.

DESCRIPTION

Embodiments of thin film batteries 20 comprising one or more battery cells 24a-c on a planar surface 26 of a substrate 28 are illustrated in FIGS. 1 A, 1 B and 2. The thin film battery 20 can also have a single battery cell 24 on a single side of a substrate 28 as shown in FIG. 1A; multiple battery cells 24a, b on opposing surfaces of a substrate 28 as shown in FIG. 1 B; or multiple battery cells 24a-c on the same surface of a substrate 28 as shown in FIG. 2. Referring to FIG. 1A, the battery cell 24 comprises a plurality of battery component films 30 formed on an adhesion layer 34. The battery component films 30 cooperate to form a battery to receive, store, or discharge electrical energy. The films 30 can be employed in a number of different arrangements, shapes, and sizes. At a minimal level, the battery component films 30 include at least a pair of electrode films with an electrolyte film 44. The electrode films can include one or more of a cathode current collector film 38, a cathode film 42, an anode film 48, and a anode current collector film 52, which are all inter-replaceable. For example, the battery 20 can include (i) a pair of cathode and anode films or a pair of current collector films, (ii) both the anode/cathode films and the current collector films, or (iii) various combinations of these films, for example, a cathode film and an anode and anode current collector film but not a cathode current collector film, and so on. The exemplary versions of the battery 20 illustrated herein are provided to demonstrate features of the battery and to illustrate their processes of fabrication; however, it should be understood that the exemplary battery structures should not be used to limit the scope of the invention, and alternative battery structures as would be apparent to those of ordinary skill in the art are within the scope of the present invention. Referring to FIG. 1 B, the battery 20 can include a first battery cell 24a on a first planar surface 26 of the substrate 28, and a second battery cell 24b on a second planar surface 27 of the same substrate 28. Each battery cell 24a, b comprises a plurality of battery component films 30a, b that include one or more adhesion films 34a, b; first or cathode current collector films 38a, b; cathode films 42a, b; electrolyte films 44a, b; anode films 48a, b; and second or anode current collector films 52a, b. This version of the battery 20 with two opposing cells 24a, b can be formed using the same processes used to form the battery 20 with the single cell 24 (FIG. 1A), by flipping over the substrate 28 to form the battery film components 30b of the second battery cell 24b, during or after processing of the first battery cell 30a. Alternatively, the battery film components 30b of the second battery cell 24b can be formed simultaneously with the battery film components 30a of cell 24a, using chambers having multiple process zones as described below.

An exemplary embodiment of a method of forming the battery component films 30 on a battery substrate 28 to fabricate a battery 20, is illustrated in FIG. 3. In the first step, a suitable substrate 28 is selected, the substrate 28 being a dielectric having sufficient mechanical strength to support battery component films 30 and a smooth surface for deposition of thin films. Suitable substrates 28 can be made from, for example, ceramic oxides such as aluminum oxide or silicon dioxide; metals such as titanium and stainless steel; semiconductors such as silicon; or even polymers. One desirable substrate comprises a crystalline sheet formed by cleaving the planes of a cleavable crystalline structure. The cleavable crystalline structure splits along definite planes to create flat surfaces, and can include (i) basal cleavage crystals having cleavage planes parallel to the base of a crystal or to the plane of the lateral axes; (ii) cubic cleavage crystals having cleavage planes parallel to the faces of a cube, (iii) diagonal cleavage crystals which has cleavage planes parallel to a diagonal plane; (iv) lateral cleavage crystals which have cleavage planes parallel to the lateral planes; (v) octahedral, dodecahedral, or rhombohedral cleavage crystals in which cleavage occurs parallel to the faces of an octahedron, dodecahedron, or rhombohedron (respectively); and (vi) prismatic cleavage crystals in which cleavage occurs parallel to a vertical prism. The crystalline cleaving structure can be, for example, mica or graphite. Mica can be split into thin crystal sheets having thicknesses of less than about 100 microns or even less than about 25 microns, as described in commonly assigned US Patent no. 6,632,563 "THIN FILM BATERY AND METHOD OF MANUFACTURE", filed on Sept. 9^th, 2000, which is incorporated by reference herein and in its entirety. The selected substrate 28 is optionally annealed to temperatures sufficiently high to clean the cleavage plane surface by burning-off contaminants and impurities, such as organic materials, water, dust, and other materials formed or deposited on the planar surfaces 26, 27 of the substrate 28; or even heating to temperatures high enough to remove any water of crystallization that may be present within the substrate. The annealing temperatures can be from about 150 to about 600⁰C, even at least about 400⁰C, or even at least about 540⁰C. The annealing process can be conducted in an oxygen-containing gas, such as oxygen or air, or other gas environments, for about 10 to about 120 minutes, for example, about 60 minutes. The cleaning process can also be conducted in an oxygen plasma containing cleaning step. Suitable annealing and other cleaning processes are described, for example, in US patent application no. 11/681 ,754, "THIN FILM BATTERY AND MANUFACTURING METHOD", filed on Mar. 2^nd, 2007, which is incorporated by reference herein in its entirety.

After the substrate cleaning and annealing step, a plurality of battery component films 30 are deposited on the surfaces 26, 27 of the substrate 28 in a series of process steps to form battery cells 24 that can generate or store electrical charge. While a particular sequence of process steps is described to illustrate an embodiment of the process, it should be understood that other sequences of process steps can also be used as would be apparent to one of ordinary skill in the art.

In one embodiment, the battery component films 30 include an adhesion film 34 which is deposited on the planar surface 26 of the substrate 28 to improve adhesion of overlying battery component films 30 (FIG. 1A). The adhesion film 34 can comprise a metal or metal compound, such as for example, aluminum, cobalt, titanium, other metals, or their alloys or compounds thereof; or a ceramic oxide such as, for example, lithium cobalt oxide. When the adhesion film 34 is fabricated from titanium, the titanium film is deposited in a sputtering chamber with, for example, the following process conditions: argon maintained at a pressure of 2 mTorr; DC (direct current) sputtering plasma at a power level of 1 kW, a deposition time 30 seconds, a titanium target size of 5 x 20 inches, and a target to substrate distance of 10 cm. In the version shown in FIG. 1 B, after deposition of a first adhesion film 34a on the first planar surface 26 of the substrate 28, the substrate 28 is flipped over and a second adhesion film 34b is deposited on the second planar surface 27 which forms other side of the substrate. The adhesion film 34 can deposited on the substrate 28 not only to cover the area under the subsequently deposited battery cells 24a-c and their battery component films 30 but also the area 36 extending beyond the battery component films 30, as described in aforementioned US Patent application no. 11/681 ,754. The adhesion film 34 is deposited in a thickness of from about 100 to about 1500 angstroms.

A cathode current collector film 38 is formed on the adhesion film 34 to collect the electrons during charge and discharge process. The cathode current collector film 38 is typically a conductor and can be composed of a metal, such as aluminum, platinum, silver or gold. The current collector film 38 may also comprise the same metal as the adhesion film 34 provided in a thickness that is sufficiently high to provide the desired electrical conductivity. A suitable thickness for the first current collector film 38 is from about 0.05 microns to about 2 microns. In one version, the first current collector film 38 comprises platinum in a thickness of about 0.2 microns. The cathode current collector film 38a-c can be formed as a pattern of features 68a-c, as illustrated in FIG. 2, that each comprise a spaced apart discontinuous region that covers a small region of the adhesion film 34 as per step 106. The features 68a-c are over the covered regions 71a-c of the adhesion film 34, and adjacent to the features 68a-c are exposed regions 70a-c of the adhesion film 34. To deposit the patterned film 38a-c, a patterned mechanical mask is placed on top of the substrate 28, and a first current collector film 38 of platinum is deposited by DC magnetron sputtering to form the features 68a-c between the patterned mask regions. The sputtering conditions for the depositing a platinum film from a platinum target uses sputtering gas comprising argon at a gas pressure of 5 mTorr to form a DC plasma at a power level of 40 W for 10 minutes. After forming the features 68a-c on the adhesion film 34, the adhesion film with its covered regions 71a-c below the patterned features 68a-c and exposed surface regions 70a-d, is then exposed to an oxygen-containing environment and heated to temperatures of from about 200⁰C to about 600⁰C, for example, about 400⁰C, for about an hour, to oxidize the exposed regions 70a-d of titanium that surround the deposited platinum features but not the titanium regions covered and protected by the platinum features. The resultant structure, advantageously, includes not only the non-exposed covered regions 71a-c of adhesion film 34 below the features 68a-c of the current collector film 38, but also oxygen-exposed or oxidized regions 70a-d which form non-conducting regions that electrically separate the plurality of battery cells 24a-c formed on the same substrate 28.

The cathode film 42 comprises an electrochemically active material is then formed over the current collector film 38. In one version, the cathode film 42 is composed of lithium metal oxide, such as for example, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium iron oxide, or even lithium oxides comprising mixtures of transition metals such as for example, lithium cobalt nickel oxide. Other types of cathode films 42 that may be used comprise amorphous vanadium pentoxide, crystalline V₂O₅ or TiS₂. The cathode film can be deposited as a stack of films, with alternate deposition and annealing steps, as for example, described in aforementioned US patent application no. 11/681 ,754. The stress reducing annealing step is performed at a temperature of 200 to about 500⁰C. Typically, the cathode film stack has a thickness of at least about 5 microns, or even at least about 10 microns. The cathode film 42 can also be annealed in a defect reducing step to temperatures from about 150 to about 700⁰C, for example, about 54O⁰C, to further improve the quality of the cathode film 42 by reducing the amount of defects.

In one example, the cathode film 42 comprises crystalline lithium cobalt oxide, which in one version, has the stoichiometric formula of LiCoO₂. The crystalline lithium cobalt oxide film is fabricated using a multiple sequential deposition and stress reducing annealing step as described. The lithium cobalt oxide can be deposited using a magnetron sputtering process with a lithium cobalt oxide target, argon and oxygen at a flow rate ratio of Ar/O₂ of from about 1 to about 45; a chamber gas pressure of from about 5 to about 25 mTorr; plasma power levels of from about 200 to about 1000 Watts; a potential of -5 to -200 V on the substrate; and a substrate temperature of from about 100 to about 200⁰C.

An electrolyte film 44 is formed over the cathode film 42. The electrolyte film 44 can be, for example, an amorphous lithium phosphorus oxynitride film, also known as a LiPON film. In one embodiment, the LiPON has the stoichiometric form Li_xPO_yN_z in an x:y:z ratio of about 2.9:3.3:0.46. In one version, the electrolyte film 44 has a thickness of from about 0.1 μm to about 5 μm. This thickness is suitably large to provide sufficiently high ionic conductivity and suitably small to reduce ionic pathways to minimize electrical resistance and reduce stress.

An anode film 48 formed over the electrolyte film 44. The anode film 48 can be the same material as the cathode film, as already described. A suitable thickness is from about 0.1 μm to about 20 μm. In one version, anode film 48 is made from lithium which is also sufficiently conductive to also serve as the anode current collector film 52, and in this version the anode film 48 and anode current collector film 52 are the same. In another version, the anode current collector film 52 is formed on the anode film 48, and comprises the same material as the cathode current collector film 38 to provide a conducting surface from which electrons may be dissipated or collected from the anode film 48. For example, in one version, the anode current collector film 52 comprises a non-reactive metal such as silver, gold, platinum, in a thicknesses of from about 0.05 μm to about 5 μm. After the deposition of all the battery component films 30, a variety of protective layers or electrically conducting layers can be formed over the battery component films 30 to provide protection against environmental elements. In one example, the protective layer comprises a plurality of metal and ceramic layers that are superimposed on each other. In another example, a portion of the cathode current collector film 38 or anode current collector film 52 that extends out from under a battery cell 24 forms a contact portion that is used to connect the battery cell 24 or the battery 20 to the external environment. This contact portion is coated with an electrically conducting barrier layer in a thickness sufficiently large to prevent the pulsed laser beam from penetrating therethrough.

The thin film battery 20 can also be fabricated to provide a plurality of battery cells 24a-c on a single substrate 28. The battery cells 24a-c can be arranged horizontally across a single substrate surface 26 or fabricated on the front surface 26 and backside surface 27 of a battery substrate 28 to substantially increase the energy density and capacity of the battery cell 24. Suitable battery configurations, protective layers, and packaging, are described in for example, US Patent Application No. 11/090,408, filed on March 25, 2005, entitled "THIN FILM BATTERY WITH PROTECTIVE PACKAGING" by Krasnov et al., which is incorporated by reference herein and in its entirety.

A battery preform 76 can be cut into smaller pieces that each form battery substrates 28 having individual batteries 20 thereon, in a pulsed laser cutter 80, an embodiment of which is shown in FIG. 9. The battery preform 76 in this context is simply a larger section of battery substrate material that can be cut into the smaller battery substrates 28 before, after partial completion of, or after entirely completing, processing battery component films 30 that cooperate to form one or more battery cells 24a-c on each battery substrate 28.

Another embodiment of a thin film battery 20 comprising a battery cell 24 on a planar surface 26 of a substrate 28, is illustrated in FIG. 4. The battery cell 24 comprises a plurality of battery component films 30 that cooperate to form a battery to receive, store, or discharge electrical energy. The films 30 can be employed in a number of different arrangements, shapes, and sizes. In one embodiment, the battery component films 30 include at least a pair of electrode films with an electrolyte film 44 therebetween. The electrode films can include one or more of a cathode current collector film 38, cathode film 42, anode film 48, and anode current collector film 52, which are all inter-replaceable. For example, the battery 20 can include (i) a pair of cathode and anode films or a pair of current collector films, (ii) both the anode/cathode films and the current collector films, or (iii) various combinations of these films, for example, a cathode film and an anode and anode current collector film but not a cathode current collector film, and so on. The exemplary versions of the battery 20 illustrated herein are provided to demonstrate features of the battery and to illustrate their processes of fabrication; however, it should be understood that the exemplary battery structures should not be used to limit the scope of the invention, and alternative battery structures as would be apparent to those of ordinary skill in the art are within the scope of the present invention.

An embodiment of a process of fabricating a thin film battery 20 is shown in FIG. 5. While a particular sequence of process steps is described in FIG. 5 to illustrate an embodiment of the process, it should be understood that other sequences of process steps can also be used as would be apparent to one of ordinary skill in the art. In the first step, a suitable battery substrate 28 is selected, the substrate 28 being a dielectric having sufficient mechanical strength to support battery component films 30 and a smooth surface for the deposition of thin films, as described above. Referring to FIG. 5, in an optional step, a substrate 28 is cleaned to remove surface contaminants or even annealed to remove impurities prior to processing, to obtain good adherence of deposited films. After a suitably clean surface is obtained, a plurality of battery component films 30 are deposited on the surface 26 of the substrate 28, as illustrated in FIG. 6A. One or more of the films 30 can be shaped in between deposition steps for additional films 30, or even after deposition of all the films 30, to remove portions of each film or even the substrate 28, to create shaped features that can cooperate with other film layers or connector elements to form the battery 20, as illustrated in FIG. 6B.

The substrate 28 and one or more deposited battery component films 30 make up a battery preform 76, which can be shaped to form shaped features 54, for example to remove portions of the battery component films 30 as shown in FIG. 6A. Shaping the deposited films 30 after their deposition on the substrate 28 provides shaped features 54 that can be obtained substantially without the use of a mask. While a mask can still be used to improve the shape of the features, the present process can be performed without any mask. The shaped features 54 are positioned and sized so that they shape the battery films 30 through which the features are cut to form a battery cell 24. For example, shaped features 54 comprising holes can be used to form terminals 68, 68a, b, as shown in FIG. 6B, by depositing material into the holes. A battery preform 76 comprising substrate 28, anode current collector film 52, anode film 48 and electrolyte film 44 is shown in these drawings; however, the preform 76 can be any combination of film and substrate layers as the shaping process is easily adapted to shaping other battery film configurations and structures. After shaping the battery preform 76, the remaining battery component films 30 are deposited onto the shaped preform 78 to construct the thin film battery cell(s) 24. An anode film 48 is formed on the shaped battery preform 78 on the electrolyte film 44. The anode film 48 can be the same material as the cathode film, as already described. A suitable thickness is from about 0.1 microns to about 20 microns. In one version, anode film 48 is made from lithium which is also sufficiently conductive to serve as the anode current collector film 52, and in this version the anode film 48 and anode current collector film 52 are the same. In another version, the anode current collector film 52 is deposited onto a region of the electrolyte and an anode film is deposited onto the electrolyte and onto a portion of the anode current collector film, wherein the anode current collector film comprises the same material as the cathode current collector film 38 to provide a conducting surface from which electrons may be dissipated or collected from the anode film 48. For example, in one version, the anode current collector film 52 comprises a non-reactive metal such as silver, gold, platinum, in a thickness of from about 0.05 microns to about 5 microns.

In the version shown in FIG. 6B, an anode current collector film 52 is selectively deposited onto the shaped battery preform 78 onto a region of the electrolyte film 44 that is away from the shaped feature 54. The anode film 48 is then deposited onto the electrolyte 44 and part of the anode current collector film 52.

In another embodiment, the battery 20 can include a first battery cell 24a on a first planar surface 26 of the substrate 28, and a second battery cell 24b on a second planar surface 27 of the same substrate 28, as shown in FIG. 7. The multiple battery cells can also be placed on the same surface or side of the substrate 28 (not shown). Versions of the battery 20 with two opposing cells can be formed using the same processes used to form the battery 20 with the single battery cell 24 by flipping over the substrate 28 to form the battery film components of the second battery cell, or after processing of the first battery cell 24. Alternatively, the battery film components of the second battery cell can be formed simultaneously with the battery component films 30 of the first cell 24, using chambers having dual or multiple process zones covering each side of the substrate 28.

The battery preform 76 and deposited component films 30 can be shaped using a pulsed laser process. The pulsed laser process can also be used to cut the battery substrate. In the pulsed laser process, portions of the deposited component films 30 and even portions of the substrate 28 can be removed to shape the films 30 and cut or drill through the substrate 28. The pulsed laser bursts are applied at a sufficiently high power level to vaporize portions of the battery preform 76 to form shaped features from the deposited films 30 substantially without causing fractures along the cleavage planes of the battery substrate 28. Also, the power level of the pulsed laser beam bursts are controlled to vaporize a predetermined depth of the battery preform to form shaped features in individual films 30 to remove a portion of a film 30 or a stack of films that have been sequentially deposited onto the surface 26 of the substrate 28. The laser process can be used to shape the films 30 by controlling the power level of the laser bursts, and the location of the pulsed laser, to ablate the films deposited on the substrate 28. For example, in one embodiment, the pulsed laser beam bursts comprise beam bursts from an ultraviolet laser beam applied at a power level of from about 0.2 to about 1 watts, and with a duration of from about 40 to about 160 nanoseconds. These pulsed bursts can be provided at a pulse rate of from about 5 to about 200 Hz. The pulsed laser bursts can be moved across the battery substrate with a vectorial velocity of from about 2 to about 10 mm/s.

The pulsed laser process is conducted in a dry box or dry room which is absent oxygen or moisture when the battery preform 76 includes previously deposited battery component films 30 that can oxidized, such as lithium or LIPON films. A gas nozzle 93 can also be used to blow a gas stream 95 of blowing gas onto the lased region on the battery preform 76 to remove any debris or vapors from the lased area. The gas nozzle 93 obtains the blowing gas from a gas source 96 and the gas flow rate or pressure can be controlled by a gas flow controller 97. The blowing gas can be air, argon, nitrogen, or a mixture of such gases, and the pressure of the gas can be, for example, at least 2 Kg/cm³. In the pulsed laser process, a low power laser (not shown) can also be used to indicate the position of the pulsed laser beam 98 on the battery preform 76, such as for example, a He-Ne laser.

In the pulsed laser process, the battery preform 76 is placed on a movable stage 84 that is capable of moving the battery preform 76 during laser shaping. The movable stage 84 can comprise a table that can be moved in the x and y directions. The movable stage 84 is positioned by a stage motor 92 which can be controlled by a programmable controller 88. The movable stage 84 and programmable controller 88 can include interpolative program code to enable movement of the table in the x-y plane using velocity or even acceleration vectors. In one embodiment, the movable stage 84 can be set to provide different levels of vectorial velocity for example from about 0.1 to about 400 mm/s, or even from 2 mm/sec to about 10 mm/sec. In another embodiment, the vectorial acceleration of the stage can be set with levels ranging from about 0.5 to about 50 mm/sec², for example, at 0.8, 4, 20, and 40 mm/sec². In one embodiment the movable stage is capable of being positioned to an accuracy of greater than about 12 microns.

The pulsed laser beam 98 provides pulsed laser bursts which have an output energy corresponding to a series of energy spikes that may be partially overlapping or entirely separated in time; in contrast to continuous wave lasers which produce a continuous laser output having a steady state equilibrium. The pulsed laser beam 98 comprises pulsed laser bursts, which for example, can have a duration in the range of nanoseconds (10^~9 sec) or femtoseconds (10 ¹⁵ sec). The pulsed laser beam 98 can be used to remove portions of the preform 76 with reduced delamination or micro-crack formation. For example, the pulsed laser beam 98 can cut the battery substrate preform 76 with reduced delamination or micro-crack formation. The pulsed laser beam was also found to work well on thin substrates which are sized less than 100 microns because such a thin substrate would absorb too much energy from a continuous laser beam and melt or otherwise deteriorate during the cutting operation. For example, it was determined that using a high power CO₂ laser operated in a continuously turned-on mode to cut portions of a substrate 28 comprising cleavage planes and having a thickness of less than 100 microns, caused excessive localized heating and the resultant thermal shock often caused cracking and delamination of the cleavage planes of the substrate 28 or even delamination of the battery component films 30 from the battery preform 76.

In substrate cutting, the pulsed laser beam 98 was set up to provide pulsed laser bursts having an energy level sufficiently high to form a rapidly expanding thermal plasma of substrate material which then collapses to form shock waves that cut through the battery substrate 28 by mechanical disruption at the cutting region. The pulsed laser bursts provide sufficient energy to transform the substrate from a solid to a plasma phase which then expands away from the substrate 28 taking most of the heat away from the substrate 28. Essentially, the cut portions of the battery substrate preform 76 vaporize without going through a melting phase transition because the short duration of the pulses transmits less energy to the battery substrate 28 or preform 79 than a continuous laser beam.

In the pulsed laser process, the pulsed laser source 82 is positioned above the movable stage 84 and is powered by a laser power supply 102 to generate a pulsed laser beam 98 as shown in FIG. 9. An exemplary pulsed laser source 82 that can provide pulsed laser bursts comprises a lasing medium 104 and laser light source 108 positioned at the twin focal points of a light resonator 110. The lasing medium 104 can be a solid-state rod material such as a titanium doped sapphire, Nd:YAG, a chrominum ion doped ruby; or a gas laser which uses a combination of an inert gas and reactive gas to generate the laser beam. The light resonator 110 comprises an elliptical cavity 112 having reflective surfaces 114 which reflect photons emitted from the light source toward the lasing medium 104. These photons resonate in the lasing medium 104 between a highly reflective mirror 116 and a partially reflective output coupler 118 at either end of the lasing medium 104. The generated laser beam 120 is emitted through the partially reflective output coupler 118. For efficiency, the composition and concentration of the lasing medium 104, as well as the construction of the elliptical cavity 112 of the light resonator 110, the mirror 1 16, and the coupler 118, is optimized for pulsed laser operation. The continuous laser beam 120 generated by the laser source 82 is passed through a laser optical system 86 which comprises a neutral density filter 122, one or more focusing lenses 124, and a shutter 128. The neutral density filter 122 reduces the intensity of all wavelengths or colors equally. The focusing lens 124 can have a focal length of from about 1 to about 20 cm, such as for example, 10 cm. The shutter 124 comprises a mechanical shutter capable of rapidly opening and closing, such as a mode locking or electro-optical shutter. By opening and closing rapidly, the shutter 124 can generate a pulsed laser beam 98 having laser pulses with pulse durations in nanoseconds or femtoseconds, as an output of the input continuous laser beam 120.

In one version, the pulsed laser source 82 is a femtosecond laser comprising a diode- pumped solid-state laser with a lasing medium 104 comprising a rod of titanium doped sapphire. The femtosecond pulsed laser is set up to provide pulsed laser bursts having peak intensities of from about 1 to about 10 GigaWatts. However, the pulsed laser bursts are so short in duration that the delivered laser energy does not have sufficient time to dissipate across more than one film 30 if so desired, or even across the thin battery preform 76 from the laser cutting beam spot to surrounding inter-lamellar cleavage planes of the battery substrate 28 via thermal conduction. Consequently, not enough heat is transferred to other battery films 30 or to the substrate 28 to ablate or otherwise damage the other films 30 or damage the planar cleavage structure of the battery substrate 28. This provides a clean laser cut with low residual fracturing about the lased region and the absence of melting reduces splatter which would otherwise result from molten film and substrate material formed around the lased region of the battery preform 76.

The pulsed laser source 82 can also use an ultraviolet laser to generate a continuous laser beam which is then formed into pulsed laser bursts as described above. The ultraviolet laser can be, for example, an excimer or 'excited dimer' laser, which is a chemical laser that uses a combination of an inert gas, such as argon, krypton, or xenon; and a reactive gas such as fluorine or chlorine, to generate a laser beam. Under appropriate electrical stimulation, a pseudo-molecule called a dimer - which exists only in an energized state - gives rise to laser light in the ultraviolet range which is well focused and capable of delicate control. Rather than burning or cutting material, the excimer laser adds enough energy to disrupt the molecular bonds of the surface of the battery preform 76, which then effectively ablate and disintegrate into vapor rather than burn. Thus, the ultraviolet laser can be used to remove fine layers of surface material with almost no heating or change to the material left behind. From battery substrate cutting energy calculations it was determined that a suitable ultraviolet laser beam can be an excimer laser beam having a power level of from about 5 to about 80 microJoules, which is operated with a pulse duration of from about 1 to about 50 nanoseconds, and a pulse rate of from about 5 to about 200 Hz.

In one example, a pulsed laser source 80 comprising a femtosecond laser source was set to energy levels and pulse durations that allowed ablation of portions of a battery preform 76 with good results. In this example, the femtosecond pulsed laser beam 98 was set to provide an irradiance level of from about 1 to about 800 J/cm², and pulsed laser bursts having a pulse duration of from about 50 to about 600 femtoseconds, for example, about 150 femtosecond. Based on this pulse duration, a suitable fluence level for the femtosecond pulsed laser beam 98 was calculated to be from about 10 to about 800 J/cm². The pulse can be set to be from about 2 microjoules to about 100 millijoules, in one example, about 750 microjoules. The pulse repetition rate should also be set to provide good cutting, and in one example, the pulse repetition rate was set to be from about 50 to about 1000 Hz, for example, about 125 Hz.

The pulsed laser beam 98 can be set to provide laser pulses having a desired peak laser fluence that is selected in relation to the type of battery component films 30 and substrate 28 to be shaped, and the desired shaping parameters. As the pulsed laser cutting process can also be employed at any of several different stages of the battery fabrication process, the energy density required for the pulsed laser beam 98 depends on the thickness of, and layers formed on, the battery substrate 28. The energy density or fluence of a pulsed laser beam 98 which was needed to shape a battery preform 76 comprising a mica substrate with titanium adhesion film, platinum cathode current collector film and a lithium metal oxide cathode film thereon, was estimated to be at least about 8 J/cm². As another example, shaping a thin adhesion layer 34 or cathode current collector film 38 required a pulsed laser beam 98 having a peak laser fluence of less than 0.2 J/cm². Without the thicker cathode layer 42, a much lower threshold of energy level was needed. However, the energy density required to shape a battery preform 76 comprising a mica substrate 28 and additionally, a cathode film 42 of platinum or titanium in a thickness of less than about 40 micron, was estimated to be less than 1.5 J/cm². Thus, when shaping a battery preform 76 of mica with battery component films 30 including the adhesion film 34, cathode current collector film 38, and cathode film 42, and having a total thickness of about 40 microns, the pulsed laser beam 98 was set to provide a peak laser fluence of at least about 8 J/cm².

Thin battery substrate preforms 78 sized with thicknesses less than 100 microns, as well as battery substrate having cleavage planes joined by weak Van der Walls forces, were both found to be particularly well cut using controlled pulsed laser bursts from a pulsed laser beam 98. When cutting such battery substrates, the pulsed laser beam 98 is controlled to apply the pulsed power in energy and duration levels that do not cause the thin substrate to melt or splatter across it's cutting edge, or cause fracture of the cleavage planes that occur between the crystal sheets of the substrate material. Thus, the pulsed laser beam 98 is set to provide pulses of sufficient power and duration to cut through the substrate without melting or fracturing the cleavage planes by excessive heat loading. Several power measures can be used to set the power levels of the pulses of pulsed laser beam 28. As one example, the irradiance of the pulsed laser beam which is the power density of the pulsed laser source 82 and can be expressed in Joules/unit area can be used. Another measure is the fluence of the pulsed laser beam 98 which is the irradiance multiplied by the laser pulse duration or exposure time and is measured in J/cm². Yet another laser power level measure is the average energy output per pulse or Epulse, in joules.

In one example, a pulsed laser source 82 comprising a femtosecond laser source was set to energy levels and pulse durations that allowed cutting thin battery substrates 28 having cleavage planes with good results. In this example, the femtosecond pulsed laser beam 98 was set to provide an irradiance level of from about 1 to about 440 J/cm², and pulsed laser bursts having a pulse duration of from about 50 to about 600 femtosecond, for example, about 150 femtosecond. Based on this pulse duration, a suitable fluence level for the femtosecond pulsed laser beam 98 was calculated to be from about 10 to about 800 J/cm². The Epulse can be set to be from about 2 microjoules to about 100 millijoules, in one example, about 750 microjoules. The pulse repetition rate should also be set to provide good cutting, and in one example, the pulse repetition rate was set to be from about 50 to about 1000 Hz, for example, about 125 Hz. The vectorial velocity of the movable stage 84 was set to be from about 0.1 to about 40 mm/s, or even from 0.2 mm/sec to about 20 mm/sec.

In these examples, the pulsed laser beam 98 was also set to provide laser pulses having a peak laser fluence that depends on the type of battery substrate preform 76 being cut and the desired cutting parameters. Generally, the smoothest laser cut with least delamination or cleavage plane fracturing along the laser beam cutting edge was achieved with a pulsed laser beam 98 having a relatively low power density combined with slow beam traverse velocity across the stage surface 90. Also, the pulsed laser beam 98 was usually set to produce a laser cut having a surrounding damage area limited to a set distance, for example, less than about 50 microns from the cutting boundary. The pulsed laser cutting process can also be employed at any of several different stages of the battery fabrication process and the energy density required for the pulsed laser beam 98 depends on the thickness of, and layers formed on, the battery substrate 28. In one cutting process, a battery substrate preform 76 comprising mica is pre-cut into a plurality of smaller sized battery substrates 28 that each have a desired shape. The energy density or fluence of a pulsed laser beam 98 which was needed to cut a battery substrate preform 76 comprising only mica in a thickness of 10 to 15 microns, was estimated to be at least about 8 J/cm². As another example, cutting a thin adhesion layer 34 or cathode current collector film 38 required a pulsed laser beam 98 having a peak laser fluence of less than 0.2 J/cm². Without the thicker cathode layer 42, a much lower threshold of energy level was needed. However, the energy density required to cut a battery substrate preform 76 comprising a mica substrate and additionally, a cathode film 42 of platinum or titanium in a thickness of less than about 40 micron, was estimated to be less than 1.5 J/cm². Thus, when cutting a battery substrate preform 76 of mica having battery component films 30 including the adhesion film 34, cathode current collector film 38, and cathode film 42, and having a total thickness of about 40 microns, the pulsed laser beam 98 was set to provide a peak laser fluence of at least about 8 J/cm².

Microphotographs of a cut circular region on a battery substrate preform 76 which was cut using a femtosecond laser, as shown in FIGS. 10A to 10E, demonstrated that a pulsed laser beam 98 operated to provide femtosecond laser pulse bursts significantly improved cutting edges as compared to cuts from CO₂ laser which provided continuous laser power. In these examples, the pulsed laser cutter 80 used a laser source 82 comprising a CPA-21 10 model titanium and sapphire laser, commercially available from Clark-MXR, Inc. The pulsed laser beam 98 had a wavelength of 775 nm, a power density of 19 J/cm², and a polarization which was linear and horizontal, and was used in the transverse mode, TEM00. The pulsed laser beam also had a beam diameter of 4 to 6 mm and a beam divergence of less than 100 microradians. The pulsed laser cutter 80 also used a movable stage 84 capable of providing a vectorial velocity of about 0.2 mm/sec. The pulsed laser cutter 80 was capable of providing a pulsed laser beam 98 with a pulse energy of greater than 0.8 mJ, pulse repetition rates of less than 1000 Hz, a pulse width of less than 150 fsec. In one example, the laser pulsed beam was set to provide a pulse duration of less than about 150 femtoseconds, an Epulse of 750 microjoules and a pulse repetition rate of 125 Hz. The pulsed laser beam 98 was operated at various laser fluence levels ranging from about 10 to about 500 J/scm², and including levels of 19, 27, 91 , 210 and 440 J/cm². The movable stage 84 results is set to provide different levels of vectorial velocity ranging from about 0.2 to about 20 mm/sec, for example, at 0.2, 1 , 5, 10 and 20 mm/sec. The vectorial acceleration of the stage was set to levels ranging from about 0.5 to about 50 mm/sec², for example, at 0.8, 4, 20, and 40 mm/sec². The laser optical system 86 was set to provide normal incidence and the focusing lens 124 was a plano-convex lens with a focal length set to 10 cm.

As seen from FIGS. 10A to 10E, the pulsed laser beam 98 operated at femtosecond laser pulses provided a clean laser cut with minimal surrounding damage to the substrate, while the CO₂ laser provided a cut with a large damaged area with splattering that exceeding 50 microns, or even 100 microns. FIG. 10A is a scanning electron micrograph of the top view of a hole cut in a battery substrate by a continuous laser beam of a CO₂ laser. It is seen that the carbon dioxide laser uses a cutting edge that is a rough and scarred, and contains bubbles and other defects. The splattering caused by the energy provided by the CO2 laser also caused damage extending a considerable distance into the substrate from the cutting edge. In contrast, FIG. 10B is a scanning electron micrographs of the top view of a hole cut in a battery substrate using a pulsed laser beam 98 operated at femtosecond pulses. This laser cut is much better one with a cleanly defined edge that is smooth and continuous and does not extend deep into the substrate. FIGS. 10C and 10D are optical microscope images of detailed sections of the holes cut in the battery substrate in FIGS. 10A and 10B, respectively, and these images also show the much better quality of cut obtained by the pulsed laser beam. FIG. 10E is another more detailed view of a scanning electron micrograph of a hole cut in a battery substrate by a pulsed femtosecond laser showing the clean cut and lack of delamination through cleavage planes.

Thus, as shown, the pulsed laser beam 98 provided significantly improved results with much less debris resulting from the splattered and molten material around the laser cut because the rapidly pulsed bursts of laser caused vaporization of substrate material without the splattering that otherwise occurred from the molten material generated by the carbon dioxide laser. These results are unexpected because the total energy provided by the pulsed laser beam far exceeded than provided by the carbon dioxide laser beam. Further, because the molten debris produced by the long pulse carbon dioxide laser was extremely hot as it landed on the substrate surface, it was difficult to remove this debris and such removal requires considerable post processing efforts and also often damages the substrate surface. The pulsed laser beam 98 generated fine dust which did not carry much heat, and consequently, did not melt and bond around the cut substrate surface. There were also much less observed delamination along cleavage planes because of the lower total energy transferred across the substrate preform 76 by the pulsed laser beam 98.

Another battery substrate 28 with overlying films 30 (having a thickness of 20 microns) was cut using a pulsed laser source with a pulsed ultraviolet laser operated to provide a laser beam 98 having a wavelength of 193nm (CaF₂ was used), power level of 20 microJoules, and pulse width of about 8 nanoseconds. Good cutting results were obtained by cutting initially from a top side and then from the reversed bottom side to finish the cut. With this procedure, the bottom polished surface of the substrate 28 was not broken through, reducing the cleavage fracture and damage that would otherwise occur with such breakthrough.

Various exemplary cutting processes will now be described referring to the process flow charts of FIGS. 11A to 11C. In one cutting process, a battery substrate preform 76 of mica is partially pre-cut by a pulsed laser beam 98 into a loosely connected smaller battery substrates 28 that each have a desired shape but are still attached to one another in the large substrate preform 76, as shown in FIG. 11A. The whole larger area of the substrate preform 76 is then used to deposit all the battery component films to construct a thin film battery 20. When completed, the smaller thin film battery cells 20 are easily cut off from the large substrate preform 76 by the pulsed laser cutter 80.

In another example, some of the battery component films 30 are formed on a battery substrate preform 76 of mica which is then cut into smaller battery substrates 28 that each have a desired size and shape, as described in FIG. 11 B. The remaining battery component films 30 are then deposited on the cut battery substrates 28 to construct a plurality of thin film batteries 20. For example, a cathode current collector film 38, cathode film 42, and an electrolyte film 44a can be deposited on a battery substrate preform 76 of mica, and only after such deposition, the preform 76 is cut into smaller pieces having the desired shapes and sizes. The width of the margin between the cut line along the battery substrate 28 and the nearest edge of a battery cells 24 is between about 1 and about 4 mm. After cutting the individual substrate pieces, the remaining battery component films 30 are deposited on the individual substrate pieces to construct various thin film battery cells 24. In yet one more version, a battery substrate preform 76 of mica is deposited with all the battery component films 30 to construct one or more thin film battery cells 24 and then cut into a few smaller cells. In this example, the battery substrate preform 76 is deposited with battery component films 30 comprising a cathode current collector film 38, a cathode film 42, a metal film (not shown) to block the lithium ions from moving to the anode current collector layer covering a small area of the cathode film 42, and a electrolyte 44 layer covering the cathode film 42 and metal film. The substrate preform 76 with the deposited battery component films 30 is then cut with the pulsed laser beam. A small area of the stacked electrolyte and cathode films, away from the metal film, is then etched away by the pulsed laser beam 98 to expose the cathode current collector film. The anode current collector film 52 covering the electrolyte 44 in the same area as the metal layer. An anode film 48 covers the electrolyte film 44 and is in contact with the anode current collector film but not in contact with the cathode current collector film. After deposition of these films, the battery substrate preform 76 is then cut into smaller pieces that each form a battery substrate 28 comprising a battery 20.

In the example of FIG. 11C, a battery substrate preform 76 of mica is deposited with all the battery component films 30 needed to construct a thin film battery 20 as well as overlying protective layers is cut by a pulsed laser beam and the laser cut edges are sealed, as shown in FIGS. 12A to 12D. The battery 20 includes first and second battery cells 24a, b both formed on a first planar surface 26 of the substrate 28. Each battery cell 24a, b comprises a plurality of battery component films 30. For example, the battery 24a comprises an adhesion film 34a, cathode current collector film 38a, cathode film 42a, electrolyte film 44a, anode film 48a, and anode current collector films 52a. The cathode and anode current collector films 38a, 52a, respectively, have contact portions 160,162 that extend out from the battery cell 24a to form electrical contacts that serve as positive and negative terminals for connecting the battery 20 to the external environment. An electrically conducting barrier layer 164a,b is formed on the contact portions 164a,b in a thickness that is sufficiently large to prevent the pulsed laser beam 98 from cutting through the underlying contact portions 160,162. The electrically conducting barrier layer 164a,b can be for example, a silver epoxy or silver paste, and is applied in a thickness of from about 5 to about 100 microns. An overlying protective multilayer coating 166 conforming to the external shape of the battery cells 24a, b is deposited over the battery component films 30 to protect them from erosion by the environment. The protective multilayer coating 166 can be for example, multiple ceramic and polymer layers which are deposited superimposed on one another, polymer layers, or other packaging layers. The whole battery substrate preform 76 with the deposited battery component films 30, electrically conducting barrier layer 164a,b covering the contact portions 160, 162 that will serve as terminals, and the protective multilayer coating 166, is cut into smaller battery substrates that each include one or more of the battery cells 24a, b. In one step of the cutting process, as shown in FIGS. 12A and 12B, the protective conformal coating 166 covering the contact portions 160,162 extending out from the battery cell 24a is burned off by the pulsed laser beam 98 to expose the underlying electrically conducting barrier layer 164a,b, respectively. An edge sealant 170 is then formed over the exposed region 172 of the protective multilayer coating 166 and a perimeter edge 174 of the contact portion 164a,b to sealed the laser cut edge while still exposing the contact portions 164a, b to serve as electrical terminals. In another step of the cutting process, as shown in FIGS. 12C and 12D, a portion of the protective multilayer coating 166 extending beyond the battery cell 24a and in direct contact with the underlying substrate 28 is cut by the pulsed laser beam 98 from the pulsed laser cutter 80. After the cutting operation, an edge sealant 170 is formed over the exposed region 170 of the laser cut edge to seal this region.

The edge sealant 170 is applied over the laser cut edge of the battery 20, as shown in FIGS. 12B and 12D, to reduce moisture seepage from the cut edge into the battery component films 30a. The edge sealant 170 can also be used to prevent the protective multilayer coating 166 from cracking or splitting as a result of the post laser cutting operation. In one example, the edge sealant 170 comprises an epoxy that is applied by hand painting, dipping or spraying along the path of the laser cut before/after the laser cut. The epoxy can be a thermosetting UV cured polymer, or an epoxy filled with ceramic or metal particles. The edge sealant 170 can also be applied as an epoxy strip simultaneously with or during the laser cutting operation. The sealing and simultaneously applied edge sealant 170 melts in the instantaneous heat provided by the pulsed laser beam 98, and as a result, seals the laser cut edge.

FIG. 13A shows a version of a shaped battery preform configured for a substrate with battery terminals accessible from top and bottom sides of the substrate. This version can be used for stacked batteries in which the battery substrates are layered one on top of the other and the anode and cathode terminals are electrically connected to each other along the stack. Alternately, this version can be used for substrates having a battery cell on both the top and bottom sides of the substrate, where the through-holes serve to electrically connect the anode and the cathode of the first cell to the anode and the cathode of the second cell. An electrical connection is formed between the top and bottom surfaces of the battery cell 24 by filling the through-holes 74a, b with an electrically conductive material. The connection and can even be selectively polarized by selectively coating the sides of one or more through-hole 74a, b with electrically insulating adhesive 66 prior to insertion of the conductive material. In the version shown in FIG. 13B electrically insulating adhesive 66 is applied to the sidewalls of a first through-hole 74a and an anode current collector film deposited thereon 52.

A pulsed laser, as described herein, can be used to form through-holes 74a, 74b that extends through the thickness of the battery preform 76. For battery preform 76 comprising mica substrate with deposited films on a single surface of the substrate 28, good through-hole formation results were obtained by applying the pulsed laser initially from a top side and then from the reversed bottom side to finish the cut. With this procedure, the second planar surface 27 of the substrate 28 was not broken through, reducing the cleavage fracture and damage that would otherwise occur with such breakthrough.

After formation of the shaped features 54, portions of the features can be coated to create selectively insular or conductive regions on the shaped battery preform 78. Insulating adhesive can be applied to selected surfaces of the shaped preform to change the electrical contact properties of the surface. As shown in FIG. 13B, the sidewalls of through-hole 74a were coated with electrically insulating adhesive 66 to allow electrical connectors 72a to extend through the battery from a top surface to a bottom surface of the shaped preform 78 substantially without contacting the intermediary layers, as shown in FIG. 7. The electrically insulating adhesive 66 can be an epoxy or any insulating resin or ceramic thin film and is applied in a thickness sufficiently large to prevent current drain therethrough. A suitable electrically insulating adhesive 66 comprises an electrical specific resistivity larger than 10⁸ ohm-cm. In one version the electrically insulating adhesive 66 comprises an epoxy resin such as Hardman® low viscosity epoxy, available from Royal Adhesives & Sealants, LLC of South Bend, Indiana, USA. The electrically insulating adhesive 66 can be applied in a thickness of from about 0.2 to about 10 microns. In one embodiment the electrically insulating adhesive comprises epoxy and is applied in a thickness of from about 0.5 to about 5 microns.

The configuration shown in FIGS. 7 and 13B enables electrical contact between the anode and an anode contact material. The anode contact material can comprise an electrically conductive post or a blob of electrically conducting adhesive 64 that is inserted into the through- hole 74a to substantially contact the anode current collector film 52 on the sidewalls of the through-hole 74a and which can even form a terminal of the battery 20. Electrical contact pads 68, 68a,b can be formed by application of an electrically conductive material to the shaped features 54 or exposed regions of the current collector films. The electrical contact pad 68 of FIG. 6B comprises an electrically conductive adhesive 64 that is flowed into the shaped feature of the battery preform 76. The electrically conductive adhesive contacts 64 the cathode current collector film 38 and provides a conductive pathway between the cathode current collector film 38 and the top surface of the battery 20. The upper surface of the electrically conductive adhesive 64 can serve as a contact pad 68 for electrical connection of the battery cell 24 to other battery cells or electrical circuit elements.

After the deposition of all the battery component films 30, or even after electrically conductive adhesive 64 is applied to form electrical contact pads 68a, b, a variety of protective layers or electrically conducting layers can be formed over the battery component films 30 to provide protection against environmental elements. The protective layer can comprise polymer, ceramic or metal layers or combinations of layers. In one example, the protective layer comprises a plurality of polymer and ceramic layers that are superimposed on each other.

The thin film battery 20 can also be fabricated to provide a plurality of battery cells 24a-c on a single substrate 28, as shown in FIGS. 14A and 14B. The battery cells 24a-c are be arranged horizontally across a single substrate surface 26, however they can alternately be fabricated on the front surface 26 and backside surface 27 of a battery substrate 28 (not shown) to substantially increase the energy density and capacity of the battery cell 24.

A plurality of battery cells can be deposited on a wafer of battery substrate and thereafter the wafer can be cut into smaller pieces that each form battery substrates 28 having one or more battery cells 24 thereon, or to form individual batteries 20. A pulsed laser cutter 80 can be used to cut the substrate wafer, which is simply a larger section of battery substrate material. The wafer can be cut into individual battery wafers before, after partial completion of, or after entirely completing, processing battery component films 30 that cooperate to form one or more battery cells 24a-c on each battery substrate 28. In one embodiment the laser cutter 80 comprises a pulsed laser source 82, a movable stage 84, a laser optical system 86, and a programmable controller 88 that are operated to cut the substrate to the desired cutting pattern.

Examples:

The following examples are provided to illustrate an application of the present battery and fabrication methods, but should not be used to limit the scope of the invention. The multi-cell battery 20 shown in FIG. 14A and 14B comprises a mica substrate with adhesion layer, cathode current collector, cathode, electrolyte, anode current collector and anode films. The mica substrate has a thickness of about 15 microns. An adhesion layer was applied to the substrate, comprising lithium cobalt oxide with a thickness of from about 0.1 to about 0.2 microns. A cathode current collector comprising platinum with a thickness of about 0.2 microns was deposited onto the adhesion layer. A cathode film comprising LIPON film with a thickness of about 2 microns was deposited onto the cathode current collector.

After deposition of the adhesion layer, cathode current collector, cathode and electrolyte, the battery preform was shaped using a pulsed laser source 82 comprising a UV solid-state diode pumped laser comprising a Nd:YAG (neodymium-doped yttrium aluminium garnet) lasing medium 104. The UV Nd: YAG laser is capable of emitting light in a wavelength of about 355 nm. An exemplary Nd:YAG UV laser is, for example, a 3W Hawk-ll UV laser, available from Quantronix®, Long Island, New York. The pulsed laser source 82 was operated with a pulse frequency of about 6kHz and pulse duration of about 80 nanoseconds, and with an average output power of about 0.5 W while shaping.

After laser shaping, a thin layer of insulating material was applied to a hole in the battery preform. Additional films comprising an anode current collector film followed by an anode film were then deposited onto the shaped preform. The anode current collector film comprises a copper film with a thickness of about 0.2 microns. An anode film comprising lithium with a thickness of from about 2 to about 3 microns was deposited onto the electrolyte and covering a portion of the anode current collector film.

The battery was measured to provide an output voltage in the range of from about 3.8 to about 4.2 Volts. Each battery cell 24 had a capacity of about 0.1 mA hr and corresponding energy density of about 200 W^»hr/liter. The complete cells 24 have a diameter of about 7.5 mm.

While illustrative embodiments of the thin film battery are described in the present application, it should be understood that other embodiments are also possible. Also, the packaging assembly of the present invention can be applied to contain and hermetically seal other type of batteries, as would be apparent to those of ordinary skill in the art. Thus, the scope of the claims should not be limited to the illustrative embodiments.

Claims

What is claimed is:

1. A method of fabricating a battery on a battery substrate, the method comprising:

(a) selecting a battery substrate having cleavage planes;

(b) applying a plurality of pulsed laser bursts of a pulsed laser beam to the battery substrate, the pulsed laser bursts having sufficient power and duration to cut through the battery substrate substantially without causing fractures along the cleavage planes of the battery substrate; and

(c) before or after (b), depositing a plurality of battery component films on the battery substrate, the battery component films comprising at least a pair of electrodes about an electrolyte that cooperate to form a battery cell.

2. A method according to claim 1 wherein the battery substrate comprises at least one of the following:

(i) a mica substrate;

(ii) a thickness of less than about 100 microns.

3. A method according to claim 1 comprising applying a pulsed laser beam comprising an ultraviolet laser beam.

4. A method according to claim 1 comprising applying a pulsed laser beam comprising at least one of the following:

(i) a power level of from about 5 to about 80 microJoules;

(ii) a fluence of from about 10 to about 800 J/cm²;

(ii) a duration of from about 1 to about 50 nanoseconds; and

(iii) a pulse rate of from about 5 to about 200 Hz.

5. A method according to claim 1 comprising applying a pulsed laser beam generated by a lasing medium comprising titanium doped sapphire, and wherein the pulsed laser beam provides pulsed laser bursts having a duration of from about 50 to about 600 femtoseconds.

6. A method according to claim 5 comprising moving the pulsed laser bursts across the battery substrate with a vectorial velocity of from about 0.1 to about 40 mm/s.

7. A method according to claim 1 wherein (c) is performed before (b), and to deposit on the substrate in the order of deposition, battery component films comprising a cathode current collector film, a cathode film, an electrolyte, an anode, an anode current collector film, and a protective multilayer coating.

8. A method according to claim 1 further comprising applying an edge sealant to seal a laser cut edge formed by the pulsed laser beam, the edge sealant comprising epoxy, ceramic particle filled epoxy, metal particle filled epoxy, or thermoset UV cured polymer.

9. A method according to claim 1 wherein (c) comprises forming a plurality of spaced apart battery cells on the substrate, each battery cell comprising a set of cooperating battery component films, and wherein (b) comprises directing the pulsed laser bursts around each battery cell to form semi-circular cuts.

10. A method according to claim 1 wherein the anode or cathode current collector comprise a contact portion, and wherein (c) comprises applying an electrical conducting epoxy over the contact portion in a thickness sufficiently large to prevent the pulsed laser bursts from penetrating therethrough.

11. A method of fabricating a battery on a battery substrate, the method comprising:

(a) selecting a battery substrate having cleavage planes;

(b) cutting the battery substrate by applying a plurality of pulsed laser bursts having a fluence of from about 10 to about 800 J/cm²; and

12. A method according to claim 11 wherein the battery substrate comprises a thickness of less than about 100 microns, and comprising applying pulsed laser bursts having a pulse duration of from about 50 to about 600 femtoseconds and a pulsed laser bursts having a pulse repetition rate of from about 50 to about 1000 Hz.

13. A method according to claim 11 wherein the pulsed laser beam has a power density of from about 1 to about 440 J/cm², and wherein (b) comprises moving the pulsed laser bursts across the battery substrate with a vectorial velocity of from about 0.1 to about 40 mm/s.

14. A method of fabricating a battery on a battery substrate, the method comprising:

(a) providing a battery substrate having cleavage planes;

(b) depositing one or more battery component films on the battery substrate, the battery component films comprising electrode films at least partially surrounding an electrolyte film;

(c) applying a plurality of pulsed laser beam bursts to the battery component films of the battery preform, the pulsed laser bursts being applied at a sufficiently high power level to vaporize portions of the battery component films to form shaped features substantially without causing fractures along the cleavage planes of the battery substrate.

15. A method according to claim 14 wherein the battery substrate comprises a mica substrate having a thickness of less than about 100 microns.

16. A method according to claim 14 comprising applying pulsed laser beam bursts comprising an ultraviolet laser beam at a power level of from about 0.2 to about 1 watts, and wherein the pulsed laser beam bursts have a duration of from about 40 to about 160 nanoseconds.

17. A method according to claim 16 comprising applying the pulsed laser beam bursts at a pulse rate of from about 5 to about 200 Hz.

18. A method according to claim 14 comprising applying a pulsed laser beam burst having a fluence of from about 1 to about 800 J/cm², at a duration of from about 50 to about 600 femtoseconds.

19. A method according to claim 18 wherein the pulsed laser bursts are moved across the battery substrate with a vectorial velocity of from about 2 to about 10 mm/s.

20. A method according to claim 14 wherein the battery component films comprise (i) electrode films that include one or more of a cathode current collector film, cathode film, anode film, and anode current collector film, and (ii) an adhesion film.