Embodiments of the present disclosure relate generally to methods and equipment for manufacturing electrochemical devices, and more specifically, although not exclusively, to thermography methods and equipment for manufacturing thin film batteries.
Thin film batteries (TFB), with their unsurpassed properties, have been projected to dominate the μ-energy application space. As the technology is at the verge of transitioning from R&D to a manufacturing environment, cost effective, in-line characterization of the layers and stacks becomes more critical in achieving cost efficient, high-yielding and high-volume manufacturing of TFBs. There is a need for effective in-line characterization tools and methods for improving the yield of TFBs.
According to some embodiments and as described herein, thermographic analysis of electrochemical devices may be integrated into the process flow to detect defects for improvement of device yield. Electrochemical devices include thin film batteries (TFBs), electrochromic devices, etc.
According to some embodiments, a method of fabricating thin film electrochemical devices may comprise: depositing a stack on a substrate, the stack comprising, a cathode current collector layer, a cathode layer, an electrolyte layer, an anode layer and an anode current collector layer; laser die patterning the stack to form a multiplicity of die patterned stacks; laser patterning the multiplicity of die patterned stacks to reveal contact areas of at least one of the cathode current collector layer and the anode current collector layer for each of the multiplicity of die patterned stacks, the laser patterning the multiplicity of die patterned stacks forming a multiplicity of device stacks; depositing a blanket encapsulation layer over the multiplicity of device stacks; laser patterning the blanket encapsulation layer to reveal contact areas of the anode current collector layer and the cathode current collector layer for each of the multiplicity of device stacks, the laser patterning of the blanket encapsulation layer forming a multiplicity of encapsulated device stacks; and identifying hot spots by thermographic analysis of one or more of the multiplicity of device stacks and the multiplicity of encapsulated device stacks.
According to some embodiments, a method of fabricating thin film electrochemical devices may comprise: depositing a stack on a substrate, the stack comprising, a cathode current collector layer, a cathode layer, an electrolyte layer, an anode layer and an anode current collector layer; patterning the stack to open at least one of a common cathode current collector contact area and a common anode current collector contact area; and identifying hot spots by thermographic analysis of the stack.
According to some embodiments, an apparatus for forming thin film electrochemical devices may comprise: a first system for blanket depositing a stack of a cathode current collector layer, a cathode layer, an electrolyte layer, an anode layer and an anode current collector layer on a substrate; a second system for laser die patterning the stack to form a multiplicity of die patterned stacks; a third system for laser patterning the multiplicity of die patterned stacks to reveal contact areas of at least one of the cathode current collector layer and the anode current collector layer for each of the multiplicity of die patterned stacks, forming a multiplicity of device stacks; a fourth system for depositing a blanket encapsulation layer over the multiplicity of device stacks; a fifth system for laser patterning the blanket encapsulation layer to reveal contact areas of the cathode current collector layer and the anode current collector layer for each of the multiplicity of device stacks, forming a multiplicity of encapsulated device stacks; and a sixth system for thermographic analysis of one or more of the multiplicity of device stacks and the multiplicity of encapsulated device stacks for identifying hot spots, the sixth system comprising: probes for applying a voltage between the cathode current collector layer and the anode current collector layer, and an infrared camera.
These and other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with the accompanying figures, wherein:
Embodiments of the present disclosure will now be described in detail with reference to the drawings, which are provided as illustrative examples of the disclosure so as to enable those skilled in the art to practice the disclosure. The drawings provided herein include representations of devices and device process flows which are not drawn to scale. Notably, the figures and examples below are not meant to limit the scope of the present disclosure to a single embodiment, but other embodiments are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present disclosure can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present disclosure will be described, and detailed descriptions of other portions of such known components will be omitted so as not to obscure the disclosure. In the present disclosure, an embodiment showing a singular component should not be considered limiting; rather, the disclosure is intended to encompass other embodiments including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, it is not intended for any term in the present disclosure to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present disclosure encompasses present and future known equivalents to the known components referred to herein by way of illustration.
Thin film batteries (TFB), with their unsurpassed properties, have been projected to dominate the μ-energy application space. As the technology is at the verge of transitioning from R&D to manufacturing environment, cost effective, in-line characterization of the layers and stacks becomes more critical in achieving cost efficient, high-yielding and high-volume manufacturing of TFBs. Thermography tools and process flows using the same may in embodiments provide in-line characterization for improving the yield of TFBs and other electrochemical devices. Herein the term thin film is used to refer to films with thicknesses less than or equal to 30 microns. A thin film solid state battery herein refers to a battery in which all component films are thin films.
A description of TFB devices that may advantageously utilize embodiments of the present disclosure is provided below with reference to
According to embodiments the TFB device of
According to embodiments the TFB device of
The specific TFB device structures and methods of fabrication provided above with reference to
Furthermore, a wide range of materials may be utilized for the different TFB device layers. For example, a cathode layer may be a LiCoO2 layer (deposited by e.g. RF sputtering, pulsed DC sputtering, etc.), an anode layer may be a Li metal layer (deposited by e.g. evaporation, sputtering, etc.), and an electrolyte layer may be a LiPON layer (deposited by e.g. RF sputtering, etc.). However, it is expected that the present disclosure may be applied to a wider range of TFBs comprising different materials. Furthermore, deposition techniques for these layers may be any deposition technique that is capable of providing the desired composition, phase and crystallinity, and may include deposition techniques such as PVD, PECVD, reactive sputtering, non-reactive sputtering, RF sputtering, multi-frequency sputtering, electron and ion beam evaporation, thermal evaporation, CVD, ALD, etc.; the deposition method can also be non-vacuum based, such as plasma spray, spray pyrolysis, slot die coating, screen printing, etc. For a PVD sputter deposition process, the process may be AC, DC, pulsed DC, RF, HF (e.g., microwave), etc., or combinations thereof. Examples of materials for the different component layers of a TFB may include one or more of the following. The ACC and CCC may be one or more of Ag, Al, Au, Ca, Cu, Co, Sn, Pd, Zn and Pt which may be alloyed and/or present in multiple layers of different materials and/or include an adhesion layer of a one or more of Ti, Ni, Co, refractory metals and super alloys, etc. The cathode may be LiCoO2, V2O5, LiMnO2, Li5FeO4, NMC (NiMnCo oxide), NCA (NiCoAl oxide), LMO (LixMnO2), LFP (LixFePO4), LiMn spinel, etc. The solid electrolyte may be a lithium-conducting electrolyte material including materials such as UPON, LiI/Al2O3 mixtures, LLZO (LiLaZr oxide), LiSiCON, Ta2O5, etc. The anode may be Li, Si, silicon-lithium alloys, lithium silicon sulfide, Al, Sn, C, etc.
The anode/negative electrode layer may be pure lithium metal or may be a Li alloy, where the Li is alloyed with a metal such as tin or a semiconductor such as silicon, for example. The Li layer may be about 3 μm thick (as appropriate for the cathode and capacity balancing) and the encapsulation layer may be 3 μm or thicker. The encapsulation layer may be a multilayer of polymer/parylene and metal and/or dielectric, and may be formed by repeated deposition and patterning, as needed. Note that, between the formation of the Li layer and the encapsulation layer, in some embodiments the part is kept in an inert or very low humidity environment, such as argon gas or in a dry-room; however, after blanket encapsulation layer deposition the need for an inert environment will be relaxed. The ACC may be used to protect the Li layer allowing laser ablation outside of vacuum and the need for an inert environment may be relaxed.
Furthermore, the metal current collectors, both on the cathode and anode side, may need to function as protective barriers to the shuttling lithium ions. In addition, the anode current collector may need to function as a barrier to oxidants (e.g. H2O, O2, N2, etc.) from the ambient. Therefore, the current collector metals may be chosen to have minimal reaction or miscibility in contact with lithium in “both directions”—i.e., the Li moving into the metallic current collector to form a solid solution and vice versa. In addition, the metallic current collector may be selected for its low reactivity and diffusivity to the oxidants from the ambient. Some potential candidates for acting as protective barriers to shuttling lithium ions may be Cu, Ag, Al, Au, Ca, Co, Sn, Pd, Zn and Pt. With some materials, the thermal budget may need to be managed to ensure there is no reaction/diffusion between the metallic layers. If a single metal element is incapable of meeting both needs, then alloys may be considered. Also, if a single layer is incapable of meeting both needs, then dual (or multiple) layers may be used. Furthermore, in addition an adhesion layer may be used in combination with a layer of one of the aforementioned refractory and non-oxidizing layers—for example, a Ti adhesion layer in combination with Au. The current collectors may be deposited by (pulsed) DC sputtering of metal targets (approximately 300 nm) to form the layers (e.g., metals such as Cu, Ag, Pd, Pt and Au, metal alloys, metalloids or carbon black). Furthermore, there are other options for forming the protective barriers to the shuttling lithium ions, such as dielectric layers, etc.
In embodiments one or more of the component device layers such as anode, cathode, ACC, CCC, electrolyte and encapsulation layer may comprise multiple layers. For example, a CCC layer may comprise a layer of Ti and a layer of Pt or a layer of alumina, a layer of Ti and a layer of Pt, an encapsulation layer may comprise multiple layers as described above, etc.
Having considered the TFB structures of
One of the key detriments to the yield of electrochemical devices is the internal electrical short, especially through the electrolyte layer, which can be caused by various defects (both mechanical and in-film defects). Such defects can form at any steps along the fabrication flow. However, these defects are generally more critical when they are formed in the LiCoO2 (cathode) and LiPON (electrolyte) deposition steps—this can be manifested for example by incomplete, non-conformal coating of the LiPON layer around such defects in the LiCoO2 layer, leading to pinholes and subsequent internal electrical shorting in finished devices. Some pinholes may not be percolated at the end of the fabrication processes but can develop into fully percolated pinholes during device operation either from breakdown potential limitation or by mechanical breathing of the device structure from cycling and handling.
Outside of pinholes and misalignments of the deposited layers that can cause an internal electrical short within the device stack, it is also possible for a post deposition process, such as a scribing step, by mechanical means, or by laser, which can generate defects such as: smears, burrs or redeposition that can create shunts in the device. Thermography and lock-in thermography can locate these faults. In a high volume manufacturing environment, a simple and fast characterization of such defects is very beneficial in identifying the root causes of said defects and eliminating them, potentially enabling a high yielding manufacturing process flow. Thermography may be the metrology for such a purpose. Thermography measures the surface temperature, including the temperature changes and the extent of localization and the distribution of any “hot spots”, when external stimuli are applied to the device. (A “hot spot” may be due to an internal electrical leakage current leading to resistive heating and the spot becoming “hotter in temperature” than the location where no internal leakages exist, although a “hot spot” may not necessarily be due only to internal electrical leakage. For example, if there is a spot where the resistance is significantly higher than in surrounding material, when current passes through the material, more resistive heating is generated in the “spot” and therefore a higher T is observed at the location of the “spot”.) For TFBs, this external stimulus would be current and/or voltage applied across the device/location electrodes (generally between ACC and CCC), which induces, if electrical pinholes are present, current flow/leak, followed by local resistive heating and a corresponding measurable temperature change—these localized variations in temperature are what would be captured by thermography. The applied stimulus may be a pulsed/cyclic voltage signal, for example, which is interlocked with the thermographic measuring system. A thermographic image of the device surface is captured by heat sensors showing the position of such defects. The locational of these defects is provided for root cause analysis and for the prediction of stack/device integrity for device yield. Such information can be fed forward to predict known-good-dies and known-good-die-regions vs. known-bad-dies and known-bad-die-regions to minimize performing unnecessary processing and device characterization. This is particularly important for the “maskless integration” (not using physical shadow masks for patterning) as the depositions are typically blanket, followed by ex situ device patterning steps. The location of defects acquired using thermography may be provided to a marking/scribing tool so that known defects and surrounding portions of the device can easily be marked—by ink or laser scribing, for example—and eliminated from further processing and characterization. In some embodiments in the case of laser marking this may be done by a direct laser patterning tool, but at lower power than used for patterning since only a surface scribing sufficient for visual effect may be needed and not a full stack ablation. In some embodiments the laser patterning tool may be used for both marking and patterning of devices. Marking may in embodiments be open or closed circles around the defects. (In embodiments the marking may be in layers 106 in
With reference to
With reference to
As discussed previously, some pinholes may not be percolated at the end of the TFB fabrication process, but can develop into fully percolated pinholes during operation of the battery either from voltage breakdown or mechanical breathing of the structure from cycling and handling. To test for such incipient defects, one may apply voltages (or perhaps current, but with additional limitations on voltage and device operation) consistent with the battery operation and cycle the battery to induce early failure and potentially eliminate the need for subsequent test/cycling based cell integrity testing (currently the Li-Ion battery industry does extended shelf life testing to eliminate devices with defects that result in early failure). This process may be integrated into the fabrication methods described above. For example, a voltage signal may be applied between ACC and CCC to cycle the TFB devices/structures so as to more fully develop defects prior to thermographic analysis.
The thermography tool for defect detection in a vertical stack TFB may be operated in embodiments as follows. The signal, current and/or voltage, is applied consistent with the stability window of the battery operation. The voltage applied does not exceed the material-dependent electrical/electrochemical stability windows of the active components (cathode, anode and electrolyte) and the battery operating voltages limitation. For LiCoO2, this would be a 3.0V to 4.2V operating window. The applied polarity of the voltage is controlled as well: on the manufacturing line, the applied polarity may be set to induce “charging of the cell” as the cell is fabricated in a “discharged” state when a LiCoO2 cathode is used—use of the incorrect (opposite) polarity can potentially damage the cell. Furthermore, the current level is also limited to ensure that it is just sufficient to see the thermographic response but not high enough to affect the cell's depth of discharge. This appropriate current level for testing will depend on the location of the test in the process flow—first thermography test 807 or second thermography test 810 in the process flow of
An example of defect maps generated for a TFB is provided in
Although the examples of tools provided herein are for an in-line processing system, in embodiments thermography tools may be incorporated in cluster tools or as a stand-alone tool.
According to some embodiments, an apparatus for forming thin film electrochemical devices may comprise: a first system for blanket depositing a stack of a cathode current collector layer, a cathode layer, an electrolyte layer, an anode layer and an anode current collector layer on a substrate; a second system for laser die patterning the stack to form a multiplicity of die patterned stacks; a third system for laser patterning the multiplicity of die patterned stacks to reveal contact areas of at least one of the cathode current collector layer and the anode current collector layer for each of the multiplicity of die patterned stacks, forming a multiplicity of device stacks; a fourth system for depositing a blanket encapsulation layer over the multiplicity of device stacks; a fifth system for laser patterning the blanket encapsulation layer to reveal contact areas of the cathode current collector layer and the anode current collector layer for each of the multiplicity of device stacks, forming a multiplicity of encapsulated device stacks; and a sixth system for thermographic analysis of one or more of the multiplicity of device stacks and the multiplicity of encapsulated device stacks for identifying hot spots, the sixth system comprising: probes for applying a voltage between the cathode current collector layer and the anode current collector layer, and an infrared camera. Furthermore, a plurality of sixth systems may be used for thermographic analysis, each of the plurality of sixth systems being dedicated to thermographic analysis of the electrochemical device at different particular stages of fabrication. Furthermore, the plurality of sixth systems may be positioned in-line. Furthermore, the apparatus may further comprise a laser patterning system for marking the hot spots on the thin film electrochemical devices. Furthermore, the apparatus may further comprise a seventh system for laser patterning the stack to form a patterned stack with a common current collector contact area, and the sixth system may be configured for thermographic analysis of the patterned stack with a common current collector contact area. Furthermore, the first system may form a patterned stack by depositing the cathode layer, the electrolyte layer, the anode layer and one or more of the anode current collector layer and the anode current collector layer through shadow masks to form at least one of an open common cathode current collector contact area and an open common anode current collector contact area, and wherein the sixth system is configured for thermographic analysis of the device stack with at least one of an open common cathode current collector contact area and an open common anode current collector contact area.
Although embodiments of the present disclosure have been described herein with reference to specific examples of TFB devices, process flows and manufacturing apparatus, the teaching and principles of the present disclosure may be applied to a wider range of TFB devices, process flows and manufacturing apparatus. For example, devices, process flows and manufacturing apparatus are envisaged for TFB stacks which are inverted from those described previously herein—the inverted stacks having ACC and anode on the substrate, followed by solid state electrolyte, cathode, CCC and encapsulation layer. For example, devices, process flows and manufacturing apparatus are envisaged for TFB stacks with coplanar current collectors, such as shown in
Although embodiments of the present disclosure have been described herein with reference to TFBs, the teaching and principles of the present disclosure may also be applied to improved devices, process flows and manufacturing apparatus for fabricating other electrochemical devices, including electrochromic devices. Those of ordinary skill in the art would appreciate how to apply the teaching and principles of the present disclosure to generate devices, process flows and manufacturing apparatus which are specific to other electrochemical devices.
Although embodiments of the present disclosure have been particularly described with reference to certain embodiments thereof, it should be readily apparent to those of ordinary skill in the art that changes and modifications in the form and details may be made without departing from the spirit and scope of the disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/159,804 filed May 11, 2015, incorporated in its entirety herein.
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/031934 | 5/11/2016 | WO | 00 |
Number | Date | Country | |
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62159804 | May 2015 | US |