Embodiments of the present disclosure relate generally to methods for manufacturing microelectronic and electrochemical devices, and more specifically, although not exclusively, to methods and apparatuses for improved laser ablation of transparent materials without damaging underlying metal layers in the manufacturing of thin film batteries.
Lasers can be used to remove thin and thick film materials from substrates or other films Typically the type of laser to be used is dependent on the absorption characteristic of the film or material to be removed. High absorption with minimal reflectance or transmission is generally desired so that the laser energy reacts directly with the material to be removed. Many polymer films are transparent to the commonly used laser wavelengths within the range of 355 nm to 1070 nm; consequently, the conventional thinking is that these polymer films need lasers with shorter wavelengths, less than 355 nm, for ablation processing. Such shorter wavelengths can be generated using complex crystal materials for fourth harmonic generation from 1064 nm fundamental lasers or using expensive gas based cavities such as excimer lasers, which excimer lasers need complex masks to create the desired ablation patterns. Using a Q-switched focused laser beam typically results in MW peak energy levels that will at a minimum cause thermal effects on surrounding materials if not complete ablation of unintended layers below the targeted polymer material. There thus remains a need for methods and apparatuses that can remove transparent materials without significant damage to the underlying materials and without using expensive equipment and complex processes.
According to certain aspects, embodiments of the present disclosure relate to methods and apparatuses for laser ablation of transparent materials using laser wavelengths that have a low absorption characteristic with respect to such materials. Embodiments of the present disclosure use standard industrial lasers with common optics and scanners for flexible pattern generation to remove transparent materials without significant damage to the underlying materials. In these and other embodiments, methods according to the present disclosure include defocusing or shaping the laser beam, effectively reducing the energy density of the laser beam below the ablation threshold of the underlying metal layers and using multiple passes over the targeted material.
According to some embodiments, a method of selectively ablating an optically transparent material covering a metal layer of a device may comprise: providing a layer of optically transparent material on a metal layer; and irradiating a portion of the layer of optically transparent material with a defocused laser beam and ablating the portion of the layer of optically transparent material; wherein the ablating leaves the metal layer completely intact and wherein the laser light has a wavelength within a range of 355 nm to 1070 nm.
According to some embodiments, a method of selectively ablating an optically transparent material covering a metal layer of a device may comprise: providing a layer of optically transparent material on a metal layer; and irradiating a portion of the layer of optically transparent material with a shaped laser beam and ablating the portion of the layer of optically transparent material; wherein the ablating leaves the metal layer completely intact and wherein the laser light has a wavelength within a range of 355 nm to 1070 nm.
According to some embodiments, an apparatus for forming thin film electrochemical devices comprising: 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; and a fifth system for laser ablating 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; wherein the encapsulation layer is optically transparent, wherein the fifth system for laser ablation comprises a laser providing laser light with a wavelength within a range of 355 nm to 1070 nm, and wherein the fifth system for laser ablation is configured to provide a laser beam selected from the group consisting of a defocused laser beam and a shaped laser beam.
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.
According to certain general aspects, the author of the present disclosure has discovered that it is possible to use standard industrial lasers with common optics and scanners for flexible pattern generation to remove transparent materials without significant damage to the underlying materials. The author has further recognized that certain materials such as metals which are normally reflective to many laser wavelengths may be directly ablated by direct ionization of the normally reflective metal if sufficient energy is directed to the material surface—such as in the case of a high energy pulsed laser focused on the material. Alternatively, it is possible to super heat the metal inducing a molten state that has different absorption characteristics than the solid state of the material resulting in “explosive boiling”.
According to certain other aspects of the present disclosure, the author has discovered that by defocusing the laser beam (effectively reducing the energy density) and using multiple passes over the targeted material, it is possible to avoid damage to the reflective metal layers below the transparent material thus reflecting and redirecting the beam back again into the transparent material. In the case of transparent polymers these materials will melt much faster than the metal below. After sufficient heating of the transparent material the author discovered that the absorption characteristic of the material changes, causing it to directly absorb the laser light and then rapidly be ablated from the substrate. This can be considered as a pre-conditioning of the normally transparent polymer layer into a highly absorbing state that then results in actual ablation without damage to the metal layers below. One advantage of this solution is it allows for use of inexpensive and manufacturing proven lasers producing light in the visible wavelength range instead of expensive excimer lasers needing shadow masks or of unproven solid state lasers using 266 nm or below that also need expensive optics and maintenance.
These and other aspects of the present disclosure will be described in more detail below in connection with an example embodiment of ablating transparent encapsulation material in a single sided thin film battery to expose contact areas to the battery anode current collector and cathode current collector layers. However, the disclosure is not limited to this example, and one skilled in the art will understand how to extend the principles thereof to double sided TFBs and, as well as to other technologies using polymer coatings over metal, such as FET manufacturing.
Herein, in some embodiments optical transparency of a layer of optically transparent material is defined as the layer absorbing less than or equal to 50% of the laser light from a laser beam on a single pass of the laser light through the layer of optically transparent material, and in embodiments optical transparency of a layer of optically transparent material is defined as the layer absorbing less than or equal to 20% of the laser light from the laser beam on a single pass of the laser light through the layer of optically transparent material. Since the optical transparency of materials varies as a function of wavelength, this definition of optical transparency is specific to the particular wavelength of the laser light. The laser light is at a wavelength within the range of 355 nm to 1070 nm.
Most solid state thin film batteries (i.e. TFBs) have encapsulation with a polymer coating to protect the electrolyte components from environmental contamination that will cause premature failure of the devices. However, the deposition of these protective layers completely covers the contact areas that still need to be opened in order to physically connect the battery to end user components.
According to embodiments the TFB device of
The specific TFB device structure 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 LiPON, 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.
As further shown in
It should be noted that the present disclosure is not limited to a single transparent material removal step. For example, a plurality of stack-up cycles of depositing an encapsulation layer, using the same or different materials in each cycle, and opening contact areas in the deposited encapsulation layer can be performed after one or more of the cycles. For example, a first cycle can deposit parylene followed by a second cycle of depositing alumina. As another example, a first cycle can deposit alumina followed by a second cycle of depositing parylene. As a further example, a first cycle can deposit parylene followed by a second cycle of depositing silicon nitride followed by a third cycle of depositing alumina.
Returning to
According to aspects of the present disclosure, rather than focusing the laser beam near the surface of the transparent material, the beam is defocused. For example, with a beam spot size of about 100 μm, the beam is defocused by about 400%. More particularly, with a 2 mm focus window, the laser is placed 8mm out of focus. Other relevant settings, specifically for a 355 nm laser, include pulse energy of about 30 μJ and 12 ps pulse duration. To ablate the transparent material in the pad areas using these settings, the laser is operated over the pad areas in a cross-hatch pattern, with 20 micron steps. In one example, six completions of the pattern elapsing a total time of about 100 ms are needed to fully ablate a 10-20 micron thick layer of parylene material in each pad area using the 355 nm laser with operating parameters as given above.
As shown in
As shown in
As further shown in
Although the examples of tools provided herein are for an in-line processing system, in embodiments laser ablation 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 comprising: 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; and a fifth system for laser ablating 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; wherein the encapsulation layer is optically transparent, wherein the fifth system for laser ablation comprises a laser providing laser light with a wavelength within a range of 355 nm to 1070 nm, and wherein the fifth system for laser ablation is configured to provide a laser beam selected from the group consisting of a defocused laser beam and a shaped laser beam. Furthermore, the laser beam can be formed by a 355 nm laser and the laser beam can provide a dose rate in the range of 4×108 Jm−2s−1 to 6×108 Jm−2s−1 at the blanket encapsulation layer. Furthermore, the apparatus may be an in-line processing apparatus. As above, in some embodiments the layer of optically transparent material can absorb less than or equal to 50% of the laser light from the defocused or shaped laser beam on a single pass of the laser light through the layer of optically transparent material, and in embodiments absorb less the or equal to 20% of the laser light. Furthermore; in some embodiments the fifth system for laser ablation is configured to scan the laser beam across the layer of optically transparent material during ablation of the layer of optically transparent material.
Furthermore, in some embodiments an apparatus for selectively ablating an optically transparent material covering a metal layer of a device may comprise a system for laser ablating a portion of a layer of optically transparent material, wherein the laser ablation tool comprises a laser providing laser light with a wavelength within a range of 355 nm to 1070 nm, and wherein the system for laser ablation is configured to provide a laser beam selected from the group consisting of a defocused laser beam and a shaped laser beam. Furthermore, the laser beam can be formed by a 355 nm laser and the laser beam can provide a dose rate in the range of 4×108 Jm−2s−1 to 6×108 Jm−2s−1 at the blanket encapsulation layer. Furthermore, the apparatus may be an in-line processing apparatus. As above, in some embodiments the layer of optically transparent material can absorb less than or equal to 50% of the laser light from the defocused or shaped laser beam on a single pass of the laser light through the layer of optically transparent material, and in embodiments absorb less the or equal to 20% of the laser light. Furthermore, in some embodiments the system for laser ablation is configured to scan the laser beam across the layer of optically transparent material during ablation of the layer of optically transparent material.
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. Furthermore, those of ordinary skill in the art would appreciate how to apply the teaching and principles of the present disclosure to generate a wide range of devices, process flows and manufacturing apparatus.
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 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 devices, including: microelectronic devices such as field effect transistors (FETs), and thermoelectric 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 devices.
Although embodiments of the present disclosure have been described herein with reference to parylene, specifically parylene-C, as an example of an optically transparent material, both parylene-N and silicone have also been demonstrated to behave as optically transparent materials as described in the present disclosure: Furthermore, it is expected that hexamethyldisiloxane (HMDSO), 1,4-butanediol diacrylate (BDDA), and other similar materials are expected to behave as optically transparent materials as described in the present disclosure.
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. 62/161,449 filed May 14, 2015, incorporated in its entirety herein.
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/032792 | 5/16/2016 | WO | 00 |
Number | Date | Country | |
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62161449 | May 2015 | US |