Embodiments of the present disclosure relate generally to methods for manufacturing microelectronic and electrochemical devices, and more specifically, although not exclusively, to modification of encapsulation and dielectric materials for improved laser ablation selectivity to underlying metal layers in the manufacturing of thin film batteries.
In microelectronics and electrochemical device fabrication, dielectric layer(s) are frequently used in between metallization layers and also as part of encapsulation layers. Using laser ablation to drill vias or holes in dielectric layer(s), and stop precisely on metallization layer(s), can be very challenging, and undesirable damage to, or even removal of, the metallization layers and metal splatter and redeposition may be an undesirable side effect of the ablation process—reducing the manufacturing yield of devices. There is a need for improved dielectric materials and laser ablation processes to improve the yield.
In some embodiments, laser light absorption within the visible and near UV part of the spectrum may be enhanced for encapsulation and dielectric materials, such as parylene and alumina, which ordinarily are transparent within this part of the spectrum, to improve selectivity of removal by laser ablation of a portion of a layer of the encapsulation/dielectric material over a metallization layer, by using one or more of: (1) UV exposure of the encapsulation/dielectric layer prior to laser ablation; (2) inclusion of dyes and similar light absorbing materials into the encapsulation/dielectric material; (3) formation of an encapsulation/dielectric layer with a compositional gradient. Encapsulation/dielectric layers modified as above may be incorporated into electrochemical devices such as solid state thin film batteries (TFBs). Methods for fabricating electrochemical devices may utilize material modification for encapsulation/dielectric layers as described herein.
According to some embodiments, a method of fabricating electrochemical devices may comprise: providing a layer of dielectric material on a metal electrode; enhancing light absorption in the layer of dielectric material within the visible and near UV range, forming a layer of enhanced dielectric material; and laser ablating substantially all of the enhanced dielectric material in select areas of the layer using a laser with a wavelength in the visible and near UV range, wherein the laser ablating leaves the metal electrode substantially intact.
According to some embodiments, a method of fabricating electrochemical devices may comprise: providing a layer of dielectric material on a metal electrode, the layer being engineered for higher laser light absorption within the visible and near ultraviolet range; and laser ablating substantially all of the dielectric material in select areas of the layer using a laser with a wavelength in the visible and near UV range, wherein the laser ablating leaves the metal electrode substantially intact.
According to some embodiments, an electrochemical device may comprise: a substrate; a stack of device layers formed on the substrate, the stack comprising a cathode current collector layer, a cathode layer, an electrolyte layer, an anode layer and an anode current collector layer; and an encapsulation layer covering the stack, the encapsulation layer being engineered to strongly absorb laser light within the visible and near ultraviolet range.
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.
In microelectronics and electrochemical device fabrication, dielectric layer(s) are frequently used in between metallization layers and also as part of encapsulation layers.
Using laser ablation to drill vias or holes in dielectric layer(s), and stop precisely on metallization layer(s), can be very challenging, and undesirable damage to, or even removal of, the metallization layers and metal splatter and redeposition may be an undesirable side effect of the ablation process—reducing the manufacturing yield of devices.
In order to improve the laser light absorption of the encapsulation/dielectric layer the encapsulation/dielectric material can be modified, as described in more detail below, thus allowing more efficient laser ablation of vias by a process that stops at the interface between encapsulation/dielectric layer and the metal and leaves the underlying metallization layer(s) substantially intact and undamaged. For example,
In embodiments, laser ablation of transparent (in the visible and near UV wavelengths) encapsulation layer(s) such as parylene and Al2O3 over active metallization layer(s), while preserving the active metallization layer's integrity, is enhanced by increasing the laser light absorption within the encapsulation layer. (This is when using visible and near UV lasers, which are cheaper and easier to use than deep UV lasers, which can be technologically challenging and expensive. Some examples of lasers that may be used in embodiments described herein are 532 nm green laser, 355 nm laser, DPSS (diode-pumped solid state) pulsed picosecond and femtosecond lasers at 1064 nm, 532 nm and 355 nm.) Increasing the laser light absorption within the encapsulation layer may be in the wavelength range of 250 nm to 750 nm, in embodiments in the wavelength range of 200 nm to 1000 nm, and in embodiments in the wavelength range of 200 nm to 1064 nm.
Referring again to
A description of TFB devices that may take advantage of 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 UPON 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/or metal and/or dielectric, such as alumina. Other polymers that are expected to be usable as encapsulation layers in some embodiments of the present disclosure include: thereto-polymerizable materials, such as polystyrene resins, acrylic resins, urea resins, isocyante resins, and xylene resins; different forms of parylene; epoxy materials; and organic lamination layers. Other inorganic dielectrics that are expected to be usable as encapsulation layers in some embodiments of the present disclosure include: silicon oxide (SiOx), silicon nitride (SiNx), magnesium oxide (MgO), zirconium oxide (ZrO2), zinc oxide (ZnO), and inorganic lamination layers. Note that, between the formation of the Li layer and the encapsulation layer, the part should be 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 the protective barrier 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 functioning as both a protective barrier to shuttling lithium ions and to oxidants, then alloys may be considered, also, 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.
Although embodiments of the present disclosure have been described herein with reference to specific examples of TFB devices and process flows, the teaching and principles of the present disclosure may be applied to a wider range of TFB devices and process flows. For example, devices and process flows 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. 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 and process flows,
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 and process flows for other electrochemical devices, including electrochromic devices, although electrochromic devices will have the added constraint that the devices be transparent in the visual spectrum. In the latter case, a near UV laser may be used for ablation of encapsulation/dielectric layer and it is expected that the near UV light absorption may be enhanced using the methods described above without increasing light absorption within the visible spectrum. Those of ordinary skill in the art would appreciate how to apply the teaching and principles of the present disclosure to generate devices and process flows 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. 62/159,865 filed May 11, 2015, incorporated in its entirety herein,
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/031935 | 5/11/2016 | WO | 00 |
Number | Date | Country | |
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62159865 | May 2015 | US |