Patent Description:
Lithium-ion battery technologies, with their high charge capacity levels and rechargeability, have evolved storage of electrical energy and played a significant part in enabling mobile electronic devices such as portable computers and telephones. Lithium-ion batteries have also been of importance for the resurgence of electric vehicles. However, the by now conventional lithium-ion battery technology comes with its own range of issues. In order to achieve battery improvements, essentially across the entire board, battery device designs featuring solid electrolytes, as opposed to traditional liquid electrolytes, are gaining popularity. Batteries comprising a solid electrolyte are generally referred to as solid-state batteries. While solid electrolytes may be very favorable for e.g. reducing the fire risk of batteries, they also come with a need for novel battery designs in regard to morphology and materials in order to realize their full potential of improved performance compared to liquid electrolyte batteries. In particular, improving solid-state battery charge capacity, defined as a ratio of storable charges to a weight of the battery, has not yet been adequately addressed in the prior art. Additionally, material dependent volume expansion is another issue facing prior art solid-state batteries. There is thus need for improvements within the technical field.

<CIT> discloses a lithium-ion battery, comprising two electrodes and an electrolyte disposed between said two electrodes, wherein one of said electrodes comprises at least one elastic film that makes up outermost layer of said electrode such that said film abuts against the electrolyte. A plurality of gas-phase synthesized nanowires comprising silicon is partially immersed in said film and extend from said film into the electrolyte. Said plurality of nanowires is elastically deformable at least in the radial direction of the nanowires. The invention further relates to a method of manufacturing a lithium-ion battery.

<CIT> discloses a solid-state battery, and methods of fabricating embodiments of the solid-state battery. Embodiments of the present disclosure may include an electrode for a solid-state battery, the electrode including: a current collector region including a conductive, lithium electroactive material; and a plurality of nanowires contacting the current collector region.

<CIT> discloses a method for fabricating a battery that includes growing (<NUM>) wires on a substrate to form a three-dimensional skeleton structure to increase a surface area. A battery stack is deposited (<NUM>) on the skeleton structure and may be thinner to increase stability and a lifetime of the battery.

An object of the present invention is to at least mitigate some of the aforementioned issues and to provide solid-state battery layer structures that enable improved battery charge capacity as well as methods of fabricating the same structures.

According to a first aspect of the invention there is provided a solid-state battery layer structure (<NUM>) comprising:an anode current collector metal layer (<NUM>);an anode layer (<NUM>) arranged on the anode current collector metal layer;a solid electrolyte layer (<NUM>) arranged on the anode layer laterally;a cathode layer (<NUM>) arranged on the solid electrolyte layer; and a cathode current collector metal layer (<NUM>); and a plurality of nanowire structures (<NUM>) comprising silicon and/or gallium nitride, wherein said nanowire structures (<NUM>) are arranged on the anode layer (<NUM>) and, wherein said nanowire structures (<NUM>) are laterally and vertically enclosed by the solid electrolyte layer (<NUM>),wherein the anode layer comprises silicon and a plurality of metal vias (<NUM>) connecting the plurality of nanowire structures with the anode current collector metal layer (<NUM>).

The term "arranged on" may refer to having the layers or structures arranged above each other in a vertical direction of the layer structure or stack. The vertical direction may be substantially perpendicular and normal to the surfaces of the layers or structures in the layer structures. The word "comprises" may throughout this disclosure refer to layers and structures at least partially comprising a certain material. The word does not exclude the layer or structure from containing impurities of other materials nor does it exclude the layer or structure substantially consisting of the comprised material.

Such a structure may mitigate some of the issues in the prior art. Silicon anodes may be advantageous for increasing the charge capacity for e.g. lithium-ion based batteries. This is due to silicon atoms, often alloyed to form compound anode materials, are better than carbon atoms, in conventional graphite anodes, at binding to and thus holding a larger number of lithium atoms. Battery charge capacity may be recorded in the units ampere hours or coulombs. Additionally, the use of silicon anodes, may simplify production of the battery layer structure and improve yield as sophisticated techniques and methods commonly used in microelectronic fabrication may be utilized. As such, solid-state batteries may be effectively minaturized. Silicon anodes may be based on monocrystalline substrates. As such, solid-state battery layer structures may be formed more integrally with silicon-based microelectronics. Thus, electronic circuits and devices with integrated solid-state batteries may be both enabled and miniaturized.

The anode layer may comprise gallium nitride.

The use of gallium nitride in the anode layer, e.g. as a thin upper layer of the anode layer otherwise mainly comprising silicon, may mitigate issues in the prior art. The charge capacity of a solid-state battery with a gallium nitride anode material may be ~<NUM> times larger than that of a solid-state battery with conventional graphite anodes. The diffusion barrier for lithium-ion diffusion may also be lower with a gallium nitride anode compared to the same barrier for a graphite anode. This may be advantageous for rapid battery charging.

The term "nanowire structure", also referred to as just nanostructures, may refer to elongated structures with a dimension such as a diameter or a length on the nanometer scale, i.e. <NUM>-<NUM>. Nanowire structures may be simple and substantially one-dimensional or contain, along its length, at least one node from which at least two separate branches extend. Such a nanowire structure may be referred to as a nanotree or a nanowire tree structure.

The term "laterally and vertically enclosed" may refer to enclosing the nanowire structures both laterally or radially and vertically or longitudinally. The whole nanowire structures, including all eventual branches, faces, and surfaces, may be covered by solid electrolyte material forming the solid electrolyte layer.

Such an addition of nanowire structures may advantageously increase the effective interface area between the anode and the solid electrolyte and hence also the battery charge capacity and potentially also increase the rate at which charge carrying ions, e.g. lithium ions, may alloy with the anode material. Additionally, the use of nanowire structures may mitigate the volume expansion of some materials during battery operation. bulk silicon anodes may expand <NUM>-<NUM>% during lithiation, i.e. the process of charging a battery when the charge carriers are lithium ions. Nanostructures, such as e.g. nanowires are advantageous as their volume expansion may be much less severe than that of bulk materials. This advantage of nanostructures may be attributed to their volume expansion being more local and distributed as compared to when a bulk layer expands as one piece. This mitigation of the volume expansion issue may be even more relevant for solid electrolyte batteries as solids generally allow for less mechanical movement than liquids. Furthermore, nanostructures such as these may be produced in a structured and well-defined manner and the effective interface area may still be increased even if irregularities would somehow occur.

Each nanowire structure of said plurality of nanowire structures may comprise a vertical stem and a plurality of branches extending from said vertical stem, wherein the vertical stems of said plurality of nanowire structures are arranged perpendicularly to a top surface of the anode layer.

The term "arranged perpendicularly" may refer to arranging the whole nanowire structures, and in particular vertical stems, such that they extend in a substantially perpendicular and normal direction to the top surface of the anode layer. This direction may alternatively be understood as corresponding to the vertical direction of the layer structure. Including tree shaped nanowire structures, comprising both stems and branches, may further increase the effective interface area between the anode and the solid electrolyte and the battery charge capacity. Additionally, the tree shaped nanowire structures may further mitigate the volume expansion issue described in the above.

The plurality of tree shaped nanowire structures, or nanotrees, may be visually compared or likened to a nanoforest.

Said plurality of nanowire structures comprise silicon and/or gallium nitride.

Such silicon nanowire structures may be advantageous for being relatively easy to form due to the numerous silicon formation and processing methods that are available. As the silicon nanowire structures would effectively extend the anode, the same advantages as those of using silicon as an anode material apply, i.e. the charge capacity may be increased.

Similarly to the above, gallium nitride nanowire structures extending the anode may also improve the charge capacity of the solid-state battery.

The anode layer comprises a plurality of metal vias connecting the plurality of nanowire structures with the anode current collector metal layer.

As such, a lower resistance or more ohmic conduction path may be provided to the base of the nanowire structures.

The solid electrolyte layer may comprise lithium phosphate.

Lithium phosphate, or compounds comprising lithium phosphate, may be considered advantageous materials for the solid electrolyte layer in a solid-state battery layer structure. Lithium phosphate may allow transport of lithium ions between the anode and cathode of the solid-state battery by solid state diffusion via atomic vacancies in the solid electrolyte material lattice.

The cathode layer may comprise lithium cobalt oxide or another metal oxide.

Lithium cobalt oxide may be be considered an advantageous material for the cathode layer.

The cathode current collector metal layer may comprise aluminium.

Aluminium may provide a low resistance or adequately ohmic conduction path to the cathode layer.

The anode current collector metal layer may comprise copper.

Copper may provide a low resistance or adequately ohmic conduction path to the anode layer and if present also to the nanowire structures.

According to a second aspect of the present invention there is provided a a method for producing a solid-state battery layer structure (<NUM>), the method comprising:providing (S1002) an anode layer (<NUM>) comprising silicon;forming (S1004) a plurality of nanowire structures (<NUM>) comprising silicon and/or gallium nitride on the anode layer, wherein the nanowire structures (<NUM>) are formed perpendicularly to a top surface (<NUM>) of the anode layer;depositing (S1006) a solid electrolyte layer (<NUM>) on the anode layer, the solid electrolyte layer laterally and vertically enclosing said plurality of nanowire structures;depositing (S1008) a cathode layer (<NUM>) on the solid electrolyte layer;depositing (S1010) a cathode current collector metal layer (<NUM>) on the cathode layer;etching (S3002), from a bottom surface (<NUM>) of the anode layer, holes (<NUM>) through the anode layer (<NUM>); and depositing (S1012) an anode current collector metal layer (<NUM>) on a bottom surface (<NUM>) of the anode layer and filling the holes with a same material as a material of the anode current collector metal layer.

The word "forming" may refer to any method or technique for forming a layer or structure. The word "depositing" may refer to any method or the use of a technique for forming a layer or structure by addition of material. Examples of deposition techniques may include chemical vapor deposition (CVD), physical vapor deposition (PVD), metalorganic vapor-phase epitaxty (MOVPE), sputtering, evaporation, etc. Thus, a step of forming may refer to depositing. The anode current collector metal layer should be understood as beeing deposited on the bottom surface of the anode layer, i.e. not on or above the anode layer when considering the vertical direction of the layer structure or stack.

Such a method may be used to produce solid-state battery layer structures according to the first aspect. Therefore, advantages may closely correspond to those described for the first aspect. In summary, the method may provide a relatively low complexity way to produce a solid-state battery layer structure by using existing, microelectronic, fabrication methods and techniques. Close integration with electronic devices and miniaturization may be enabled by the method.

This addition of etching and filling may be understood as corresponding to forming the vias to the bases of the nanowire structures as described in the first aspect. Thus, similar advantages and beneficial effect apply. Such backside wafer vias may be provided by plasma etching of silicon oxide or silicon nitride as a hard mask for deep reactive-ion etching (DRIE) of silicon.

The method may further comprise aligning the holes through the anode layer with said plurality of nanowire structures.

As such, a more ideal conduction path between anode contacts and nanowire strucutres may be obtained.

The step of forming said plurality of nanowire structures may comprise:.

Forming nanowire structures by particle formation, e.g. deposition, and subsequent particle mediated epitaxy may be an effective way to form tree shaped nanowire structures comprising first order nanowire structures, i.e. vertical stems, and second order nanowire structures, i.e. branches wherein the first order nanowire structures act as bases for second order nanowire structures.

The branches may be understood as being grown substantially radially out from the vertical stems. The branch seed particles may be understood as being deposited on radial or lateral surface faces, and along the entire length, of the vertical stems.

It must be noted that, as used in the specification and the appended claims, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements unless the context clearly dictates otherwise.

The above and other aspects of the present invention will, in the following, be described in more detail with reference to appended figures. The figures should not be considered limiting; instead they should be considered for explaining and understanding purposes.

As illustrated in the figures, the sizes of layers and regions may be exaggerated for illustrative purposes and, thus, are provided to illustrate the general structures.

<FIG> shows a cross sectional view of a solid-state battery layer structure <NUM>. The solid-state battery layer structure comprises:.

wherein the anode layer comprises silicon.

The anode current collector metal layer <NUM> may comprise or substantially consist of copper. The anode current collector metal layer <NUM> may alternatively or additionally comprise one of the other metal materials: gold, silver, platina, nickel, titanium, zinc, chromium, tin, lead, manganese, cobalt, and iron. The anode current collector metal layer <NUM> may comprise an alloy material.

The anode layer <NUM> may comprise <<NUM>> silicon. The anode layer <NUM> may be a crystaline silicon substrate or wafer. The anode layer <NUM> may comprise or substantially consist of gallium nitride. The anode layer <NUM> may comprise a thin upper sublayer of gallium nitride arranged on a lower sublayer of silicon. The anode layer comprising <NUM> GaN may be passivated with hydrogen. Lithium may be incorporated or alloyed into the anode layer <NUM>.

The solid electrolyte layer <NUM> may comprise or substantially consist of lithium phosphate (Li<NUM>PO<NUM>). The solid electrlyte layer <NUM> may additionally or alternatively comprise or substantially consist of other materials such as lithium iron phosphate (Li<NUM>FePO<NUM>) or lithium phosphorus oxynitride (LiPON).

Other lithium compounds may also be availble for the solid electrolyte layer <NUM>.

The solid electrolyte layer <NUM> may feature atomic vacancies at lithium atom lattice locations to allow for conduction by diffusion of lithium ions through the solid electrolyte layer <NUM>. The solid electrolyte layer <NUM> may comprise magnesium replacment or impurity atoms to restore the equlibrium of charges in the lattice that may be lost by introducing the lattice lithium vacancies.

The solid electrolyte layer <NUM> may have a thickness in the range <NUM>-<NUM>.

The cathode layer <NUM> may comprise or substantially consist of lithium cobalt oxide (LiCoO<NUM>). The cathode layer <NUM> may alternatively or additionally comprise other metal oxide based materials.

The cathode current collector metal layer <NUM> may comprise or substantially consist of aluminium. The cathode current collector metal layer <NUM> may alternatively or additionally comprise one of the other metal materials: gold, silver, platina, nickel, titanium, zinc, chromium, tin, lead, manganese, cobalt, and iron. The cathode current collector metal layer <NUM> may comprise an alloy material.

<FIG> shows the solid-state battery <NUM> layer structure further comprising a plurality of nanowire structures <NUM>. Said nanowire structures <NUM> may be arranged on the anode layer <NUM>. Said nanowire structures <NUM> may be laterally and vertically enclosed by the solid electrolyte layer <NUM>.

Each nanowire structure <NUM> of said plurality of nanowire structures may comprise a vertical stem <NUM> and a plurality of branches <NUM> extending from said vertical stem <NUM>. The vertical stems of said plurality of nanowire structures may be arranged perpendicularly to a top surface <NUM> of the anode layer <NUM>.

The nanowire structures <NUM> may be arranged in a hexagonal pattern on the top surface <NUM> of the anode layer <NUM>. The vertical stems <NUM> of the nanowire structures <NUM> may be arranged with a spacing to the nearest other vertical stem <NUM> in the range <NUM>-<NUM>. More preferably, the spacing is in the range <NUM>-<NUM>. Most preferably, the spacing is in the range <NUM>-<NUM>.

The nanowire structures <NUM> may alternatively be arranged on the anode layer <NUM> with arbitrary orientations of each individual nanowire structure <NUM>. Such formation may be less complex while still increasing the effective anode-electrolyte interface area.

The vertical stems <NUM> may have a length in the range <NUM>-<NUM>. More preferably, the the length is in the range <NUM>-<NUM>. Most preferably, the length is in the range <NUM>-<NUM>.

The branches <NUM> may have a length in the range <NUM>-<NUM>. More preferably, the lenth is in the range <NUM>-250n. Most preferably, the length is in the range <NUM>-<NUM>.

Said plurality of nanowire structures may comprise or substantially consist of silicon. Said nanowire structures <NUM> may comprise crystaline silicon with a crystal lattice direction <<NUM>> corresponding to the vertical direction of the nanowire structures.

Said plurality of nanowire structures may comprise or substantially consist of gallium nitride. Said nanowire structures <NUM> may comprise crystaline gallium nitide with a crystal lattice direction <<NUM>> corresponding to the vertical direction of the nanowire structures. Gallium nitride nanowire structures <NUM> may feature a hydrogen passivation layer on the surfaces and faces of the nanowire structures <NUM> to saturate unsaturaed dangling bonds at the gallium nitride surface.

The nanowire structures <NUM> may incorporate or alloy Li into their surface or bulk lattice.

<FIG> shows the anode layer <NUM> comprising a plurality of metal vias <NUM> connecting the plurality of nanowire structures <NUM> with the anode current collector metal layer <NUM>. The metal vias <NUM> may comprise or substantially consist of a same material existing in the anode current collector metal layer <NUM>.

<FIG> shows a flowchart of a method for producing a solid-state battery layer structure <NUM>. The method is shown to comprise steps of:.

The plurality of nanowires structures <NUM> may be formed by a MOVPE, or a CVD process. The process may be seed particle mediated. The pattern in which the nanowire structures <NUM> are arranged may be formed using lithography techniques such as ultra-violet lithography (UVL), electron beam lithography (EBL), and nanoimprint lithography (NIL). Pattern transfer may be achieved through etching methods.

Nanosphere lithography (NSL) may be used together with chlorine-based plasma etching to etch out entire vertical stems <NUM>. As such, the need for MOVPE may be circumvented, at least for the formation of the vertical stems <NUM>. The nanowire structures <NUM> may be passivated in-situ before, during, or after MOVPE processing. The nanowire structure <NUM> may be passivated with hydrogen.

The method may further comprise incorporating or alloying lithium into the surface or bulk lattice of the nanowire structures <NUM>. This may be achieved through electrochemical processing. Lithium may be deposited onto the nanowire structures <NUM> before solid electrolyte layer <NUM> deposition S1006. Lithium may be deposited by thermal evaporation.

The solid electrolyte layer <NUM> may be deposited S1006 by a CVD process. The solid electrolyte layer <NUM> may be deposited by PVD or sputtering process. The sputtering process may be a pulsed DC (direct current) or RF (radio frequency) based sputtering process. The solid electrolyte layer <NUM> may encapsulate any lithium deposited onto the nanowire structures <NUM>.

The cathode layer <NUM> may be deposited S1008 by a CVD process. The cathode current collector metal layer <NUM> may be deposited S1010 by a PVD process. The anode current collector metal layer <NUM> may be deposited S1012 by a PVD process.

<FIG> also shows how the method may further comprise etching S3002, from the bottom surface <NUM> of the anode layer <NUM>, holes <NUM> through the anode layer <NUM>. In this eventuallity, the step of depositing S1012 the anode current collector metal layer <NUM> on the bottom surface <NUM> of the anode layer <NUM> further comprises filling the holes <NUM> with a same material as a material of the anode current collector metal layer <NUM>. The filled in holes <NUM> may correspond to the vias <NUM> in <FIG>.

Also shown in <FIG>, the method may further comprise aligning S4002 the holes <NUM> through the anode layer <NUM> with said plurality of nanowire structures <NUM> i.e. so that each hole <NUM> corresponds to the position of a nanowire structure <NUM>.

The holes <NUM> may be etched S3002 by a reactive ion etching (RIE) process. The RIE process may be a dry RIE process.

<FIG> show cross sectional views of layers and structures of the solid-state battery layer structure <NUM> during various stages of its production.

<FIG> shows the anode layer <NUM> having been provided S1002, the anode layer <NUM> being the base for subsequent processing steps.

<FIG> shows the plurality of nanowire structures <NUM>, each comprising vertical stems <NUM> and branches <NUM>, having been formed S1004 wherein the vertical stems <NUM> of the nanowire structures <NUM> are formed perpendicularly to the top surface <NUM> of the anode layer <NUM>.

<FIG> shows the solid electrolyte layer <NUM> having been deposited S1006 on the anode layer <NUM> such that it laterally and vertically encloses the plurality of nanowire structures <NUM>.

<FIG> shows the cathode layer <NUM> having been deposited S1008 on the solid electrolyte layer <NUM>.

<FIG> shows the cathode current collector metal layer <NUM> having been deposited S1010 on the cathode layer <NUM>. The battery layer structure may be flipped after step S1010 in order to accommodate subsequent processing steps.

<FIG> shows the anode current collector metal layer <NUM> having been deposited S1012 on the bottom surface <NUM> of the anode layer <NUM>, thus completing the solid-state battery layer structure <NUM>.

<FIG> show an alternative route to complete the layer structure <NUM> compared to the route shown in <FIG>.

<FIG> shows the holes <NUM> having been etched S3002 from the bottom through the anode layer <NUM>, from its bottom surface <NUM>. The holes <NUM> are also shown to have been aligned S4002 with the nanowire structures <NUM>.

<FIG> shows the anode current collector metal layer <NUM> having been deposited S1012 on the bottom surface <NUM> of the anode layer <NUM> and into the holes <NUM> through the anode layer <NUM>, thus completing the solid-state battery layer structure <NUM>.

<FIG> shows a flowchart of the step of forming S1004 said plurality of nanowire structures <NUM>. The step S1004 may comprise:.

The stem seed and branch seed particles <NUM>, <NUM> may be e.g. gold seed particles. The stem seed and branch seed particles <NUM>, <NUM> may comprise other materials than gold such as e.g. silver, palladium, cobalt, bismuth, and platina. The stem seed and branch seed particles <NUM>, <NUM> may be deposited using aerosol deposition. Deposition or formation of the plurality of seed particles <NUM>, <NUM> may be formed with or without preferred co-alignment onto their respective surfaces or structures. The stem seed particle <NUM> may be formed using lithography-based patterning techniques. Such a technique may include forming a gold layer onto the anode layer <NUM> through electroplating, evaporation, or sputtering followed by lithography-based patterning, e.g. with resist coating, exposure, and etching steps to achieve a well-defined pattern of remaining stem seed particles <NUM> on the top surface <NUM> of the anode layer <NUM>.

The nanowire structures <NUM> may be grown using seed particle mediated epitaxy. Essentially, this may mean that crystalline nanowire structures <NUM> are epitaxially grown from the seed particles <NUM>, <NUM>. The seed particles <NUM>, <NUM> may first absorb precursor gases.

<FIG> show a cross sectional, or side views, of nanowire structures <NUM> during different stages of their formation.

<FIG> shows a plurality of stem seed particles <NUM> having been formed S2002 on the top surface <NUM> of the anode layer <NUM>.

<FIG> shows the vertical stems <NUM> having been epitaxially grown S2004.

<FIG> shows branch seed particles <NUM> having been deposited S2006 on the vertical stems <NUM>.

<FIG> shows the branches <NUM> having been epitaxially grown S2008.

Claim 1:
A solid-state battery layer structure (<NUM>) comprising:
an anode current collector metal layer (<NUM>);
an anode layer (<NUM>) arranged on the anode current collector metal layer;
a solid electrolyte layer (<NUM>) arranged on the anode layer laterally;
a cathode layer (<NUM>) arranged on the solid electrolyte layer; and
a cathode current collector metal layer (<NUM>); and
a plurality of nanowire structures (<NUM>) comprising silicon and/or gallium nitride, wherein said nanowire structures (<NUM>) are arranged on the anode layer (<NUM>) and, wherein said nanowire structures (<NUM>) are laterally and vertically enclosed by the solid electrolyte layer (<NUM>),
wherein the anode layer comprises silicon and a plurality of metal vias (<NUM>) connecting the plurality of nanowire structures with the anode current collector metal layer (<NUM>).