Device and method of manufacturing high aspect ratio structures

Abstract

A method for manufacturing a electronic device is provided having a current collector capable of a high specific charge collecting area and power, but is also achieved using a simple and fast technique and resulting in a robust design that may be flexed and can be manufactured in large scale processing. To this end the electronic device comprising an electronic circuit equipped with a current collector formed by a metal substrate having a face forming a high-aspect ratio structure of pillars having an interdistance larger than 600 nm. By forming the high-aspect structure in a metal substrate, new structures can be formed that are conformal to curvature of a macroform or that can be coiled or wound and have a robust design.

Claims

1. A method of manufacturing a 3D thin film current collector with a high-aspect ratio structure of pillars formed on a metal substrate, wherein the method comprises: forming elongate and aligned carbon nanotube pillars on a face of a seed layer covering the metal substrate with a micro-pattern mask, the micro-pattern mask arranging the carbon nanotube pillars to have a minimum interdistance in a range between 600 nm and 10 m; sensitizing the carbon nanotube pillars with a seed metal; electroless plating the sensitized carbon nanotube pillars to electrically bridge the carbon nanotube pillars across the seed layer to the metal substrate by a plated electroconductive material deposited by said electroless plating step, said plated electroconductive material electrically connecting said metal substrate to said sensitized carbon nanotube pillars to form a sensitized carbon nanotube structure of pillars; covering the sensitized carbon nanotube structure of pillars with a conductive layer deposited by an electroplating step; and conformally covering the conductive layer with subsequent layers of a coating that is a battery multilayer or a photovoltaic multilayer, wherein the subsequent layers comprise a solid state electrolyte layer.

2. The method according to claim 1, wherein the sensitizing step is carried out using a solution having a pH >3.

3. The method according to claim 1, wherein the conductive layer is porous.

4. The method according to claim 1, further comprising covering the subsequent layers of the coating on the conductive layer with a planarizing filler.

5. The method according to claim 1, wherein the metal substrate is stacked on an organic foil.

6. The method according to claim 1, wherein the steps of forming, sensitizing, electroless plating and covering are carried out in a roll-to-roll process.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows subsequent steps according to a first embodiment;

(2) FIG. 2 shows in more detail a process of providing a metal coating onto CNTs;

(3) FIGS. 3A, 3B and 3C respectively show micrographs of CNT tube structures;

(4) FIG. 4 (A-D) schematically shows a high aspect ratio structure according an embodiment of the present invention

(5) FIG. 5 (A-B) illustrates aspects of high aspect ratio structures that are wound or stacked

(6) FIG. 6 shows examples of packaging or covers with the high aspect ratio structures

(7) FIG. 7 shows an exemplary perspective schematic of a high aspect ratio structure in the form of pillars.

DETAILED DESCRIPTION OF THE DRAWINGS

(8) In FIG. 1 a first embodiment is illustrated of a method according to the present invention. More in particular, in a first step S1, by a seed layer 25 comprising an iron catalyst over an aluminium oxide layer self-aligned carbon nanotubes 11 are formed on substrate 10, for example 100 m high, with a diameter of 80 nm. The seed layer is per se known, and typically comprises an AlO.sub.x/Fe component that can form a catalyst seed for the nanotube. The Al.sub.2O.sub.3 layer 25 functions as a buffer layer.

(9) After providing the seed layer 25, its top surface may be covered with a patterned dots mask 15 (e.g. photoresist) having a hole pattern 14 with lateral dimensions of the final desired micropillars 11. A hole pattern 14 in a mask 15 creates isolated patterns of micropillars that can be formed as templates for a subsequent plating process.

(10) Subsequently, in a second step S2 a photolithographic process is carried out in a resist with a microdots mask pattern 14 masking the seed layer 25 with a micro-pattern dots mask arranged to forming pillars 11. For instance, the dot diameter may be 2 m and a pitch may be 4 m, e.g., forming seed areas with a minimum interdistance between the walls of 2 m or larger than 600 nm.

(11) In a subsequent step S3 the CNTs are grown by a conventional deposition process on the seed pattern, i.e. the Fe component of the seed layer. The deposition process relies on a selective chemical vapor deposition process with a gaseous hydrocarbon source such as methane, ethylene, acetylene or benzene.

(12) Next step S4 will render the pillars thus formed more electrically conductive by an electroless plating step as exemplified in the further embodiments. It is noted that while the CNT structure does exhibit electrical conductivity, this is insufficient to render these suitable for the application as an current collector for electrochemical or electro-optical devices; whereas this plating step solves the problem of providing a homogenously coated pillar structures.

(13) Next in step S5 optionally, an additional metal coating may now be applied to render the walls even more conductive by electroplating for which step S3 forms a critical preparation step. In addition, the electroless plating step provides an electrical bridging layer 30 that shorts the barrier layer 20 in order to form a flow path in the electroplating step. It has been found, that by after the initial electroless plating step, sufficient conductivity is obtained preventing undesired current drop in the micropillars and a homogenous coating can be provided.

(14) In the above mentioned processing methods, the shape of the final micro pillars need not be round (could have any geometric cross-section) and a wide range of pitch as well as arrangement can be chosen. it can be chosen to do the anodization process on both sides of the foil. Such a two sided anodization could result in balanced volume expansion stress caused during anodizing aluminium to porous alumina.

(15) In FIG. 2 in more detail a process is illustrated providing a metal coating onto CNT's. It is noted in particular providing a sufficiently homogenously coated electroless plated metal film onto the carbon nanotubes formed as micropillar structures is challenging because the structures can dissolve from the buffer layer into the process liquids quite fast. As well most literature works focused on metallization of CNTs do not provide an adequate solution.

(16) From a process point of view CNTs are sensitized by an activation step, and a subsequent functionalization step. These steps can optionally be combined. The activation, i.e. formation of reactive groups on the surface induced by e.g. oxidation such as carboxylic groups can be used to support further functionalization.

(17) One activation option may be being prolonged exposure to strong acids such as nitric acid or sulfuric acid (see Chemically Functionalized Carbon Nanotubes, K. Balasubramanian, M. Burghard, small 2005, 1, p 180). Alternatively other acids could be used such as SnCl.sub.2 as described by (Qunqing Li et al.; Coating of Carbon Nanotube with Nickel using electroless plating method; Jpn. J. Appl. Phys. Vol. 36 (1997) pp. L 501-L 503.). The speed of reaction can be increased by performing the reaction at elevated temperatures as well as (ultrasonically) stirring the solution. This step requires the buffer layer to be insensitive to acids.

(18) Otherwise, and preferably for a seed layer comprising an AlO.sub.x/Fe component, a reactive plasma gas may be used e.g. O.sub.2 or NH.sub.3 (Radio-frequency plasma functionalization of carbon nanotubes surface O.sub.2, NH.sub.3, and CF.sub.4 treatments, e.g. by 0.5-5 min plasma treatment by a 100-1000 W oxygen plasma. A. Felten, C. Bittencourt, J. J. Pireaux, G. Van Lier and J. C. Charlier. J. Appl. Phys. 98, 074308, 2005) as well as ozone treatments (Room temperature functionalization of carbon nanotubes using an ozone/water vapor mixture. Ke Penga, Lu-Qi Liva, Hongchao Lic, Helmut Meyerc, Zhong Zhang, Carbon, 49, 2011, p 70). It is found that by dry activation treatment, the CNT-buffer layer structure remained intact.

(19) After the activation step, a functionalizing step (b) may be carried out for supplying the carbon nanotubes with suitable catalyst. Typical catalyst needed to provide electroless plating consist of Pd, Sn, Au or Pt ions or nanoparticles. In one example, a suitable plasma, such as NH3 plasma, may provide a combined activation/functionalization process for sensitizing the CNTs.

(20) An other sensitation process may be carried out by bathing the CNT structures in a solution of SnCl.sub.2 at 45 C. for 30 min. The active CNTs can then functionalized in 0.006 mol/L PdCl2 solution at 45 C. for 30 min and dried at 110 C. before electroless plating, as e.g. described by Li et al. The resulting reaction provides a layer of reduced palladium ions on the surface, needed to initiate the electroless plating. Alternatively a procedure given by Li-Ming Ang et al can be used (Electroless Plating of Metals onto Carbon Nanotubes Activated by a Single-Step Activation Method, Li-Ming Ang et al, Chem. Mater. 1999, 11, 2115). Here Tin and palladium ions are introduced onto the oxidized CNTs from a PdCl2/SnCl2 colloidal solution. A 1 M HCl solution was used improve the catalytic PdSn operation.

(21) Alternatively functionalizing step b1 could be performed by providing a termination group for binding a seed metal such as a Pd, Sn, Au in a chloride, acetate salt. Rather than performing a single reaction, CNTs e.g. activated by oxidation or by NH.sub.3 plasma can be taken as a starting point. In case the surface is not sufficiently active by itself, the process may be enhanced by selectively terminating the surface with suitable terminations such as thiols or amines. Such terminations can be achieved onto CNTs through the usage of linkage groups such as dithiols (e.g. ethanedithiol, hexanedithiol), or diamines (e.g. ethanedithiol, hexanediamine) and solutions thereof, e.g. 1M hexanediamine in ethanol.

(22) By submerging the CNTs into a solution of which contains a Pd, Sn, Au salt such as a chloride, acetate salt binding step b2 is carried out. The process steps are preferably carried out in a pH neutral bath, with acidity above 3 pH, e.g. 0.01-0.5 g dm-3 of PdCl2 in H.sub.2O for e.g. 5-20 min. Alternatively nanoparticles could be used (New formation process of plating thin films on several substrates by means of self-assembled monolayer (SAM) process, T. Osaka, M. Yoshino, Electrochimica Acta 53, 2007 271, Formation of electroless barrier and seed layers in a high aspect ratio through-Si vias using Au nanoparticle catalyst for all-wet Cu filling technology, Fumihiro Inouea, Tomohiro Shimizua, et al. Electrochimica Acta 56, 2011, 6245, Comparative Study of Electroless Copper Film on Different Self-Assembled Monolayers Modified ABS Substrate, Jiushuai Xu et al Int. J. Mol. Sci. 2014, 15, 6412-6422, Fabrication and Catalytic Properties of Palladium Nanoparticles Deposited on a Silanized Asymmetric Ceramic Support, Rizhi Chen et al. Ind. Eng. Chem. Res. 2011, 50, 4405). After the submersion a thin uniform layer of ions or nanoparticles remain onto the CNTs. This can be used as a seed for a subsequent electroless plating step (c).

(23) In a next step (c), the sensitized carbon nanotubes are introduced into an electroless Nickel plating bath, e.g. with a NiCl.sub.2, NiSO.sub.4 solution. The procedure is carried out at 75 C. and the metal coated carbon nanotubes are washed with distilled water.

(24) Still more advantageously, the electroless plating step (c) bridges the buffer layer with a homogenously provided porous layer formed by electroless plating. A porous Ni layer may be defined in terms of poresize distribution or void-fraction. The average pore diameter can be measured by gas diffusion techniques (for nanopores of 5-20 nm). Another technique like bubble porosimetry can be used for slightly larger pores (30-100 nm). The control of the poresize may be done by controlling the amount of activation and/or Pd-seeding and/or Ni plating on the CNTs, in order to avoid a closed or non-porous layer. The porosity is tuned for optimization of subsequent process steps for manufacturing a battery layer, to prevent bursting of the plated micropillar structures. Additionally, the adequacy of the porosity of the plated layer can be even verified by a potentially destructive test of heating the plated pillars in an oven (at temperatures >20 C up to 700 C). If the pillars burst open during this test, then the inadequacy of the porosity to release all the gases could be concluded.

(25) Results are shown in FIG. 3, where in FIG. 3A a grid of homogenously coated CNT micropillar array is shown, with a pitch of approximately 20 micrometer. In FIGS. 3B and 3C respectively sectional micrographs of a CNT tube are shown, after the electroplating step. Clearly homogenous forms are provided of densily coated carbon nanotubes with a plating of about 3.5 micrometer and a nanotube diameter of about 7.5 micrometer. The heights of the pillars are approximately 65 micrometer. It will be clear to the skilled that the illustrated values are exemplary values, and not to be restricted to these dimensions, but many differing dimensions and thicknesses can be reliably produced in this way.

(26) While in the following the current collector structures are illustrated in isolated form, the skilled person will understand that they will form integral elements of an electronic device designed to a specific purpose. For example, charge collecting is an essential part of a battery structure or electro-optical devices, for example, a solar cell. For example, in an embodiment of the invention an electronic device having an high-aspect ratio structure can be covered with PhotoVoltaic (PV) multilayers yielding a higher area efficiency of the PV. For example, in another embodiment, the electronic device may have PV multilayers that are deposited on the high-aspect ratio structure already coated with battery multilayers. In another example, the electronic device may have PV multilayers that are deposited on the high-aspect ratio structure which are formed on the opposite face of the substrate already containing battery multilayers. This is an interesting concept that provides a photovoltaic foil device including a battery function, that share a common electrode in the form of the high aspect ratio structure as presently disclosed.

(27) In their simplest conceptualization, battery devices two electrodes, one that supplies electrons by virtue of an oxidation process occurring at that electrode, termed the anode, and a second one that consumes electrons by virtue of a reduction process occurring at that electrode, termed the cathode. In discharging battery mode, the anode is the negative electrode to which the positive current flows, from the cathode, being the positive electrode. During charge these functions are reversed. Irrespective charging mode, the electrochemical relationship may be characterized by charge exchange between a negative electrode material and a positive electrode material, the negative electrode material having a workfunction or redox potential that is lower than the workfunction or redox potential of the positive electrode material.

(28) For example, known negative electrode (anode during battery discharge) materials are Li4Ti5O12 (Lithium Titanate spinel or LTO); LiC6 (Graphite); Li4.4 Si (Silicon) and Li4.4Ge (Germanium) known positive electrode (cathode) materials are LiCoO2 (Lithium Cobalt oxide or LCO), LiCoPO4, (doped) LiMn2O4 (Lithium manganese oxide spinel or LMO), LiMnPO4, LiFePO4 (LFP), LiFePO4F(LFPF) or LiCO1/3Ni1/3Mn1/3O2 (LCNMO).

(29) Known (solid state) electrolytes might include lithium iodide (LiI), lithium phosphate (Li3PO4) and lithium phosphorus oxynitride (LiPON). In addition, lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate are known to have a typical conductivity of about 10 mS/cm at RT. The electrolyte decomposes on initial charging and forms a solid layer called the solid electrolyte interphase (SEI).

(30) Thin film ion batteries, including those of the thin film solid state lithium ion type, can be prepared from various deposition techniques to fabricate negative electrode, positive electrode, and electrolyte materials bonded together to form the battery. Such techniques may typically include depositing thin films of such materials using vacuum deposition or other techniques that result in similar thin films, to produce the thin film batteries. Thin film batteries are often employed in applications in which space and weight may preferably be conserved and extremely long cycle life may be desired.

(31) In the following examples in more detail aspects of the invention will be illustrated in the form of an electrochemical device, more specifically a battery device, for instance of a lithium ion type, more specifically having a 3D collector structure for enhancing the charge collecting specific area of the collector, that is in electrical contact with battery multilayer, in particular, a negative electrode layer thereof.

(32) FIG. 4 schematically shows a high aspect ratio structure according to an embodiment of the present invention. In the figure, a high aspect ratio structure 1 is formed from the coated carbon nanotube pillar structures 11 as hereabove disclosed in detail. The electronic device 100 comprising an electronic circuit equipped with a current collector 10 formed by a metal substrate foil 10 having a face forming a high-aspect ratio structure 1 of pillars 11. The walls have an interdistance d larger than 600 nm and, for example, an aspect ratio larger than 10 or even larger than 50. The carbon nanotubes can be formed by a micropattern mask 15, so that isolated carbon nanotube micro pillars 11 are formed. In the specification, the term pillars or micropillars is used to distinguish from dense nanotube structures, which have elongate tubes having diameter dimensions smaller than 300, or even smaller than 50 or 10 nm and with interdistances d smaller than about several hundreds nm, e.g. in the range of 50-300 nm, which are too densily packed without sufficient gap for conformally coating multilayer stacks on them.

(33) The pillars 11 may have lengths of more than 100 nm, arbitrary elongate shapes and diameters at least larger than the said 10 nm, typically more than 100 nm and in this respect typically qualify as high aspect ratio structures.

(34) In US2009214956, a structure is proposed wherein electrolyte material is conformally coated onto conducting nanowires and wherein cathode material, in electrical connection with a second conductive material, is interpenetrated between electrolyte-coated nanowires. In contrast, the micropillars 11 as presently discloses have interdistances substantially larger, that is larger than 600 nm. The pillars 11 are covered by a multilayer or stack 5 of a suitable composition, further detailed below. Suitably, the collector is planarized by a filling spacer material 4, for example, a conductive glue, or a plated material that is in electrical contact with a cathode of the multilayer to form opposite electrode 20. The compressibility as well as strechability of each of the layers in the device 100, the adhesion between the layers 10, 5 and 20 and the total bending stiffness of the stack will determine the maximum allowed bending radius (without damage) while winding or flexing.

(35) The filling spacer material 4 could be any organic or inorganic material. It can for example have some other extra functionality such as a current collector and may optionally, be electroplated over the pillars after the active layers of the battery stack are deposited. Also, the filling can be used as a planarizing filler that planarizes the high-aspect ratio structure 1.

(36) FIGS. 4B, C and D in more detail show a top view, side view and flexed view of clustered pillar forms 10-1 to illustrate how the substrate foil 10 of the current collector can be wound or flexed. In order to enable easy flexing, instead of having the pillars all over the substrate foil 10, isolated islands of pillar-clusters 10-1 can be patterned in a metal foil to form an integral part of it. The lower stiffness of the substrate foil 10 at locations with no pillars, i.e. a grid of planar zones 10-2, enables easy bending or rolling of a 3D battery foil formed from the substrate foil 10 for example, as illustrated in FIG. 4 D. The high aspect ratio clusters 10-1 of micropillars can optionally be further stabilized by filling a spacer material between them of the type disclosed in FIG. 4A. In an example, the high aspect ratio clusters may span an area smaller than 10 e4 micrometer2; and the planar zones may be are formed as strips having a width larger than 50 micrometer, although other ranges can be suitably used to the same effect of clustering to enable easy flexing.

(37) FIG. 5 illustrates how the high aspect ratio structures can be wound (FIG. 5A) or stacked (FIG. 5B). While winding, to avoid damage to the pillars, the pillars are made to face outwards so that the face forming the high-aspect structure is convex. The wound stack can either be concentric (as shown in the figure) or like a continuous spiral, in the figure, by tapered pillars, cones or pyramids facing outwards. In order to avoid cracking of the active layers due to strains caused while winding, optionally the deposition of (at least some of the) active layers can be done after the winding is done.

(38) Since the possibility of cracking the active layers while bending or winding is the highest in-between the pillars, it can be optionally chosen to deposit the active layers just on the pillars (and not in-between). Moreover, this will additionally also avoid cracking at the base corners around the pillars while volume expansion/contraction of the electrode layers happens during charging/discharging of the battery.

(39) In general, in order to avoid active layers cracking while flexing or while battery operation, corners of the 3D battery structure are to be designed rounder, i.e. with a radius of curvature larger than 200 nm, or even larger than 1 micrometer.

(40) FIG. 5B shows another way of increasing the energy or power density per unit volume of the 3D battery, for example by stacking separate battery foils 10 on top of each other. This stacking in the 3D battery case can be done by using optionally a conductive glue 4 (if the foils are connected in series). This conductive glue 4 could also be a filler material to stabilize the pillars on each of the foils. Accordingly, a plurality of current collectors may be provided, that are alternatingly stacked with battery multilayers.

(41) Optionally, 3D pillars could be created on both sides of the metal foil. In embodiment, this could be combined with a photovoltaic layer on one side and a battery layer on the other side or on the same side. In another embodiment this could be used to provide two battery stack layers per foil 10. In this case, the substrate foil (in case of being a metal), will act as a common electrode while stacked (see FIG. 5b). The connection of different battery foils to each other in a circuit needs to be according to the voltage desired while charging and discharging.

(42) In order to make such batteries cost-effective, it is advantageous to transfer this technology to large area metal foils e.g. for roll-to-roll processing.

(43) FIG. 6 shows examples of using packaging or covers or frames of devices/machines/equipments as substrates for 3D thin-film batteries. Nowadays, since products are getting compacter, the demand on small and more compact batteries (providing the same power or capacity needed) is growing. The ideas mentioned in this patent intake is about fabricating these 3D micropillar structures on the package or cover of a device that uses these batteries. One of the areas that has been looked into is the integration of batteries into the package/cover of a device. A device could be as small as a mobile phone 300 and as big as an electric car 200. For example in a car, aluminium or aluminized covers, such as a side panel 230, roof panel 210, bonnet 220 etc., may be used for providing battery structures on large areas. Or, in a mobile phone 400, an aluminized rear panel of the mobile phone 300 having the high aspect ratio structure as presently disclosed may be forming the battery, or may be provided as a switchable cover for extra power.

(44) The 3D structured substrate could contain pillar structures or aligned porous structures achieved by anodization as the base technology.

(45) For instance, since the 3D battery structures can be formed directly by anodizing the body frame of a car. The material of the frame can be of steel, coated with a layer of Aluminium needed for anodization. Subsequent electroplating and oxide etching steps can create the 3D pillar structures on the car body (preferably interior).

(46) Accordingly the metal substrate having the high aspect ratio structure may monolithically formed as a casing structure. There are other devices that have covers made of aluminium, where this concept may be applied. Alternatively a metal substrate may be stacked on an organic foil, i.e. containing a hydrocarbon content, for example, PEN, PET etc. or plastic mould structure. Even if the packages/covers of most of the devices today are moulded of plastic, still 10 s of micrometers of aluminium can be electroless plated by ionic liquids on plastics to create the battery on it or in it.

(47) FIG. 7 shows an exemplary perspective schematic of a high aspect ratio structure 1 in the form of pillars 11 that are covered with a conformal battery multilayer as shown in the 4A, giving a schematic cross-sectional view along I-I. The high-aspect ratio structure 1 disclosed is formed by geometrically ordered micropillars 11 on a substrate foil 10 having a base b conformal with a surface s but can alternatively be trenches, ridges, tapered structures and forming a planar faces. In the embodiment, the metallized carbon nanotube pillars 11 have a radius of curvature larger than 50 nanometer. A minimum interdistance d is larger than 600 nm to accommodate a conformal coating of about 300 nm thickness. A practical interdistance may be about 2-3 micron. The metal pillars 11 may have a height h as high as 25 micrometer or higher, for example, 50 or 100 micrometer and can be formed with a pitch p in the range of 3-12 micrometer. Gaps g between pillars 11 are preferably filled, in particular, after depositing the active battery multilayer 5 of the battery stack with cushion or filling spacer material 4 to avoid contact between them while bending or flexing the 3D battery stack. A gap between adjacent conformal coatings of the battery multilayer 5 may be in the order of 100-500 nanometer. The gap may be completely filled with a conductive material.

(48) In the example, preferably, the battery multilayer 5 comprises a solid state electrolyte layer 5-2 interposed between a negative electrode layer 5-1 in electrical contact with the pillar 11 and a positive electrode layer 5-3. It is found that the battery multilayer 5 preferably comprises a first electrode 5-1 layer coated on the high-aspect ratio structure and having a thickness that matches, for a given C-rate, the effective volumetric storage capacity of second electrode layer 5-3 that is separated from the first electrode layer by an electrolyte layer 5-2. In this way electrode thicknesses in the battery multilayer may be varied and are correlated to match their effective volumetric storage for a given C-rate capacities for Lithium-ions while charging and/or discharging, while at the same time, due to curvature, the manufacturability is enhanced. The thickness of the negative electrode layer can be typically less than the positive electrode layer due to a higher theoretical density. For LixTiO2 and or LixMnO2 the densities and thicknesses are similar. For example, the first layer 5-1 may be the negative electrode layer ranging between 80 and 300 nm; and the second layer 5-2 may be an electrolyte layer ranging between 60 and 200 nm. The positive electrode layer, 5-3 may range between 30 and 200 nm. The battery stack could be integrated into any other device (e.g. PV) substrate, which can then be further integrated into other structures.

(49) Instead of a battery layer that is formed conformally to the high aspect ratio structure, such structure may be used as a charge collector structure when combined with a negative electrode layer that is formed to planarize the high aspect structurei.e. not a conformal layer. For instance such negative electrode layer could be in contact with an electrolyte of solid state type but alternatively could be in a liquid form.

(50) Aspects of the present invention are characterized by the following clauses:

(51) A method of manufacturing a current collector with a high-aspect ratio structure of pillars formed on a metal substrate, wherein the method comprises: forming elongate and aligned carbon nanotube structures on a face of a seed layer covering the metal substrate; with a micro-pattern mask arranged to forming the carbon nanotube pillars having a minimum interdistance larger than 600 nm; and a rendering step to render the pillars electrically conductive by sensitizing the carbon nano tube pillars with a seed metal; electroless plating the sensitized carbon nano tubes to bridge the seed layer and an electroplating step so that the carbon nanotube pillars are rendered electrically conductive by covering the pillar walls with a conductive layer.

(52) An electronic device comprising an electronic circuit equipped with a current collector formed by a metal substrate having face forming a high-aspect ratio structure of pillars, the walls having a minimum interdistance larger than 600 nm said carbon nanotube pillars being electrically conductive.

(53) An electronic device as before, wherein the high-aspect ratio structure is formed by trenches or geometrically ordered micropillars.

(54) An electronic device as before, wherein the high-aspect ratio structure comprises pillars having a radius of curvature larger than 50 nanometer.

(55) An electronic device as before, wherein the pillars are higher than 25 micrometer.

(56) An electronic device as before, wherein the pillars are formed in high aspect ratio clusters that are separated by a grid of planar zones.

(57) An electronic device as before, wherein the high aspect ratio clusters span an area smaller than 10 e4 micrometer2; and wherein the planar zones are formed as strips having a width larger than 50 micrometer.

(58) An electronic device as before, wherein the face forming the high-aspect structure is convex.

(59) An electronic device as before, wherein the substrate is a foil having both faces forming a high-aspect ratio structure.

(60) An electronic device as before, wherein the high-aspect ratio structure and the metal substrate are formed monolithically.

(61) An electronic device as before, wherein the high aspect ratio structure is covered with a coating that is conformal to the pillars of the high aspect ratio structure.

(62) An electronic device as before, wherein the coating is a battery multilayer or a PV multilayer or both.

(63) An electronic device as before, wherein the battery multilayer comprises a solid state electrolyte layer.

(64) An electronic device as before, wherein the battery multilayer comprises a first electrode layer coated on the high-aspect ratio structure and having a thickness that matches the effective volumetric storage capacity of a second electrode layer at a battery charging rate larger than 10 C-rate.

(65) An electronic device as before, wherein the first layer is an negative electrode layer ranging between 80 and 300 nm; wherein the second layer is an electrolyte layer ranging between 60 and 200 nm; and wherein a positive electrode layer ranges between 30 and 200 nm.

(66) An electronic device as before, having a plurality of current collectors, that are alternatingly stacked.

(67) An electronic device as before, wherein the multilayer structure is covered with a planarizing filler that planarizes the high-aspect structure.

(68) An electronic device as before, wherein the filler is a metal forming an electrode part.

(69) An electronic device as before, wherein the filler is a conductive glue that functions to stack the current collector and while stabilizing the high aspect structure.

(70) An electronic device as before, wherein the metal substrate is stacked on an organic foil.

(71) An electronic device as before, wherein the metal substrate is monolithically formed as a casing structure. The claimed battery stack could be integrated into any other device (e.g. PV) substrate, which can then be further integrated into other structures.

(72) It will be appreciated that while specific embodiments of the invention have been described above, that the invention may be practiced otherwise than as described. In addition, isolated features discussed with reference to different figures may be combined.