Method and apparatus for manufacturing a patterned substrate or patterned device

Abstract

An apparatus for forming a conductive element on a substrate is disclosed. In one example, the apparatus includes an insulator substrate, an electrode integrated with the insulator substrate, and an insulating pattern formed on the electrode, wherein the insulating pattern defines a feature corresponding to a conductive element to be formed on the substrate.

Description

Technical Field

[0001] The present invention relates to methods and apparatus for manufacturing patterned devices or patterned substrates for devices.

[0002] The present invention specifically, but in no way exclusive, relates to a method and apparatus for additive manufacturing of patterned devices or patterned substrates for devices, the method and apparatus utilizing an electrochemical reaction to form a pattern on the surface of the substrate.

[0003] The present invention also specifically, but in no way exclusive, relates to a method and apparatus for additive manufacturing of conductive patterned devices or conductive patterned substrates for electronic devices, the method and apparatus utilizing an electrochemical reaction to form conductive patterns on the surface of the substrate. Background Technology

[0004] The current state of electronic device manufacturing is fraught with inefficiencies and limitations, primarily stemming from the widespread use of subtractive manufacturing methods for producing the circuitry used in these devices. Traditional methods are characterized by multiple sequential steps and the use of different tools to pattern and deposit (or etch) conductive surfaces, typically resulting in long production times and high costs.

[0005] Additive manufacturing promises to revolutionize the industry by simplifying processes, reducing steps, and minimizing capital requirements, paving the way for more cost-effective electronic device manufacturing. However, effectively adopting additive manufacturing in electronics faces significant challenges. As electronic devices require smaller feature sizes to enhance performance, the inherent speed limitations of existing additive manufacturing technologies at high resolutions hinder scalable high-resolution production. Furthermore, most additive technologies simply cannot achieve the feature sizes required for electronic devices.

[0006] Current solutions primarily rely on photolithography to fabricate high-resolution devices, and on screen printing or roll-to-roll methods to achieve high-volume manufacturing of lower-resolution devices. However, these methods are plagued by inefficiencies and limitations. While photolithography can achieve high resolution, it involves multiple sequential steps and significant capital investment, resulting in a slow and expensive process. Conversely, while screen printing offers higher throughput, its resolution and material compatibility are limited, restricting its applications and leading to increased material costs and compromised conductivity of the printed structure.

[0007] High-resolution structures are desirable because they allow for more complex architectures that can enhance device performance. This can significantly increase the overall value of manufacturing output.

[0008] Given these challenges and limitations, there is a need for a cost-effective and scalable manufacturing process in electronic device manufacturing, and in particular, a high-volume additive manufacturing technology with high-resolution capabilities. Summary of the Invention

[0009] In summary, the present invention provides a method and apparatus for fabricating patterned devices or patterned substrates for devices using an electrochemical reaction. The geometry of the pattern is determined by a corresponding pattern embedded in the device.

[0010] In one example, an apparatus for forming a conductive element on a substrate includes: an insulating substrate; an electrode integrated with the insulating substrate; and an insulating pattern formed on the electrode, wherein the insulating pattern defines a feature corresponding to the conductive element to be formed on the substrate.

[0011] In one example, the electrode has a two-dimensional footprint on the outward-facing surface of the device, and multiple features are located within the two-dimensional footprint on the outward-facing surface of the device.

[0012] In one example, the electrode has a two-dimensional occupied area at the front of the device, and multiple features are located within the two-dimensional occupied area at the front of the device.

[0013] In one example, the electrode has a front portion having a two-dimensional area at the front side of the device and a rear portion having a two-dimensional area at the rear side of the device, wherein the two-dimensional area of ​​the rear portion of the electrode is greater than the two-dimensional area of ​​the front portion of the electrode.

[0014] In one example, the insulating pattern comprises an insulating layer of insulating material, wherein the features are formed via photolithography.

[0015] In one example, the feature has a size on the order of micrometers.

[0016] In one example, the feature has a size on the nanometer scale.

[0017] In one example, the device also includes electrodes, which correspond to discrete conductive regions on the outward-facing side of the device.

[0018] In one example, the device also includes multiple electrodes, which correspond to discrete conductive regions on the front side of the device.

[0019] In one example, the device also includes a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions on the outward-facing surface of the device, and wherein the electrodes are configured to be independently modulated with potential and current.

[0020] In one example, the device also includes a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions on the front side of the device, and wherein the electrodes are configured to be independently modulated with potential and current.

[0021] In one example, the device also includes a fluid channel within an insulating substrate, wherein the end of the fluid channel is located on the outward-facing side of the device.

[0022] In one example, the device also includes a fluid channel extending from the front side of the device through an insulating substrate to the rear side of the device, wherein the fluid channel is configured to provide an ion source to the front side of the device.

[0023] In one example, the device also includes a fluid channel through an insulating substrate, wherein the fluid channel is configured to provide an ion source to the outward-facing side of the device near the electrodes.

[0024] In another example, an apparatus for forming a conductive element on a substrate includes: an insulating substrate; an electrode integrated with the insulating substrate, wherein the electrode corresponds to a discrete conductive region of the apparatus; and an insulating pattern formed on the electrode, wherein the insulating pattern defines a feature corresponding to a conductive element to be formed on the substrate.

[0025] In one example, each electrode has a front portion having a two-dimensional area at the front of the device and a rear portion having a two-dimensional area at the rear of the device, and each electrode is individually controllable.

[0026] Other aspects of the invention will become apparent from the following detailed description taken in conjunction with the accompanying drawings, which illustrate the principles of the invention by way of example. Attached Figure Description

[0027] The embodiments of the present invention are described below by way of example only with reference to the accompanying drawings, wherein: Figure 1 (a) illustrates a predetermined pattern on the conductive surface of the molding electrode.

[0028] Figure 1 (b) illustrates different ways of forming a conductive patterned substrate according to one form of the invention.

[0029] Figure 2 Various geometries of a molded electrode according to one form of the invention are illustrated.

[0030] Figure 3 An exemplary device according to one form of the invention is shown, illustrating the location of the electric field.

[0031] Figure 4 An example of a stepwise rapid layer manufacturing process according to the present invention is illustrated.

[0032] Figure 5It is a cross-sectional image of a patterned substrate formed using a contact technique according to one form of the invention, the contact technique using a continuous current.

[0033] Figure 6 It is a cross-sectional image of a patterned substrate formed using a contactless technique according to one form of the invention, the contactless technique using a continuous current.

[0034] Figure 7A This is a side cross-sectional view of a molded electrode, which includes an insulating substrate, an electrode, and an insulating pattern.

[0035] Figure 7B This is a plan view of an example of the front side of the molding electrode, showing various features formed by the insulating pattern at the front side of the molding electrode.

[0036] Figure 7C This is a plan view of an example of the rear side of a molding electrode, showing a portion of one or more electrodes of the molding electrode.

[0037] Figure 8A This is a plan view of an example of the front side of the molding electrode, which shows multiple discrete conductive regions, each of which has various features formed by an insulating pattern at the front side of the molding electrode.

[0038] Figure 8B It comes from Figure 8A A plan view of an example of the rear side of the molding electrode 800, showing a portion of the electrode of the molding electrode.

[0039] Figure 9 This is a side cross-sectional view of a molded electrode, which includes an insulating substrate, two electrodes, and an insulating pattern.

[0040] Figure 10 Is with Figure 2 The electrode shown is a side sectional view of an example of a die-cast electrode, similar to an example of an electrode.

[0041] Figure 11A This is a plan view of an example of the front side of a molding electrode, showing multiple features formed by an insulating pattern, one end of each of the four fluid channels, and the outline of the front portion of the electrode.

[0042] Figure 11B It comes from Figure 11A A plan view of an example of the rear side of a molding electrode, showing the opposite ends of each of the four fluid channels and the rear portion of the electrode visible at the rear side of the molding electrode.

[0043] Figure 12 It is a reference Figure 10 , Figure 11Aand Figure 11B The described example is a side cross-sectional view of an example of a molded electrode.

[0044] Figure 13 This is a plan view of an example of the front side of the molding electrode, showing one end of multiple fluid channels and the outline of the front portion of the two electrodes.

[0045] Figure 14A This is a side cross-sectional view of a molding electrode, which includes an insulating substrate, two electrodes, and an insulating pattern defining a feature portion.

[0046] Figure 14B This is a plan view of an example of the front side of the compression molding electrode, showing the outlines of the front portions of the four electrodes and the rear portions of the four electrodes.

[0047] Figure 14C It comes from Figure 14B A plan view of an example of the rear side of a molding electrode, showing the outlines of the rear portions of the same four electrodes and the front portions of the four electrodes.

[0048] Figure 15A This is a side cross-sectional view of a molding electrode, which includes an insulating substrate, two electrodes, and an insulating pattern defining a feature portion.

[0049] Figure 15B This is a plan view of an example of the front side of a molding electrode, showing the features defined by an insulating pattern and the outline of the front portions of the four electrodes of the molding electrode.

[0050] Figure 15C It comes from Figure 15B A plan view of an example of the rear side of a molding electrode, showing the outlines of the rear portions of the same four electrodes and the corresponding front portions of the four electrodes. Detailed Implementation

[0051] Those skilled in the art will understand that many modifications can be made without departing from the spirit and scope of the invention.

[0052] In summary, the present invention provides a method and apparatus for fabricating patterned devices or patterned substrates for devices using an electrochemical reaction. The geometry of the pattern is determined by a corresponding pattern embedded in the device.

[0053] The present invention also provides a method and apparatus for additive manufacturing of coated devices or coated substrates for electronic devices, the method and apparatus using an electrochemical reaction to form a conductive coating having a predetermined pattern on the surface of the device or substrate.

[0054] The device or substrate may provide a patternable conductive or non-conductive surface.

[0055] In this specification, any reference to a patterned substrate also refers to a patterned device, which may consist of or include the patterned substrate itself and one or more other components of the device. Accordingly, any reference to the patterning of a substrate also refers to the patterning of a device composed of the substrate.

[0056] In this specification, the term "device" encompasses optical devices, magnetic devices, electronic devices, data storage devices, optical metamaterials, sensors, chips, lasers, LEDs, quantum sensing communication and computing devices.

[0057] In this specification, the term "electronic device" covers any conductive device. Non-limiting examples of electronic devices include printed circuit boards, solar cells, sensors, antennas, displays, batteries, and light-emitting diodes.

[0058] In this specification, the term "pattern" encompasses both 2D and 3D structures.

[0059] Specifically, the present invention provides a method and apparatus for modifying the surface of a device or substrate to form a predetermined pattern using a spatially selective electrochemical reaction.

[0060] In this specification, modification of the device or substrate surface may cover any of the following methods: (i) Modify existing materials on a device or substrate to change the shape of the material into a predetermined pattern; (ii) etching material from the surface of a device or substrate to form a predetermined pattern; and (iii) Depositing solid material on a device or substrate to form a coating with a predetermined pattern.

[0061] The present invention ideally provides a means of electrochemically modifying the surface of a device or substrate by applying a localized electric field to trigger the formation of a patterned coating on the device or substrate. Suitably, the localization of the electric field is facilitated by a molded electrode comprising a patterned electrode surface having different regions of insulation or conductivity. This provides a predetermined pattern to which the electrochemical reaction is subject. Suitably, the formed pattern can be reused for a variety of applications.

[0062] This invention was developed to address the problems associated with separate deposition and patterning steps for forming patterned layers on devices or substrates, particularly for semiconductor interconnects, which can be expensive and time-consuming. For example, photolithography requires an initial step to form a photoresist layer, which is then etched in subsequent steps. In contrast, this invention allows for the combination of patterning and reactive steps to form patterned devices or substrates, wherein the layer for etching can be pre-formed or is part of the device or substrate. The reactive steps encompass depositing material on the device or substrate, and etching and modifying the device or substrate or the material on the device or substrate, such as through oxidation or substitution.

[0063] This invention utilizes spatially selective electrochemical reactions to provide means for combining reaction and patterning steps. It is particularly applicable to additive manufacturing by providing means for forming 3D structures comprising multilayered deposited materials on devices or substrates. Suitably, each layer of deposited material is formed with a predetermined pattern.

[0064] This invention also improves the localization of material deposited on a device or substrate to improve the resolution of the pattern on the device or substrate. In this specification, the term "high resolution" has a lower limit of <1,000 μm, preferably <200 μm, more preferably <100 μm, even more preferably <50 μm, even more preferably <20 μm, and further even more preferably <1 μm. The upper limit of the term "high resolution" has an upper limit of >10 nm, preferably >100 nm, more preferably >1 μm, and even more preferably >5 μm. Resolution may be independent of electrode area or reaction rate.

[0065] Another potential benefit of this invention is the ability to produce high aspect ratio structures in a single step through etching or deposition. The invention also allows for control of the reaction process by adjusting operating parameters such as voltage, pulse shape, and ink formulation, as well as etching depth, the height of the deposited material, and the morphology of the formed structure.

[0066] In a first aspect of the invention, an apparatus is provided for forming a high-resolution patterned device or a high-resolution patterned substrate for a device, the apparatus comprising: A molded electrode is configured to form a pattern on a device or substrate, the electrode having an outward-facing surface on which a mask with a predetermined pattern is applied, wherein the molded electrode is further configured to confine an electrochemical reaction to a region less than 200 μm wide on the device or substrate, or to deliver a high current density greater than 10 kA / dm2 (or greater than 1 A / mm2) to a selected region of the device or substrate during an electrochemical reaction; An ion source, used to supply ions for patterning on a device or substrate; and A power source is used to initiate the movement of ions between an ion source and a device or substrate, as well as electrochemical reactions, to form a pattern on the device or substrate, wherein the pattern is identical to or inverted from a predetermined pattern of a mask.

[0067] The molded electrode can be configured to confine the electrochemical reaction to a region less than 200 μm wide, preferably less than 100 μm wide, more preferably less than 50 μm wide, or even more preferably 20 μm wide, of the device or substrate. This facilitates the production of high-resolution patterned devices or high-resolution patterned substrates by enabling the fabrication of complex patterns within a limited space.

[0068] The die-cast electrode can be configured to deliver high current densities greater than 10 kA / dm² (or greater than 1 A / mm²), suitably greater than 20 kA / dm² (or greater than 2 A / mm²), more preferably greater than 50 kA / dm² (or greater than 5 A / mm²), and even more preferably greater than 80 kA / dm² (or greater than 8 A / mm²). The current density is proportional to the deposition rate, and therefore proportional to the production speed. Combined with the ability to form patterns in areas less than 200 μm wide on a device or substrate, this invention provides a means to achieve scalable, high-resolution production.

[0069] The molded electrode can be configured to confine the electrochemical reaction to a region of the device or substrate with an aspect ratio greater than 0.1, preferably greater than 0.2, more preferably greater than 0.5, or even more preferably greater than 1.0.

[0070] The mask can be conductive or insulating. The properties of the mask will depend on the properties of the outward-facing surfaces of the electrodes. Specifically, the conductivity of the mask will be opposite to the conductivity of the outward-facing surfaces of the electrodes. Therefore, the mask will allow for the formation of both conductive and insulating regions on the outward-facing surfaces of the electrodes.

[0071] By confining the reaction to the exposed conductive region of the die-cast electrode or mask and restricting the reaction to the insulating region (i.e., providing spatially selective reaction), the die-cast electrode provides an active region for electrochemical reactions. This allows for the combination of deposition (or etching, anodizing, etc.) and patterning steps.

[0072] The molding electrode may include a conductive, semi-conductive, or insulating base, with conductive and insulating regions located on the base.

[0073] The conductive region can be part of the base or an additional layer on the base, such as an electrode.

[0074] Insulating regions can be formed by applying a patterned insulating mask to the conductive surface of an electrode. The insulating mask pattern enables the formation of electrochemical transition regions on the surface of a device or substrate during an electrochemical reaction, these regions having a pattern that is the inversion of the insulating mask pattern.

[0075] Suitably, when a reduction reaction (such as metal deposition) is to be performed on the device or substrate, the die-casting electrode is the anode and the device or substrate is the cathode. In another embodiment, if electropolymerization or any other oxidation reaction is to be performed on the device or substrate, the die-casting electrode is the cathode and the device or substrate is the anode.

[0076] The outward-facing surface can be substantially flat. In some embodiments, the outward-facing surface includes non-planar features. Suitably, the non-planar features are raised or recessed areas.

[0077] The outward-facing surface can include multiple discrete conductive regions, each of which can have its potential and current modulated independently. By providing multiple independent conductive regions, the electrochemical reaction at each region can be tuned as needed. For example, the current delivered to each region can be adjusted to address voltage drops and ensure uniform reaction conditions across the discrete regions. The reverse is also true, where multiple conductive regions allow for non-uniform deposition, thereby creating regions with different film thicknesses during a single patterning step. This is not possible with photolithography and screen printing.

[0078] The base may be made of an inert material. Suitably, the material is a noble metal, a conductive polymer, a semiconductor, or a carbon allotrope. Non-limiting examples of suitable materials include metals (such as nickel, copper, platinum, gold, silver, and steel alloys), conductive polymers (such as poly(3,4-ethylenedioxythiophene) (PEDOT)), semiconductors (doped or undoped) (such as silicon, gallium arsenide, indium phosphide, and germanium), conductive oxides (such as indium tin oxide (ITO)), and carbon allotropes.

[0079] The die-cast electrode may include a conductor located between the base and the insulating mask. Suitably, the conductor comprises an inert material. More suitably, the inert material may include a noble metal, a conductive polymer, a semiconductor, or a carbon allotrope. Even more suitably, the inert material differs from the material of the conductive base. Non-limiting suitable examples of the inert material used for the conductor are the same as those used for the conductive base.

[0080] Having a base and / or intermediate conductor that is inert to electrochemical conditions improves the durability of the die-cast electrode over multiple deposition cycles.

[0081] Combining a masked, outward-facing surface can create a morphology that is aligned with and adapted to the surface of a device or substrate, or aligned with and adapted to the products of a previous electrochemical reaction on the surface of a device or substrate.

[0082] The applicant recognizes that molded electrodes with different surface morphologies are advantageously suited for multilayer electrochemical modification. In this respect, the morphology of the outward-facing surface can be advantageously manipulated to accommodate non-uniform and / or uneven device or substrate morphologies, or to accommodate products on previously electrochemically modified devices or substrates.

[0083] The pattern formed on the device or substrate is defined by the arrangement of conductive and non-conductive regions on the die-cast electrode relative to each other.

[0084] The pattern can be conductive. Suitablely, the pattern is formed from a conductive material.

[0085] A mask is a feature of a device that defines a pattern formed on a device or substrate.

[0086] A mask forms a spatially selectively patterned surface on the outward-facing surface of a molded electrode, which defines the electrochemical transition region on the surface of the device or substrate.

[0087] During the electrochemical reaction, depending on the conductivity of the outward-facing surfaces of the mask and die electrodes, the electrochemical reaction can occur at the device or substrate location above the mask, or in the exposed area surrounding the mask. For example, the area of ​​the device or substrate located above the electrode insulating mask is isolated from the electrochemical reaction and remains substantially unmodified. The exposed device or substrate area located above the conductive surface of the electrode is modified by the electrochemical reaction. Conversely, the area of ​​the device or substrate located above the electrode conductive mask is modified by the electrochemical reaction, while the exposed device or substrate area located above the insulating surface of the electrode is shielded from the effects of the electrochemical reaction.

[0088] A mask may be applied to the surface of the die-casting electrode and protrude from the surface of the die-casting electrode. In some embodiments, the mask is recessed into the electrode surface.

[0089] There are no particular restrictions on the material of the mask. The insulating material can be mechanically rigid (i.e., exhibiting a high Young's modulus) or mechanically flexible and / or elastic (i.e., exhibiting a low Young's modulus). Suitable materials for forming insulating masks may include inorganic dielectrics such as silicon dioxide, alumina, tantalum oxide, silicon nitride, and silicon carbide, and include polymers such as SU-8, polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), epoxy resins, polytetrafluoroethylene (PTFE), polyethylene (PE), polyetheretherketone (PEEK), rubber, polyimide, and polyolefins. Suitable materials for forming conductive masks may include materials such as nickel, copper, tin, chromium, aluminum, molybdenum, tungsten, indium, platinum, gold, silver, and steel alloys, conductive polymers (such as poly(3,4-ethylenedioxythiophene) (PEDOT)), semiconductors (doped or undoped) (such as silicon, gallium arsenide, indium phosphide, and germanium), conductive oxides (such as indium tin oxide (ITO)), and carbon allotropes.

[0090] Advantageously, when the mask is flexible and / or elastic, the mask should preferably deform upon contact with the device or substrate and at least partially conform to the surface of the device or substrate.

[0091] Flexible and / or elastic masks that can conform to the topology of a device or substrate offer significant advantages, including: (i) Align the molded electrode with the device or substrate; (ii) Mechanically level the material on the device or substrate; (iii) The electric field is defined by confining the reaction medium to the conductive region of the molding electrode; and (iv) Creates clear edge boundaries in an electric field, confining ions within the field to provide clear and high-resolution patterning and reduce unwanted reactions such as over-deposition and / or damage or contamination of the target surface.

[0092] The mask may comprise a rigid polymer. In embodiments where the rigid polymer used for the mask protrudes from the outward-facing surfaces of the electrodes and the mask contacts the device or substrate during an electrochemical reaction, the polymer allows the mask to be used to establish an inter-electrode gap.

[0093] Masks may contain soft polymers that can conform to the surface of a device or substrate.

[0094] The soft polymer can have a Young's modulus of less than 1,000 MPa, preferably less than 100 MPa, and more preferably less than 10 MPa. This enables the soft polymer to achieve the desired strain of less than 5%, preferably less than 3%, and more preferably less than 1% to conform to the target device or substrate surface, or even more preferably in the range of 5% to 0.01%.

[0095] The platform can be movable to adjust the position of the device or substrate relative to the molded electrode.

[0096] The device can be configured to adjust the position of the molded electrode relative to the device or substrate. Suitablely, the molded electrode is mounted to a movable arm of the device.

[0097] The device may include a platform for supporting the device or substrate.

[0098] The platform can be configured to receive an ion transfer medium to facilitate the movement of ions between the device or substrate and the ion source, thereby forming a coating. Suitably, the platform forms a container to hold the ion transfer medium and allows the device or substrate to be immersed in the medium. Alternatively, the ion transfer medium can be applied directly to the device or substrate. Suitably, the ion transfer medium is applied to the device or substrate such that it is confined to the top surface of the device or substrate. More suitably, at least one thin layer of the ion transfer medium is applied to the device or substrate without contacting the bottom and side edges of the device or substrate.

[0099] Non-limiting examples of ion transfer media include ion-containing inks, one or more organic, ionic, and aqueous solvents (such as water, aqueous solutions, polar or nonpolar hydrocarbon solutions, eutectic solvents, inorganic hot melts, and ionic liquids), ionic solid conductors (such as superionic polymers and oxides), and supercritical fluids (such as CO2). Ion transfer media may include selective membranes that can be used with solvents.

[0100] The ion source can be a solid material deposited on a die electrode, part of the die electrode, or in the form of ink. If ink is used (the ink is both the ion source and the medium for ion transport), a separate ion transfer medium may not be necessary.

[0101] The ink may contain a mixture of at least two substances. Non-limiting examples of substances used in inks include water, sulfuric acid, hydrochloric acid, copper sulfate, potassium chloride, copper nitrate, copper chloride, copper cyanide, potassium hydroxide, potassium carbonate, nickel sulfate, nickel chloride, boric acid, and nickel sulfamate. The ink may also include one or more of the following: organic, ionic, and aqueous solvents (such as aqueous solutions, polar or nonpolar hydrocarbon solutions, eutectic solvents, inorganic hot melts, and ionic liquids), solid conductors of ions (such as superionic polymers and oxides), and supercritical fluids (such as CO2).

[0102] Inks may contain one or more additives to modify their liquid properties. Suitable additives include surfactants for modifying wetting properties, humectants for modifying viscosity, and cosolvents for modifying the solubility of ink components.

[0103] The molding electrode can be configured, for example, to deliver ink to the outward-facing surface of the molding electrode by jetting.

[0104] A suitable die electrode construction may include one or more of the following features: (i) A channel for delivering ink to a surface; (ii) A microfluidic circuit for delivering ink to a surface; (iii) porous structure; and (iv) Diaphragm.

[0105] The same die-cast electrode construction can also deliver ink to the device or substrate.

[0106] The device is configured for use with a series of devices or substrates.

[0107] The device or substrate may contain a conductive material. The device or substrate itself may act as an electrode, optionally as a counter electrode or working electrode. For example, the device or substrate may contain indium tin oxide (ITO), silicon, aluminum, carbon, steel, copper, gold, nickel, platinum, indium, or combinations thereof. Those skilled in the art will understand that the size and shape of the device or substrate can be selected for the pattern intended to be fabricated on the device or substrate. In some embodiments, the device or substrate may provide a substantially flat surface on which the pattern is formed. The device or substrate may be rigid or flexible.

[0108] The device or substrate may be able to retain an ion source or ion transfer medium on its surface. Suitablely, the device or substrate is shaped to retain an ion transfer medium on its surface.

[0109] Surface treatments can be applied to devices or substrates to alter the wettability of liquid ion sources deposited on the surface of devices or substrates.

[0110] The power source is configured to generate an electric field. Preferably, the power source creates a potential difference between the die-casting electrode and the device or substrate, allowing ions to flow from the ion source to the device or substrate and trigger an electrochemical reaction. More preferably, the potential difference facilitates electron transfer that triggers the electrochemical reaction. The voltage delivered by the power source can depend on many factors, including the reaction type, solvent, ion pair, temperature, pH, pressure, and electrode spacing.

[0111] Broadly speaking, the voltage used for copper deposition ranges from 0.2V to 15V, and suitably from 0.4V to 2V. Those skilled in the art will understand that other reactions may require negative voltages.

[0112] The power supply can deliver time-varying currents, including but not limited to AC signals, current value sequences, and / or ultrashort current pulses. Unbound by theory, it is believed that ultrashort pulsed currents (suitably with pulse lengths ranging from nanoseconds to milliseconds) can help localize the electric field by only locally polarizing / depolarizing the bilayer. The distance the transient electric field travels from the electrode on the die-casting electrode is proportional to the pulse time; therefore, shorter pulses translate into smaller fields, i.e., higher degrees of localization. More generally, ultrashort pulsed currents can also help improve reaction rates, uniformity, and control over the reaction. An AC signal superimposed on the plating voltage can improve the quality of the deposited film by disrupting the Debye layer and altering z-axis uniformity.

[0113] The ultrashort pulse current can be alternating current. Suitablely, the alternating current signal is superimposed on the voltage delivered to the die electrode.

[0114] Ultrashort pulse currents can have pulse lengths in the millisecond range. Suitablely, ultrashort pulse currents have pulse lengths in the range from nanoseconds to microseconds to milliseconds. The duty cycle of the pulse current can take values ​​in a wide range from less than 0.1% to close to one.

[0115] In a second aspect of the invention, a method is provided for forming a high-resolution patterned device or a high-resolution patterned substrate for a device using an apparatus, the apparatus comprising: a molding electrode having an outward-facing surface on which a mask having a predetermined pattern is applied; an ion source for supplying ions for forming a pattern on the device or substrate; and a power source for initiating ion movement between the ion source and the device or substrate, and an electrochemical reaction to form a pattern on the device or substrate, the method comprising: Provide devices or substrates; Positioning the molded electrode relative to the device or substrate to allow ions to move between the ion source and the device or substrate; and During an electrochemical reaction, a high current density greater than 10 kA / dm2 (or greater than 1 A / mm2) is delivered to a selected region of the device or substrate to generate an electric field, and / or the electrochemical reaction is confined to a region less than 200 μm wide of the device or substrate to form a pattern on the device or substrate, wherein the pattern is identical to or inverted from a predetermined pattern of a mask.

[0116] This method can be performed using the apparatus described previously.

[0117] This method is characterized by a spatially and temporally defined electrochemical reaction induced by an electric field. Unlike vector- or array-based additive manufacturing techniques that form patterns row by row or pixel by pixel, this reaction enables the formation of predetermined patterns on a device or substrate in the form of layers (e.g., in the form of imprinting).

[0118] The potential difference between the die-cast electrode and the device or substrate provides the impetus for the electrochemical reaction. The potential difference generates an electric field that drives the electrochemical reaction. This reaction can add, subtract, or modify materials on the device or substrate to form a predetermined pattern.

[0119] Electrochemical reactions can be one or more of the following: electrochemical deposition, etching, and / or in-situ transformation of solid materials on a device or substrate.

[0120] Deposition refers to the addition of solid material to the surface of a device or substrate, such as by electrochemically reducing a solid metal or electropolymerizing a polymer onto the surface. Etching refers to the removal of solid material from the surface of a device or substrate, such as by electrochemical oxidation and partial dissolution of solid material pre-existing on or on the surface of the device or substrate. In-situ transformation refers to any electrochemical reaction that suitably alters the surface of a device or substrate by reduction or oxidation without substantially adding or removing solid material from the device or substrate. Suitable techniques for achieving in-situ transformation include anodizing, surface functionalization, and photoresist development.

[0121] The method may include providing a device or substrate capable of retaining an ion source or ion transfer medium on its surface.

[0122] The method may include surface treatment of the device or substrate to alter the wettability of a liquid ion source deposited on the surface of the device or substrate.

[0123] The method may include providing a mask comprising a soft polymer conformable to the surface of a device or substrate. Suitably, the soft polymer conforms to the surface of the device or substrate by pressing it onto the surface of the device or substrate using a pressure suitably in the range of 0.01 MPa to 10 MPa.

[0124] This method may include applying a mask to the outward-facing surface of a molded electrode. During the electrochemical reaction, regions of the device or substrate located above the outward-facing surface of the molded electrode or the insulating region of the mask do not participate in the electrochemical reaction. Regions of the device or substrate located above the surrounding exposed conductive regions undergo the reaction.

[0125] The method may include applying or forming a mask directly onto the outward-facing surface of the molding electrode.

[0126] In an embodiment where the die-cast electrode includes a conductive base and an outward-facing conductor, the method includes applying or forming an insulating mask onto the conductor.

[0127] This method may include altering the morphology of the surface of the molded electrode. The step of altering the morphology of the molded electrode surface may be to provide a substantially planar or non-planar outward-facing surface of the molded electrode for initiating an electrochemical reaction.

[0128] The method may include altering the morphology of the outward-facing surface of the molding electrode to form a substantially planar outward-facing surface of the molding electrode. In this embodiment, the outward-facing surface may have a pattern reversed with that of the mask, such that a recessed pattern applied to the surface by the mask provides a substantially planar outward-facing surface of the molding electrode.

[0129] This method may include altering the morphology of the outward-facing surface of a molded electrode to form a substantially non-planar outward-facing surface of the molded electrode. This adapts to interactions with non-planar devices or substrates or with devices or substrates that have been previously electrochemically modified. This can be achieved through any one or more of the following operations: (i) Provide a molding electrode with a non-planar, outward-facing surface; (ii) Using a mask with varying thickness, the mask having conductivity opposite to the outward-facing surface of the molding electrode; and (iii) Selectively apply a mask to the surface of the die electrode to provide a surface morphology that mirrors the surface morphology of the device or substrate.

[0130] In embodiments where the outward-facing surface of the molded electrode comprises multiple discrete conductive regions, the method may include applying a current to each individual conductive region. Suitably, the method includes modulating the current applied to each individual conductive region to provide uniform electrochemical conditions across the entire device or substrate surface. More suitably, the step of modulating the current includes taking into account the voltage drop across each region.

[0131] The method may include providing a molded electrode formed of an inert material. Suitably, the method may include providing a molded electrode having a conductive base formed of an inert material.

[0132] The method may include providing a molded electrode comprising a conductor located between a base and an insulating mask. Preferably, the method includes providing a molded electrode comprising a conductor comprising an inert material located between a base and an insulating mask. More preferably, the method includes providing a molded electrode comprising a conductor made of an inert material different from the material of the base.

[0133] The method may include providing an ion transfer medium. Suitably, the method may include delivering the ion transfer medium to a platform.

[0134] The positioning step may include contacting the device or substrate with an ion source or ion transfer medium. The ion source or ion transfer medium forms a bridge between the electrode mold and the device or substrate, allowing ions to move between the two components.

[0135] This method may include positioning a device or substrate on a platform. The platform supports the device or substrate during the electrochemical reaction.

[0136] The positioning step may include moving the molding electrode such that it contacts or separates from the device or substrate from the electrode gap. Suitably, the positioning step may include moving a platform to adjust the position of the device or substrate relative to the molding electrode.

[0137] The method may include contacting a mask with a device or substrate. When an insulating material contacts the device or substrate, the inter-electrode gap (i.e., the gap between the molded electrode and the device or substrate) may be defined by the thickness of the mask.

[0138] This method may include maintaining an inter-electrode gap between the molded electrode and the device or substrate. Suitably, the gap is at most 1,000 μm. More preferably, the gap is less than 5 μm.

[0139] Minimizing the inter-electrode gap is based on the applicant's understanding that a smaller gap results in a proportionally larger electric field strength and a lower dielectric impedance, which in turn leads to a higher current density (and therefore a higher reaction rate) at a given potential voltage. For the same material quality, this significantly improves the deposition rate compared to conventional large-area electroplating.

[0140] This method may include applying an ion transfer medium to the surface of a device or substrate. Preferably, the method step includes immersing the device or substrate in the ion transfer medium.

[0141] The method may include positioning a device or substrate to retain an ion transfer medium on its surface.

[0142] This method may include providing ink as an ion source.

[0143] The method may include delivering an ion source to the outward-facing surface of a molding electrode. Suitably, the method includes delivering ink to the outward-facing surface of the molding electrode.

[0144] The method may include selectively wetting a region of the molding electrode to control the position of the ion transfer medium on the exposed surface of the molding electrode.

[0145] In embodiments where the ion transfer medium is ink, the method may include loading ink onto the surface of a molded electrode or target device or substrate. Suitably, the method includes delivering ink onto the device or substrate via one or more of the following methods: (i) Spraying; (ii) Channels in the molding electrode; (iii) Microfluidic circuits; (iv) porous structure; and (v) diaphragm.

[0146] The method may include selectively wetting areas of the outward-facing surface to control the position of the ink on the molding electrode.

[0147] The method may include determining the magnitude of the electric field by considering one or more of the following: the size and material of the molded electrode used, the size and material of the device or substrate, the conductivity of the ion transfer medium, the applied potential difference, and the inter-electrode gap between the molded electrode and the device or substrate.

[0148] This method may include measuring a time-varying current applied to create a potential difference between a device or substrate and a molding electrode. Measuring the current allows tracking the deposition rate to control the deposition thickness. It can also be used to optimize deposition parameters (such as inter-electrode gap, applied voltage, temperature, ink agitation, etc.) on a substrate-by-substrate or device-by-device basis. Suitably, the method includes measuring the current applied to create a potential difference between a device or substrate and a molding electrode at multiple intervals. The intervals are less than the pulse time. Suitable examples of time intervals are intervals of 1 μs to 10 seconds, 100 μs to 1 second, 1 ms to 1 second, or 0.1 seconds to 1 second. More appropriately, the time points are 1μs, 2μs, 5μs, 10μs, 20μs, 50μs, 100μs, 200μs, 500μs, 1ms, 2ms, 5ms, 10ms, 20ms, 50ms, 0.1 seconds, 0.2 seconds, 0.5 seconds, 1 second, 2 seconds, 5 seconds, or 10 seconds.

[0149] The method may include monitoring the current supplied to generate a potential difference.

[0150] This method may include closed-loop control of voltage and / or current.

[0151] The method may include: increasing the potential difference between the device or substrate and the molding electrode when the current is lower than a predetermined value, and / or decreasing the distance between the molding electrode and the device or substrate or the material applied to the device or substrate.

[0152] The method may include enhancing the electric field with a secondary field, which includes one or more of the following fields: a) Laser fields (pulsed and continuous); b) Magnetic field (pulsed and continuous); c) Ultrasonic fields (pulsed and continuous); d) Fluid field; and e) Secondary electric field (possibly through a dielectric).

[0153] This method may include: after forming an initial conductive pattern on a device or substrate, repeatedly applying a potential difference between the die-cast electrode and the two ends of the device or substrate. This enables the formation of a layered 3D conductive structure. Subsequent conductive patterns, suitably in the form of layers of conductive material, may partially or completely overlap with the previous conductive patterns.

[0154] The method may include connecting a power source such that the molding electrode is the anode and the device or substrate is the cathode.

[0155] In a third aspect of the invention, a method is provided for forming a patterned device or a patterned substrate for a device using an apparatus, the apparatus comprising: a molding electrode having an outward-facing surface on which a mask having a predetermined pattern is applied, wherein an insulating mask comprises a polymer selected for contacting and conforming to the surface of the device or substrate; an ion source for supplying ions for forming a pattern on the device or substrate; and a power source for generating a potential difference between the molding electrode and the device or substrate, the method comprising: Provide devices or substrates; To bring the mask into contact with the device or substrate so that the mask conforms to the surface of the device or substrate; and An electric field is generated by applying a potential difference between the die electrode and the device or substrate, thereby triggering an electrochemical reaction to form a pattern on the device or substrate, wherein the pattern is the same as or the inversion of a predetermined pattern of the mask.

[0156] The insulating mask may contain a soft polymer. The use of soft polymers is particularly advantageous for providing patterned devices or substrates with higher resolution.

[0157] In a fourth aspect of the invention, a method is provided for forming a patterned device or a patterned substrate for a device using an apparatus, the apparatus comprising: a molding electrode having an outward-facing surface on which a mask having a predetermined pattern is applied; an ion source for supplying ions for forming a pattern on the device or substrate; and a power source for generating a potential difference between the molding electrode and the device or substrate, the method comprising: Provide devices or substrates; Positioning the molded electrode relative to the device or substrate to allow ions to move between the ion source and the device or substrate; and A potential difference is applied between the die electrode and the device or substrate to generate an electric field and an ultrashort pulse current, thereby triggering an electrochemical reaction to form a pattern on the device or substrate, wherein the pattern is the same as or the inversion of a predetermined pattern of a mask.

[0158] One aspect of the present invention provides a method for forming a conductive patterned substrate for electronic devices.

[0159] This method involves locally electrochemically modifying a substrate to form a conductive pattern. The method is performed using a device including a molding electrode having an outward-facing conductive surface comprising an insulating mask with a predetermined pattern.

[0160] Electrochemical surface modification According to the present invention, substrate modification is achieved by subjecting the substrate surface to an electrochemical reaction. The electrochemical reaction may involve electrochemical deposition, etching, and / or in-situ transformation. Figure 1 (b) Exemplary illustrations of these reactions are provided.

[0161] Electrochemical reactions can be initiated by creating a potential difference across a solution containing a precursor. This allows ions to flow from the ion source to the substrate and trigger the electrochemical reaction. For copper deposition, this would consist of a precursor solution containing dissolved copper ions, which are driven toward the substrate surface by an electric field and reduced to solid copper on the surface.

[0162] Figure 1 Reaction 1 in (b) illustrates an additive reaction involving the deposition of conductive solid material 10 onto the surface of substrate 12. Material deposition can occur via the electrochemical reduction of metal cations or the deposition of solid metal onto the substrate surface.

[0163] Figure 1 Reaction 2 in (b) illustrates a subtractive reaction in the form of etching. This reaction involves removing solid material 10 from the surface of substrate 12 to leave patterned solid material 13. The etching process can occur through electrochemical oxidation and partial dissolution of the substrate surface.

[0164] Figure 1 Reaction 3 in (b) illustrates an in-situ transformation reaction involving alteration of the chemical and / or physical properties of the solid material 10 deposited on the substrate. The transformation can occur via a variety of reactions, including reduction, oxidation, conjugation, and functionalization, without substantially adding or removing material from the substrate. Figure 1 In (b), the central portion 14 of the solid material 10 is transformed into a different material.

[0165] Patterned die-cast electrodes The reaction is initiated by an electric field that enables ions to flow toward and / or out of the substrate. The electric field is generated by a device comprising: a molding electrode; a platform for supporting the substrate; an ion source for supplying ions for forming a conductive pattern; and a power source for generating the electric field by creating a potential difference between the molding electrode and the substrate.

[0166] The key component of this device is the molding electrode, which includes a conductive base and an outward-facing insulating mask with a predetermined pattern. The molding electrode, including the insulating mask, enables the inverted pattern to be copied onto a substrate.

[0167] In one example, the die electrode is formed from a metal sheet to provide a conductive body on which an insulating mask is applied.

[0168] The molded electrode may have a substantially flat, outward-facing surface. Alternatively, the morphology of the electrode surface may be manipulated to accommodate interaction with a non-planar substrate or with a previously electrochemically modified substrate, thereby forming an initial conductive pattern on the substrate, which will be further modified, for example, by additive or subtractive processes.

[0169] The choice of material used to form the insulating mask may depend on the method of patterning the substrate.

[0170] In the first example, a contactless technique is used to form the pattern, wherein an inter-electrode gap is maintained between the die-casting electrode and the substrate during the duration of the patterning step. In this example, the insulating mask can be formed from a wide variety of materials, encompassing mechanically rigid (i.e., exhibiting high Young's modulus) materials and mechanically flexible and / or elastic (i.e., exhibiting low Young's modulus) materials.

[0171] In the second example, a contact technique is used to form the pattern, wherein the die-casting electrode contacts the substrate during the duration of the patterning step. In this example, the die-casting electrode may include an insulating mask that protrudes from the outward-facing surface of the electrode to create an enclosed region for the reaction and precisely sets the inter-electrode gap.

[0172] To improve the reaction process within these enclosed regions, soft polymers, typically with a Young's modulus of less than 30 MPa, can be used for the insulating mask. The soft polymer allows the insulating mask to deform upon contact with the substrate and conform to the substrate surface to enhance the seal between the die-casting electrode and the substrate. This improved seal is particularly important for forming patterned substrates with higher resolution.

[0173] In use, the region of the substrate overlapping with the insulating mask is isolated from the electrochemical reaction and remains essentially unmodified. The substrate region overlapping with the conductive electrode material participates in the electrochemical process. Figure 1(a) illustrates an example of a pattern formed on the outward-facing conductive surface of a molded electrode by an insulating mask 16. The reaction occurs on the exposed, unshaded area 18 of the surface, while the covered, shaded area of ​​the electrode surface is protected from the reaction.

[0174] Figure 2 An exemplary illustration of a suitable molding electrode is provided.

[0175] Figure 2 The electrode 1 includes a metal base 20 and an outward-facing insulating coating 22 with a predetermined pattern that is in direct contact with the base.

[0176] Figure 2 Electrode 2 is a variation of electrode 1, and it further includes an inert conductor 24 sandwiched between the metal base 20 and the insulating mask 16. In this electrode, the insulating mask 16 is in direct contact with the inert conductor 24.

[0177] Figure 2 Electrode 3 is a variation of electrode 1, wherein the surface of the metal base 20 is wavy, and the recesses on the wavy surface are occupied by an insulating mask 16 to form a substantially flat, outward-facing conductive surface.

[0178] Figure 2 Electrode 4 is a variation of electrode 3, and it also includes an inert conductor 24 sandwiched between the metal base 20 and the insulating mask 16. The inert conductor 24 is conformable to the contour of the metal base 20, and the insulating mask 16 fills the recesses formed on the inert conductor 24 to form a substantially flat, outward-facing conductive surface.

[0179] Figure 2 Electrode 5 is a variation of electrode 2, wherein the inert conductor 24 and the insulating mask 16 are coplanar and form a substantially flat, outward-facing molded electrode surface.

[0180] Figure 2 The electrode 6 has a conductive metal base in the form of a pair of structures 28 with an I-shaped cross-section embedded within the insulator body 30. The exposed areas of the conductive metal base are covered with an inert conductor 24 to form a non-planar pattern.

[0181] Figure 2 Electrode 7 is a variation of electrode 1, wherein the insulating mask includes a soft polymer 32 configured to contact and conform to the surface morphology of the substrate.

[0182] Figure 2 Electrode 8 is a variation of electrode 7, wherein an inert metal conductor 24 is sandwiched between a metal base 20 and a soft polymer 32.

[0183] Figure 2Electrode 9 is a pre-plated variant of electrode 8, which includes deposit 34.

[0184] Figure 2 Electrode 10 is a variation of electrode 6, wherein a plurality of channels 36 extend through insulator body 30 for spraying ink onto substrate 12.

[0185] Figure 2 The electrode 11 includes a conductive metal base 20 covered with an inert conductor 24 and having a porous structure that allows ink and ions to flow through the metal base. The metal base is embedded within an insulator body 30, which has an inward-facing surface shaped as a container for holding a volume of ink 38.

[0186] Device The molding electrode is a component of the apparatus according to the invention, which enables the production of conductive patterned substrates. Another component of the apparatus is a substrate on which conductive patterns are formed.

[0187] In one embodiment, the substrate is formed of a conductive material, which may include one or more of indium tin oxide (ITO), silicon, aluminum, steel, gold, or combinations thereof. The substrate has a rigid planar surface on which the conductive pattern is imprinted.

[0188] The molding electrode and the substrate form a cathode-anode pair, where the molding electrode is the anode and the substrate is the cathode.

[0189] The device also includes an ion source for providing ions to form a conductive pattern. The ion source can be a solid material deposited on the molding electrode or a part of the molding electrode.

[0190] Alternatively, the ion source is an ion-containing fluid, preferably an ion-containing liquid. For example, Figure 2 The illustration of electrodes 10 and 11 shows an ion source in the form of ink 38. One advantage of using ink as an ion source is that the electrochemical reaction does not require a separate ion transfer medium.

[0191] Inks may include water, sulfuric acid, hydrochloric acid, copper sulfate, potassium chloride, copper nitrate, copper cyanide, potassium hydroxide, potassium carbonate, nickel sulfate, nickel chloride, boric acid, and nickel aminosulfonate.

[0192] Another component of the device is a power source that generates a potential difference between the molding electrode and the substrate, allowing ions to flow from the ion source to the substrate. This potential difference also facilitates electron transfer that triggers the electrochemical reaction. Figure 3 An example of a molding electrode in operation is shown, which illustrates electric field lines radiating from the inert conductor 24.

[0193] The device also includes a platform for supporting a substrate, which may be in the form of a container that may contain a liquid ion source and / or an ion transfer medium.

[0194] method This invention provides two main methods for forming conductive patterned substrates.

[0195] Contactless technology The first method is a contactless technique, in which an inter-electrode gap is maintained between the molding electrode and the substrate during the patterning step. During the patterning step, the molding electrode avoids contact with the substrate.

[0196] Figure 4 Examples of using including Figure 2 The device for electrode 5, and the rapid layer manufacturing process performed using contactless technology.

[0197] Step 1 involves loading ink 38 onto the outward-facing surface of a molding electrode, which includes conductors 24 and an insulating mask 16 arranged coplanarly. Different areas of the surface can be selectively wetted to control the position of the ink on the molding electrode.

[0198] Depending on the patterning pattern, the next step in this process can be either step 2A or step 2B. Step 2A involves a deposition patterning step, and step 2B involves an etching patterning step.

[0199] Depositional Patterning In step 2A, the molding electrode is positioned above the substrate 12 and pressed down until ink 38 forms a fluid bridge between the molding electrode and the substrate 12. In some embodiments, the device is configured to position the molding electrode to form a predetermined gap between the molding electrode and the substrate 12. The applicant intentionally utilizes a very small inter-electrode gap to significantly improve the deposition rate.

[0200] In step 3A, a potential difference is applied between the molding electrode and the substrate to deposit solid material 10 onto the region of the substrate that overlaps with the inert conductor 24 to form a pattern that is the inverse of the pattern of the insulating mask.

[0201] In step 4A, the die-casting electrode is removed and the patterned substrate including the deposited material 10 is washed to obtain the final product.

[0202] Etching Patterning In step 2B, the molding electrode is positioned above the substrate 12 having a pre-existing conductive material layer 10. The molding electrode is pressed down until ink 38 forms a bridge between the molding electrode and the pre-existing conductive material layer 10.

[0203] In step 3B, a potential difference is applied between the molding electrode and the substrate. This causes the region of the pre-existing conductive material layer 10 that overlaps with the inert conductor 24 to dissolve, thereby etching a pattern into the conductive material and forming a patterned conductive solid material 13.

[0204] In step 4B, the molding electrode is removed and the substrate 12 is washed to obtain the final product.

[0205] Contact technology The second method is contact technology, in which an insulating mask contacts the substrate during the duration of the patterning step.

[0206] An insulating mask protrudes from the outward-facing surface of the electrodes and encloses the conductive region of the outward-facing surface for electrochemical reactions. The mask can be made of rigid or soft materials. One advantage of using a rigid material as the mask is that it can be used to precisely set the inter-electrode gap.

[0207] Alternatively, if a higher resolution patterned substrate is required, the mask can be made of a soft material, typically with a Young's modulus of less than 30 MPa. The flexibility of the mask allows the insulating mask to better conform to the surface of the substrate and creates a better seal around the conductive areas on the outward-facing surface.

[0208] In operation, the die-casting electrode is positioned above the substrate and pressed down until the insulating mask contacts the substrate. A potential difference is then applied between the die-casting electrode and the substrate to deposit a solid material, such as copper, which is suitably derived from an ink or ion transfer medium. The ink may contain one or more of the following substances in the exposed area around the insulating mask leading to the electrode: water, sulfuric acid, hydrochloric acid, copper sulfate, potassium chloride, copper nitrate, copper cyanide, potassium hydroxide, potassium carbonate, nickel sulfate, nickel chloride, boric acid, and nickel sulfamate.

[0209] Subsequently, the molding electrode is removed and the patterned substrate is washed to obtain the final product.

[0210] Contact technology offers two main advantages over contactless technology.

[0211] The first advantage is the ability to mechanically level the deposited material on the substrate prior to the electrochemical reaction. This can improve the structural integrity of the final product by compacting the deposited material.

[0212] The second advantage is improved resolution of the final product. This is because the contact between the insulating mask and the substrate or a pre-existing conductive layer on the substrate confines the reaction medium to the region below the conductive area of ​​the die electrode and provides a clear edge definition to the electric field at the end of the reaction medium. This, in turn, reduces undesirable reactions such as over-deposition and damage or contamination of the target surface under the insulating mask.

[0213] Using a soft insulating mask offers additional benefits, including less force required for contact, better sealing of the reaction area for greater field localization, and higher feature resolution.

[0214] Figure 5 and Figure 6 It is an image showing the resolution difference between patterned substrates formed by contact and contactless techniques. Figure 6 The pattern (i.e., the fine lines) in the image has a resolution of approximately 5 μm, while Figure 5 The pattern (i.e., the blurred lines) in the image has a resolution of approximately 1 mm.

[0215] Ultrashort current pulse To improve the localization (and resolution) of electrochemical reactions in both contact and non-contact technologies, the power source can deliver ultrashort current pulses during the electrochemical reaction. Ultrashort pulsed currents (typically alternating currents with pulse lengths in the millisecond range) are thought to aid in localizing the electric field by locally polarizing / depolarizing only the bilayer. More generally, ultrashort pulsed currents can also help improve reaction rates, uniformity, and control over the reaction.

[0216] Example In one example, an apparatus according to the invention, comprising the following components, can be used to form a printed circuit board (PCB).

[0217] • Molded electrode: This comprises a highly doped silicon wafer cut to the size of the target PCB design (100mm × 100mm), with an inert platinum layer on both the top and bottom surfaces. The outward-facing surface of the silicon wafer (where the reaction occurs) has been patterned with a raised photoresist layer. This layer serves both as a field confinement and as an isolator for uniformly setting the inter-electrode gaps across the entire mold. Suitably, the photoresist layer contains a corrosion-resistant polymer, such as SU8.

[0218] • Ion source: Aqueous solution of copper sulfate precursor, pH adjuster and other additives for enhancing adhesion and surface quality.

[0219] • Substrate: ITO glass • Current: tens of amperes.

[0220] • Potential difference and electric field parameters: 60μm IEG, 30μm deposition thickness, 2V voltage, 67kV / m electric field strength.

[0221] • Ultra-short pulse current value and duration: 1µs to turn on, 10µs to turn off.

[0222] This device can be used to form PCBs using contact technology.

[0223] An ink containing an aqueous solution of copper sulfate precursor, pH adjuster, and other additives for enhancing adhesion and surface quality is applied to an ITO glass substrate.

[0224] Position the molding electrode above the substrate and press it down until the insulating layer (i.e., the mask) contacts the substrate. Apply pressure in the range of 0.01 MPa to 10 MPa to ensure that the mask conforms to the surface of the substrate.

[0225] The power supply is used to deliver a voltage of 2V to generate an electric field strength of 67kV / m. This triggers an electrochemical reaction that deposits copper onto the exposed areas of the electrodes around the insulating mask.

[0226] Subsequently, the molded electrode is lifted off the substrate, and the patterned substrate is washed to obtain the final product.

[0227] Figure 7A 、 Figure 7B 、 Figure 7C Figure 7A This is a side cross-sectional view of a molded electrode 700, which includes an insulating substrate 702, an electrode 710, and an insulating pattern 712. In one example, the molded electrode has two main surfaces: a first main surface 714 and a second main surface 716. The first main surface is an outward-facing surface (also referred to as the front side of the molded electrode), and the second main surface is opposite to the first main surface and is referred to as the rear surface of the molded electrode. In one example, the first main surface of the molded electrode (e.g., the outward-facing surface or the front side) is the side of the molded electrode that is placed in close proximity to the substrate on which a conductive element will be formed, and the second main surface of the molded electrode (e.g., the rear side) is the opposite side of the molded electrode.

[0228] In one example, the insulator substrate 702 may be a reference. Figure 1 The described substrate 12 and reference Figure 2 The described insulator 30 is a similar insulating material. For example, the insulating substrate may be made of a flexible polymer (such as polydimethylsiloxane (PDMS) or polyimide or FR4) or a more rigid insulating material (such as glass or ceramic). In one example, the substrate may be 20 μm to 2 mm thick.

[0229] Each electrode in electrode 710 may be formed of a conductive material (such as a metal, including, for example, copper, nickel, platinum, gold, silver, ruthenium, tungsten; or a conductive nonmetal, such as SiN, TiN, ITO, or Si). Each electrode may be formed using, for example, metal deposition techniques (such as electroplating, plasma-enhanced chemical vapor deposition (PECVD), sputtering, evaporation), but other techniques are also possible. Figure 7A In the example, there are two discrete electrodes that can be controlled independently of each other. That is, current can be applied independently to each of the two electrodes. Each of the two electrodes includes a front portion 720, a rear portion 722, and a conductive element 724 (e.g., a conductive via and / or conductive trace) that electrically couples the front portion of the electrode to the rear portion of the electrode. The front portion of each electrode is in Figure 7A The middle part is shown as being located at the bottom of the molding electrode, and the rear portion of each electrode is in Figure 7A It is shown as being positioned at the top of the molding electrode.

[0230] The insulating pattern 710 may be an insulating material, such as a photoresist material or a hard dielectric (such as SiO2), which is deposited as an insulating layer on a first primary surface of the mold (e.g., the front or outward-facing side) and then patterned using photolithography or other patterning techniques (such as nanoimprint lithography or direct writing). The insulating pattern defines a feature 726 corresponding to a conductive element to be formed on the substrate. For example, the conductive element may be a conductive pad, bump, or trace formed on the substrate to conduct electricity. In one example, the feature defined by the insulating pattern may have a size in the nanometer or micrometer range. For example, the feature may define a two-dimensional region (e.g., from a planar view) corresponding to a conductive pad having a large size range (between 200 nm and 100 mm (e.g., by side length or by diameter)) or a conductive trace, for example, 20 nm to 100 nm wide or 1 micrometer to 20 micrometer wide, depending on the application. Furthermore, conductive traces can have narrow widths but can be very long, for example, on the order of centimeters or meters or longer. In one example, the feature is defined by the absence of material in the insulating pattern, allowing current to flow from the electrode through an ion transport medium (such as an electrolyte) and onto the target substrate where the conductive element will be formed. That is, the area without insulating material (e.g., photoresist) is the area defining the feature of the insulating pattern.

[0231] Figure 7B This is a plan view of an example of the front side of the molding electrode 701, showing various features 728 formed by the insulating pattern at the front side of the molding electrode. Figure 7BIn the plan view, the feature portion of the pattern is defined by areas lacking the insulating material that forms the insulating pattern (e.g., lacking photoresist). In one example, portions of one or more electrodes are visible at the feature portion (e.g., areas of the insulating pattern lacking photoresist). Figure 7B As shown, depending on the desired application, various features of different shapes and sizes can exist on the front side of the molding electrode. It should be noted that... Figure 7B The number, shape, and layout of the features shown are for illustrative purposes only.

[0232] Figure 7C This is a plan view of an example of the rear side of a molding electrode, showing a portion of one or more electrodes 723. For clarity, all twelve rear portions of electrode 723 are not labeled with reference numerals. Figure 7C The example illustrates a portion of multiple electrodes and an insulating substrate. The electrodes can be multiple different electrically isolated electrodes that can be individually controlled, or the electrodes can be connected via electrodes from... Figure 7C One or more portions of the planar diagram that are not visible are all electrically coupled to each other. In one example, each electrode visible on the rear side of the molding electrode corresponds to a different discrete conductive region of the molding electrode. For example, in Figure 7C The rear portion of the electrode shown at the rear side of the molding electrode corresponds to the front portion of the same electrode at the front side of the molding electrode.

[0233] Although reference Figure 7A , Figure 7B and Figure 7C An example of an electrode has been described, but other electrode configurations are possible. Additionally, Figure 7B and Figure 7C The plan view shown may not necessarily represent the same molding electrode. However, the plan view may correspond to the same molding electrode. In one example, Figure 7A and Figure 7B This represents four electrically independent electrodes, namely electrodes 1, 2, 3, and 4. Specifically, Figure 7A Four feature portions defined by an insulating pattern are shown, namely feature portions 1, 2, 3, and 4, which expose the front portions of four electrically independent electrodes, and Figure 7B The rear side of the molding electrode is shown, illustrating the rear portions of the same four electrodes 1, 2, 3, and 4. (See image.) Figure 7B and Figure 7C As illustrated, the front portion of an electrode is not necessarily spatially aligned with the rear portion of the same electrode, but the front and rear portions are electrically coupled to each other, for example, via vertical and / or horizontal conductive traces (not shown). In one example, a feature formed by an insulating pattern may define a three-dimensional region, which includes, for example, length and width dimensions (e.g., from a plan view, Figure 7B) and depth dimensions (e.g., from a side view, Figure 7A ).

[0234] Figure 8A / Figure 8B As described above, the molded electrode may include multiple discrete conductive regions, wherein the potential and current of each region can be modulated independently. Figure 8A This is a plan view of an example of the front side of the molding electrode 800, showing a plurality of discrete conductive regions 830, each of which has various features 826 formed by an insulating pattern at the front side of the molding electrode. Figure 8A In the plan view, there are eight discrete conductive regions, and the feature portion of the insulating pattern in each discrete conductive region is defined by a region lacking the insulating pattern (e.g., lacking photoresist), such that portions of one or more electrodes are exposed at the feature portion region. Figure 8A In the plan view, areas that are not pattern features are covered by an insulating material (such as photoresist). Figure 8A As shown, various features of different shapes and sizes can be present on the front side of the molding electrode, depending on the desired application. Although different features are shown in each conductive region of the molding electrode, the features do not necessarily need to be divided according to the conductive region.

[0235] Figure 8B It comes from Figure 8A A plan view of an example of the rear side of the molding electrode 800, showing a portion of electrode 820 of the molding electrode. Figure 8B In the example, a portion of multiple electrodes and a substrate are shown, and discrete conductive regions 830 are shown with Figure 8A The discrete conductive regions 830 shown are aligned such that the front portion of the electrode and the rear portion of the same electrode are electrically coupled to each other via, for example, vertical and / or horizontal conductive elements (not shown). Figure 8B In the example, one electrode corresponds to one discrete conductive region, allowing the potential and current to be individually controlled within each discrete conductive region. For instance, one electrode in a conductive region is used to apply potential and current to that region, enabling conductive elements corresponding to patterned features to be formed on the substrate. Figure 8A and Figure 8B In one example, the discrete conductive regions 830 are vertically aligned with each other, but in other examples, the rear portion of the electrode is not vertically aligned with the front portion of the electrode.

[0236] Figure 9 In some examples, the area occupied by the electrode on the front side of the die electrode is much larger than the size of the conductive elements (e.g., bumps and / or traces) that will be formed on the substrate based on the current applied from the electrode. Figure 9This is a side cross-sectional view of a molding electrode 900, which includes an insulating substrate 902, two electrodes 910, and an insulating pattern 912. In this example, the area occupied by each of the two electrodes is much larger than the size of the feature 926 defined by the insulating pattern. In one example, the feature defined by the insulating pattern may have a size in the nanometer or micrometer range. For example, the feature may include a conductive pad or conductive trace 20 nanometers to 100 nanometers wide or 1 micrometer to 20 micrometers wide, while the front portion of the electrode has a larger area than the feature and can be as large as several square centimeters. Additionally, the conductive trace may have a narrow width but can be very long, for example, on the order of centimeters or meters or longer.

[0237] As described above, refer to Figure 9 The described molding electrode 900 has two main surfaces: a first main surface 916 and a second main surface 914. The first main surface is the outward-facing surface (also referred to as the front side), and the second main surface is opposite to the first main surface and is referred to as the rear surface. Electrode 910 consists of two discrete electrodes that can be independently controlled. Each of the two electrodes includes a front portion 922, a rear portion 720, and a conductive via 724 electrically coupling the front portion to the rear portion. In one example, both electrodes have rectangular occupancy areas at both the front and rear sides of the molding electrode. Figure 9 In the example, for each electrode, the area occupied by a portion of the electrode on the front side of the molding electrode is much larger than the area occupied by a portion of the electrode on the rear side of the molding electrode, although in other examples the reverse is true. Furthermore, although in Figure 9 In the example, a portion of the electrode on the front side of the molding electrode is vertically aligned with a portion of the electrode on the rear side of the molding electrode, but the front and rear portions of the same electrode do not necessarily need to be vertically aligned. For example, a portion of the electrode on the front side of the molding electrode can be electrically coupled to a portion of the electrode on the rear side of the molding electrode via vertical and / or horizontal conductive traces.

[0238] Figure 10 Figure 10 Is with Figure 2 The examples of electrodes 10 and 11 shown are similar to the example of a molded electrode 1000 in a side sectional view. Figure 10 In one example, there are two channels 1040 that extend from the front side of the molding electrode through the insulating substrate 1002 to the rear side of the molding electrode near the electrode 1010. In one example, fluid can move in either direction through the channels. In one example, fluid is pumped through a first channel into the space 1042 between the molding electrode 1000 and the substrate 1044, and fluid exits the space between the molding electrode and the substrate through a second channel.

[0239] Figure 11A / Figure 11B Figure 11A This is a plan view of an example of the front side of the molding electrode 1100, showing a plurality of features 1126 formed by an insulating pattern, an end 1141 of each of the four fluid channels, and the outline of the front portion 1122 of the electrode. Figure 11B It comes from Figure 11A A plan view of an example of the rear side of the molding electrode 1100, showing the opposite ends 1143 of each of the four fluid channels and the rear portion 1120 of the electrode visible at the rear side of the molding electrode. Figure 11B The outline of the front portion 1122 of the electrode at the front side of the molding electrode is also shown, which is not normally visible at the front side of the molding electrode. Figure 11A and Figure 11B In the example, the fluid channels are located around the periphery of the electrode, although this is not necessary. One or more fluid channels may be positioned relative to feature 1126 in other ways designed to enhance the performance of the process for forming conductive elements on the substrate. The fluid channels may be similar to Figure 2 The fluid channels and / or references in electrodes 10 and 11 shown Figure 10 The fluid channel described.

[0240] Figure 12 Figure 12 It is a reference Figure 10 , Figure 11A and Figure 11B The described example is a side sectional view of a similar compression molding electrode 1200. Figure 12 In one example, there are two channels 1240 that extend from the front side of the molding electrode through the insulating substrate 1202 to the rear side of the molding electrode, and through the front portion 1222 of the electrode located on the front side of the molding electrode. In one example, fluid can move in either direction through the channels. In one example, fluid is pumped through a first channel into the space 1242 between the molding electrode 1200 and the substrate 1244, and fluid exits the space between the molding electrode and the substrate through a second channel.

[0241] Figure 13 Figure 13 This is a plan view of an example of the front side of the molding electrode 1300, showing the outline of one end 1341 of multiple fluid channels and the front portion 1322 of the two electrodes. For clarity, Figure 13 The plan view of the front side of the die electrode does not include features that can be formed by insulating patterns. Figure 13The examples illustrate various possibilities for the fluid channel. Regarding the shape of the fluid channel, it is shown as having a circular cross-section and a linear cross-section, but other cross-sectional shapes are also possible. As for the location of the fluid channel, it can be located outside the occupied area of ​​the front portion of the electrode (e.g., as shown in the example). Figure 10 (as shown), or the fluid channel may be located within the area occupied by the front portion of the electrode (e.g., as shown). Figure 12 (As shown). In one example, the fluid channel is configured such that an ion source (such as ink) can be delivered to the vicinity of a feature (not shown) in an insulating pattern, and / or configured to provide a nearby exit path for excess fluid when an electrode die is placed in close proximity to the substrate on which a conductive element will be formed.

[0242] Figure 14A 、 Figure 14B 、 Figure 14C Figure 14A This is a side cross-sectional view of a molding electrode 1400, which includes an insulating substrate 1402, two electrodes 1410, and an insulating pattern 1412 defining a feature portion 1426. In one example, the molding electrode has two main surfaces, namely a first main surface and a second main surface, the first main surface being the outward-facing surface (also referred to as the front side of the molding electrode), and the second main surface being opposite the first main surface and referred to as the rear surface of the molding electrode. Each of the two electrodes has a front portion 1422, a rear portion 1420, and a conductive element 1424 electrically coupling the front portion of the electrode to the rear portion of the electrode. Figure 14A As shown, the front part of the electrode is electrically coupled to the rear part of the corresponding electrode through a combination of vertical through-holes and horizontal traces.

[0243] Figure 14B This is a plan view of an example of the front side of the compression molding electrode 1401, showing the outlines of the front portion 1422 of the four electrodes and the rear portion 1420 of the four electrodes. Figure 14C It comes from Figure 14B This is a plan view of an example of the rear side of a molding electrode, showing the outlines of the rear portion 1420 of the four identical electrodes and the front portion 1422 of the four electrodes. Note that, for clarity, the plan view of the front side of the molding electrode does not show the insulating pattern and corresponding features. Figure 14B and Figure 14C In the example shown, the front portion of the electrode and the corresponding rear portion of the electrode can be connected via conductive element 1424 (such as reference 1424). Figure 14A The described conductive elements are electrically coupled to each other. The conductive elements that electrically couple the front portion of the electrode to the rear portion of the electrode... Figure 14B and Figure 14C The dashed line indicates this. For example... Figures 14A to 14CAs illustrated, from a plan view perspective, the front portion of the electrode can be offset from the rear portion of the electrode, which provides flexibility in electrode layouts that may include many different molded electrodes that can be individually controlled. (See reference...) Figures 14A to 14C In the described example, electrodes 1, 2, 3, and 4 each correspond to a discrete conductive region that is electrically insulated from each other. That is, current does not flow between the four different electrodes corresponding to the four discrete conductive regions. Figures 14A to 14C In the example, Figure 14A The die electrode 1400 shown is not necessarily the same as... Figure 14B and Figure 14C The die electrode shown is the same die electrode 1401, but it can be the same die electrode.

[0244] Figure 15A 、 Figure 15B 、 Figure 15C Figure 15A This is a side cross-sectional view of a molding electrode 1500, which includes an insulating substrate 1502, two electrodes 1510, and an insulating pattern 1512 defining a feature portion 1526. In one example, the molding electrode has two main surfaces, namely a first main surface and a second main surface, the first main surface being the outward-facing surface (also referred to as the front side of the molding electrode), and the second main surface being opposite to the first main surface and referred to as the rear surface of the molding electrode. Each of the two electrodes has a front portion 1522, a rear portion 1520, and a conductive element 1524 electrically coupling the front portion of the electrode to the rear portion of the electrode, but the rear portion of one of these electrodes and the corresponding conductive element for that one electrode are in... Figure 15A It is not visible in the side sectional view.

[0245] Figure 15B This is a plan view of an example of the front side of the molding electrode 1501, showing the outline of the feature portion 1526 defined by the insulating pattern and the front portion 1522 of the four electrodes of the molding electrode. Figure 15C It comes from Figure 15B A plan view of an example of the rear side of a molding electrode, showing the outlines of the rear portion 1520 of the four identical electrodes and the corresponding front portion 1522 of the four electrodes. Figure 15B and Figure 15C In the example shown, the front portion of the electrode and the corresponding rear portion of the electrode can be connected via conductive vias (such as reference septums). Figure 15A The described conductive vias are electrically coupled to each other. In one example, the conductive via electrically couples the front portion of an electrode to the rear portion of the electrode. Figure 15B and Figure 15C A vertical through hole, not shown in the diagram. (Example) Figures 15A to 15CAs illustrated, from a plan view perspective, the front portion 1520 of the electrode can be offset from the rear portion 1522 of the electrode, which provides flexibility in electrode layouts that may include many different molded electrodes that can be individually controlled. Figures 15A to 15C In the example, Figure 15A The die electrode 1500 shown may not necessarily be the same as... Figure 15B and Figure 15C The die electrode shown is the same die electrode 1501, but it can be the same die electrode.

[0246] Although specific embodiments of the invention have been described and illustrated, the invention is not limited to the particular form or arrangement of the components so described and illustrated. The scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An apparatus for forming a conductive element on a substrate, the apparatus comprising: Insulating substrate; Electrode, the electrode being integrated with the insulating substrate; and An insulating pattern is formed on the electrode, wherein the insulating pattern defines a feature corresponding to the conductive element to be formed on the substrate.

2. The apparatus of claim 1, wherein the electrode has a two-dimensional occupied area on the outward-facing surface of the apparatus, and wherein a plurality of features are located within the two-dimensional occupied area on the outward-facing surface of the apparatus.

3. The device according to claim 1, wherein the electrode has a two-dimensional occupied area at the front side of the device, and wherein a plurality of features are located within the two-dimensional occupied area at the front side of the device.

4. The device according to claim 1, wherein the electrode has a front portion having a two-dimensional area at the front side of the device and a rear portion having a two-dimensional area at the rear side of the device, and wherein the two-dimensional area of ​​the rear portion of the electrode is greater than the two-dimensional area of ​​the front portion of the electrode.

5. The apparatus of claim 1, wherein the insulating pattern comprises an insulating layer of insulating material, and wherein the feature is formed by photolithography.

6. The apparatus of claim 1, wherein the feature has a size on the order of micrometers.

7. The device according to claim 1, wherein the feature has a size on the nanometer scale.

8. The apparatus of claim 1, further comprising a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions on the outward-facing side of the apparatus.

9. The device of claim 1, further comprising a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions on the front side of the device.

10. The apparatus of claim 1, further comprising a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions on the outward-facing surface of the apparatus, and wherein the electrodes are configured to be independently modulated with potential and current.

11. The apparatus of claim 1, further comprising a plurality of electrodes, wherein the electrodes correspond to discrete conductive regions at the front side of the apparatus, and wherein the electrodes are configured to be independently modulated by potential and current.

12. The apparatus of claim 1, further comprising a fluid channel within the insulating substrate, wherein an end of the fluid channel is located on the outward-facing side of the apparatus.

13. The apparatus of claim 1, further comprising a fluid channel extending from the front side of the apparatus through the insulator substrate to the rear side of the apparatus, wherein the fluid channel is configured to provide an ion source to the front side of the apparatus.

14. The apparatus of claim 1, further comprising a fluid channel through the insulating substrate, wherein the fluid channel is configured to provide an ion source to an outward-facing side of the apparatus in the vicinity of the electrode.

15. An apparatus for forming a conductive element on a substrate, the apparatus comprising: Insulating substrate; An electrode, said electrode being integrated with said insulating substrate, wherein said electrode corresponds to a discrete conductive region of said device; and An insulating pattern is formed on the electrode, wherein the insulating pattern defines a feature corresponding to the conductive element to be formed on the substrate.

16. The apparatus of claim 15, wherein each of the electrodes has a front portion having a two-dimensional area at the front side of the apparatus and a rear portion having a two-dimensional area at the rear side of the apparatus, and wherein each of the electrodes is individually controllable.

17. An apparatus for forming a high-resolution patterned substrate for a device, the apparatus comprising: A molded electrode is configured to form a pattern on a substrate, the electrode having an outward-facing surface on which a mask with a predetermined pattern is applied, wherein the molded electrode is further configured to confine an electrochemical reaction to a region less than 200 μm wide on the substrate, or to deliver a high current density greater than 10 kA / dm² (or greater than 1 A / mm²) to a selected region of the substrate during the electrochemical reaction; An ion source for supplying ions to form patterns on a substrate; and A power source is provided to initiate the movement of ions between the ion source and the substrate, as well as an electrochemical reaction, to form the pattern on the substrate, wherein the pattern is the same as or an inversion of the predetermined pattern of the mask.

18. A method of forming a high-resolution patterned substrate for a device using an apparatus, the apparatus comprising: A molding electrode having an outward-facing surface on which a mask with a predetermined pattern is applied; An ion source for supplying ions to form patterns on a substrate; The method includes a power source for initiating ion movement between the ion source and the substrate, and an electrochemical reaction to form the pattern on the substrate. Provide substrate; Positioning the molding electrode relative to the substrate such that ions can move between the ion source and the substrate; and During the electrochemical reaction, a high current density greater than 10 kA / dm2 (or greater than 1 A / mm2) is delivered to a selected area of ​​the substrate to generate an electric field, and / or the electrochemical reaction is confined to a region of the substrate less than 200 μm wide to form the pattern on the substrate, wherein the pattern is the same as or inverted from the predetermined pattern of the mask.

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