Atomic layer process printer

Abstract

The invention relates to an atomic layer process printer. The present invention relates to an atomic layer process printer for atomic scale material deposition, etching and / or cleaning in selected regions. In the atomic layer process printer, a printer head plate (104) is removably attached to a printer head body (102), and a substrate plate (160) is movable relative to the printer head (101). The invention further relates to a method of atomic scale material deposition, etching and / or cleaning in selected areas using the atomic layer process printer. The atomic layer process printer can provide a high-resolution nanoscale three-dimensional structure.

Description

[0001] This application is a divisional application of the Chinese invention patent application with the application date of June 3, 2020, application number 202080041444.3, and name “Atomic Layer Process Printer” (the application number of the PCT international application corresponding to this application is PCT / EP2020 / 065396). Technical Field

[0002] The present invention relates to an atomic layer processing printer for depositing, etching and / or cleaning materials at the atomic scale in a selected area. The present invention further relates to a method for depositing, etching and / or cleaning materials at the atomic scale in a selected area using the atomic layer processing printer. Background Art

[0003] There are several prototyping and additive nanoscale manufacturing tools. However, these tools often have difficulties including: low processing speed, problems operating under atmospheric conditions, excessive use of materials, and complex processing of different materials at the same time. In addition, many of the existing methods require expensive tools.

[0004] Atomic layer deposition (ALD) is an example of a method used to print continuous thin films on flat surfaces as nanoscale manufacturing tools. The principle behind ALD is that a surface is subjected to a first precursor gas (precursor gas), which adsorbs on the surface, and then the excess of the first precursor gas is evacuated and a second precursor gas is introduced after the excess of the first precursor gas is completely evacuated, thereby completing the reaction on the surface. Generally speaking, ALD relies on a two-step reaction or a multi-step reaction to control the deposition process. ALD can be operated in two ways; time ALD and space ALD. In general, space ALD separates different gases in space, while time ALD separates gases in time.

[0005] Temporal ALD utilizes a chamber in which a substrate is positioned. The substrate in the chamber is typically subjected to a first precursor gas adsorbed on the surface, subjected to an inert gas for cleaning the chamber, subjected to a second precursor gas that reacts with the first precursor gas on the surface, and subjected to an inert gas for cleaning the chamber. This process may be repeated, or combined with other processes, until the desired product is obtained. Temporal ALD is generally viewed as a slow method and requires large amounts of gas when the entire chamber is to be filled in each step. Spatial selectivity is essentially not possible.

[0006] Spatial ALD performs the same type of steps as temporal ALD. However, instead of using a chamber to deposit the material on a surface, spatial ALD uses spatial separation of gases and moves the sample in the X, Y direction relative to the printer head. Depending on the setup, either the printer head moves or the sample moves.

[0007] Compared to temporal ALD, using spatial ALD results in faster deposition and generally reduced gas usage because deposition occurs locally rather than in a larger chamber. Using spatial ALD further eliminates the need to purge the chamber between each gas dose.

[0008] Whether using temporal ALD or spatial ALD, it is not possible to provide three-dimensional structures. Therefore, a three-dimensional structuring system that provides high-resolution nanoscale three-dimensional structures is needed. Summary of the invention

[0009] In a first aspect, an atomic layer process printer for material deposition, etching and / or cleaning at the atomic scale in selected areas is disclosed herein. The printer may include: a substrate plate for holding a substrate onto which one or more fluids can be deposited using the printer; and a printer head positioned opposite the substrate on the substrate plate.

[0010] The printer head will typically include a printer head plate having a number of openings including:

[0011] - one or more first exit openings, each of which has a first exit opening diameter of less than 900 micrometers;

[0012] - one or more second exit openings;

[0013] - one or more third exit openings;

[0014] - One or more discharge openings.

[0015] The printer may further include:

[0016] o a first inlet supply channel connected to the one or more first exit openings for directing a first precursor fluid onto the substrate through the one or more first exit openings;

[0017] o a second inlet supply channel connected to the one or more second exit openings for directing a second precursor fluid onto the substrate through the one or more second exit openings;

[0018] o a third inlet supply channel connected to the one or more third exit openings for directing an inert fluid onto the substrate through the one or more third exit openings;

[0019] o One or more outlet channels connected to the one or more exhaust openings for removing undeposited first precursor fluid, undeposited second precursor fluid, and the inert fluid from the substrate.

[0020] The substrate plate is typically movable relative to the printer head:

[0021] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0022] ○ Along the Z axis perpendicular to the X, Y plane; and

[0023] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0024] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0025] The one or more exhaust openings may include: one or more first exhaust openings, which are connected to the first outlet channel for removing undeposited first precursor fluid and possibly inert fluid from the substrate; and one or more second exhaust openings, which are connected to the second outlet channel for removing undeposited second precursor fluid and possibly inert fluid from the substrate.

[0026] In a second aspect, an atomic layer process printer for material deposition, etching and / or cleaning at the atomic scale in selected areas is disclosed herein. The printer may include: a substrate plate for holding a substrate onto which one or more fluids can be deposited using the printer; and a printer head positioned opposite the substrate on the substrate plate. The printer head typically includes a printer head plate having a plurality of openings, the openings including:

[0027] - one or more first exit openings, each of which has a first exit opening diameter of less than 900 micrometers;

[0028] - one or more third exit openings;

[0029] - One or more discharge openings.

[0030] The printer may further include:

[0031] o a first inlet supply channel connected to the one or more first exit openings for directing a first precursor fluid onto the substrate through the one or more first exit openings;

[0032] o a third inlet supply channel connected to the one or more third exit openings for directing an inert fluid onto the substrate through the one or more third exit openings;

[0033] o One or more outlet channels connected to the one or more exhaust openings for removing undeposited first precursor fluid, undeposited second precursor fluid, and the inert fluid from the substrate.

[0034] The substrate plate is typically movable relative to the printer head:

[0035] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0036] ○ Along the Z axis perpendicular to the X, Y plane; and

[0037] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0038] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0039] The one or more exhaust openings may include: one or more first exhaust openings, which are connected to the first outlet channel for removing undeposited first precursor fluid and possibly inert fluid from the substrate; and one or more second exhaust openings, which are connected to the second outlet channel for removing undeposited second precursor fluid and possibly inert fluid from the substrate.

[0040] Compared to the first aspect, the second inlet supply channel and the second exit openings may be omitted in the second aspect by having the second precursor fluid in the chamber surrounding the substrate.

[0041] In a third aspect, an atomic layer process printer for material deposition, etching and / or cleaning at the atomic scale in selected areas is disclosed herein. The printer may include: a substrate plate for holding a substrate onto which one or more fluids can be deposited using the printer; and a printer head positioned opposite the substrate on the substrate plate.

[0042] The printer head may include a printer head plate having a plurality of exit openings including one or more first exit openings each having a first exit opening diameter of less than 900 microns.

[0043] The printer may further comprise a plurality of inlet supply channels connected to the one or more first exit openings, the plurality of inlet supply channels comprising:

[0044] o a first inlet supply channel for directing a first precursor fluid onto the substrate;

[0045] o a second inlet supply channel for directing a second precursor fluid onto the substrate;

[0046] o A third inlet supply channel for directing an inert fluid onto the substrate.

[0047] The printer may further include one or more outlet channels connected to the one or more exhaust openings for removing undeposited first precursor fluid, undeposited second precursor fluid, and the inert fluid from the substrate.

[0048] The substrate plate is typically movable relative to the printer head:

[0049] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0050] ○ Along the Z axis perpendicular to the X, Y plane; and

[0051] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0052] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0053] The one or more exhaust openings may include: one or more first exhaust openings, which are connected to the first outlet channel for removing undeposited first precursor fluid and possibly inert fluid from the substrate; and one or more second exhaust openings, which are connected to the second outlet channel for removing undeposited second precursor fluid and possibly inert fluid from the substrate.

[0054] In a third aspect, the precursor fluids and the inert fluid will typically be supplied alternately to the substrate through the one or more exit openings. This third aspect is similar to a temporal ALD type process, whereas the first and second aspects are similar to a spatial ALD type process.

[0055] In a fourth aspect, a method for depositing a material on a substrate in a selected area is disclosed herein. The method comprises the following steps:

[0056] o providing an atomic layer process printer having a substrate plate and a printer head positioned opposite to each other,

[0057] Wherein the substrate plate is movable relative to the printer head:

[0058] - along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other;

[0059] - along a Z axis perpendicular to the X, Y plane; and

[0060] - A first angle to define the rotation of the X, Y plane around the Z axis

[0061] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0062] The method according to the fourth aspect further comprises:

[0063] ○ positioning the substrate on the substrate plate;

[0064] o exposing the substrate to a first precursor fluid through one or more first exit openings each having a diameter of less than 900 microns;

[0065] o removing the first precursor fluid not deposited on the substrate via one or more exhaust openings in conjunction with exposing the substrate to an inert fluid;

[0066] o exposing the substrate having the first precursor deposited thereon to a second precursor fluid;

[0067] o Removing the second precursor fluid not deposited on the substrate via the one or more exhaust openings in conjunction with exposing the substrate to an inert fluid.

[0068] Disclosed herein in a fifth aspect is a method for vertical deposition of material on a substrate in selected areas, the method comprising the steps of providing an atomic layer process printer having a substrate plate and a printer head positioned opposite each other, wherein the substrate plate is movable relative to the printer head:

[0069] - along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other;

[0070] - along a Z axis perpendicular to the X, Y plane; and

[0071] - A first angle to define the rotation of the X, Y plane around the Z axis

[0072] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0073] The method according to the fifth aspect further comprises:

[0074] ○ positioning the substrate on the substrate plate;

[0075] o exposing the substrate to a first precursor fluid through one or more first exit openings each having a diameter of less than 900 microns;

[0076] o removing the first precursor fluid not deposited on the substrate via one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first exit openings;

[0077] o exposing the substrate having the first precursor deposited thereon to a second precursor fluid through the one or more first exit openings;

[0078] o Removing the second precursor fluid not deposited on the substrate via the one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first exit openings.

[0079] Disclosed herein in a sixth aspect is a method for rapid material deposition on a substrate in a selected area, the method comprising the steps of providing an atomic layer process printer having a substrate plate and a printer head positioned opposite each other, wherein the substrate plate is movable relative to the printer head:

[0080] - along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other;

[0081] - along a Z axis perpendicular to the X, Y plane; and

[0082] - A first angle to define the rotation of the X, Y plane around the Z axis

[0083] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0084] The method according to the sixth aspect further comprises:

[0085] ○ positioning the substrate on the substrate plate;

[0086] ○ mixing the first precursor fluid with the second precursor fluid;

[0087] o Exposing the substrate to a mixture of the first precursor fluid and the second precursor fluid through one or more first exit openings each having a diameter of less than 900 microns.

[0088] Disclosed herein in a seventh aspect is a method for etching material on a substrate in selected areas, the method comprising the steps of providing an atomic layer processing printer having a substrate plate and a printer head positioned opposite each other, wherein the substrate plate is movable relative to the printer head:

[0089] - along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other;

[0090] - along a Z axis perpendicular to the X, Y plane; and

[0091] - A first angle to define the rotation of the X, Y plane around the Z axis

[0092] The substrate plate and the printer head are also typically movable relative to each other at a second angle θ, which defines a tilt of the X, Y plane about an axis in the X, Y plane.

[0093] The method according to the seventh aspect further comprises:

[0094] ○ positioning the substrate on the substrate plate;

[0095] o exposing the substrate to a first etchant through one or more first exit openings each having a diameter of less than 900 microns;

[0096] o removing the first etchant not deposited on the substrate by means of one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first exit openings;

[0097] o exposing the substrate having the first precursor deposited thereon to a second etchant through the one or more first exit openings;

[0098] o Removing the second etchant not deposited on the substrate by means of the one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first exit openings.

[0099] The term fluid also includes gases. Examples of precursor fluids may include, for example, organic precursor fluids, inorganic precursor fluids, and metal-based precursor fluids.

[0100] The one or more exhaust openings further include different types of exhaust openings, such as one or more first exhaust openings for removing excess of the first precursor fluid and one or more second exhaust openings for removing excess of the second precursor fluid.

[0101] By means of a printer according to the first, second and / or third aspects and a method according to the fourth, fifth, sixth and / or seventh aspects, a printer and a method are obtained which allow cleaning, deposition and etching of materials with, for example, a fluid phase or a gas phase to obtain thin films, patterns and 3D structure constructions with atomic scale resolution in a transverse direction and nanometer resolution in a transverse direction. The transverse direction means the direction parallel to the Z axis. The transverse direction means the direction parallel to the X, Y plane.

[0102] The possibility to move the substrate plate and the printer head relative to each other in a full 3D orientation opens up the possibility to create 3D structures in an easy way compared to conventional ALD techniques, while providing very high atomic scale resolution in the transverse direction and nanometer resolution in the lateral direction. This results in a state-of-the-art printer based on the principle of spatial ALD technology.

[0103] By enabling the substrate plate to rotate relative to the printer head in an X, Y, Z plane and at a first angle defining a rotation of the X, Y plane about the Z axis Improved control over the 3D geometry of printed structures is achieved by moving the printed structure.

[0104] US2013012029A1 discloses an ALD printer with a printer head that can move in the XYZ plane. The distribution of the exit / exhaust channels differs from the distribution in the above aspects and only provides for regional deposition extending in the XY plane (i.e., a single plane that only demonstrates 2D resolution but not 3D resolution). It is not possible to obtain 3D structures directly from printing using the ALD printer in US2013 / 012029A1.

[0105] Atomic scale thickness resolution (digital growth control) and pattern resolution down to 12 nm can be obtained by the printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects.

[0106] Having one or more first exit openings each having a diameter of less than 900 microns is essential to obtain the low resolution obtainable with the printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects.

[0107] In one or more examples, the first exit opening has a diameter less than 800 μm, such as less than 700 μm, such as less than 600 μm, such as less than 500 μm, such as less than 400 μm, such as less than 300 μm, such as less than 200 μm, such as less than 100 μm, such as less than 50 μm.

[0108] Separate channels and openings further enable accurate micro-scale / nano-scale feature printing. It provides high purity printed materials by avoiding material cross contamination. Therefore, multi-material printing can be used, where short pulse valves and gas sources at a short distance from the print head are used to quickly switch between different materials.

[0109] In contrast, in the ALD printer disclosed in US2015086716A1 having an outlet opening in the range of 1 mm to 12 mm, such resolution cannot be obtained. The millimeter opening causes the process and printer of US2015086716A1 to rely on the Bernoulli principle, which states that: in a horizontally flowing fluid, the highest velocities occur where the pressure is lowest, and the lowest velocities occur where the pressure is highest. When micro-sized openings below 100 microns are used, as in the case of printers according to the first, second and / or third aspects and methods according to the fourth, fifth, sixth and / or seventh aspects, it is expected that the Bernoulli principle will begin to fail to apply due to the increase in relevant velocities and the scattering of fast molecules caused by impact. More generally, the Bernoulli principle is only applicable to isentropic flows, and turbulent and high Mach number flows are not considered.

[0110] In US2015086716A1, the printer head moves relative to a fixed substrate plate. In the printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects, the substrate plate is instead moved relative to the printer head in the XYZ plane. This difference provides a difference in stiffness, possible speed, and simplifies the maintenance of the plane parallelism required for printer operation.

[0111] The printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects all allow for cleaning, deposition and / or etching of fluids / materials having inorganic, organic and metallic compositions. When the printer is used for etching, the term precursor fluid is meant to also include etching fluids / etchants.

[0112] The printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects can be operated without plasma and can be treated with water, for example, titanium isopropoxide (TTIP) to obtain titanium dioxide (TiO2). In addition, the printer can handle sulfide, oxide, nitride and pure metal printing as well as core complex ternary and quaternary composite materials. Therefore, in one or more instances, these precursor fluids form sulfides, oxides, nitrides, pure metals and core complex ternary and quaternary composite materials when printing.

[0113] The printer according to the first, second and / or third aspects and the method according to the fourth, fifth, sixth and / or seventh aspects also allow the formation of continuous films and patterns. Multiple stacking of materials and high conformality to any surface morphology can be obtained using the printer according to the first, second and third aspects.

[0114] The high deposition rate can be further obtained using the printer according to the first aspect, the second aspect and / or the third aspect and the method according to the fourth aspect, the fifth aspect, the sixth aspect and / or the seventh aspect. The printer can be operated at room temperature and at a higher temperature such as 400 degrees Celsius. The printer is operated at a certain temperature, meaning that at least the printer head is connected to a heating source for heating the printer head to a specific temperature. In addition, the substrate plate can also be heated to an elevated temperature.

[0115] The printer can operate at atmospheric pressure or at low vacuum pressure in an open and controlled environment. The printer operates at a specific pressure meaning that at least the printer head is kept at atmospheric pressure or at low vacuum pressure in an open and controlled environment. It has advantageously low reactive fluid consumption, and it provides material versatility. In addition, additive and subtractive processing, selected area high resolution, and conformal processing can be performed on a variety of plain and corrugated inorganic and organic substrates.

[0116] In one or more instances, the one or more exhaust openings include: one or more first exhaust openings connected to a first outlet channel for removing undeposited first precursor fluid (and possibly an inert fluid) from the substrate; and one or more second exhaust openings connected to a second outlet channel for removing undeposited second precursor fluid (and possibly an inert fluid) from the substrate.

[0117] By having a separate discharge opening for each of these precursor fluids, chemical blockage in the discharge channel and thus any possible damage to the printer is prevented. If two discharge channels merge into one discharge channel, the fluids will react in the merged channel and block the merged channel, resulting in operational failure.

[0118] The one or more exhaust channels may be driven by a vacuum pump to a pressure of at least approximately 20 mbar.The pressure will typically be measured at the inlet.

[0119] In one or more instances, the X, Y plane extends parallel to the substrate plate. Similarly, the rotation of the X, Y plane around the Z axis can be a rotation of the substrate plate. Moreover, the tilt of the X, Y plane can be a tilt of the substrate plate relative to the printer head. In one or more instances, the printer head can be tilted. The second angle θ can be in the range of 0.5 to 10 degrees, such as 1 to 5 degrees, such as 2 to 4 degrees, or such as 2.5 to 3.5 degrees.

[0120] The Z axis may extend between the printer head and the substrate plate, thereby defining a distance between the printer head and the substrate plate. The distance between the printer head and the substrate plate is in the range of 0.005 μm to 100 μm, such as 0.005 μm to 50 μm, such as 0.01 μm to 50 μm, such as 0.05 μm to 50 μm, such as 0.1 μm to 50 μm, such as 0.1 μm to 25 μm or such as 1 μm to 10 μm.

[0121] In one or more examples, the first exit opening has a diameter less than 800 μm, such as less than 700 μm, such as less than 600 μm, such as less than 500 μm, such as less than 400 μm, such as less than 300 μm, such as less than 200 μm, such as less than 100 μm, such as less than 50 μm.

[0122] In one or more instances, the first exit opening diameter is in the range of 0.005μm to 850μm, such as 0.005μm to 750μm, such as 0.005μm to 650μm, such as 0.005μm to 550μm, such as 0.005μm to 450μm, such as 0.005μm to 250μm, such as 0.005μm to 100μm, such as 0.01μm to 50μm, such as 0.01μm to 10μm, such as 0.01μm to 1μm, such as 0.015μm to 0.05μm, such as 0.02μm.

[0123] In one or more examples, the printer is adapted to provide a pattern resolution of 20 nm to 1 mm. To achieve a particular resolution, the size of the first exit opening should be approximately 0.625 to 1.25 times the size of the desired resolution.

[0124] The resolution (ie, resolution size) of the printed structure depends on both the diameter of the one or more first exit openings and the distance between the printer head and the substrate plate.

[0125] In one or more examples, the outlet surface of the printer head further includes outermost safety escape passages positioned around the first, second and third exit openings and the exhaust openings. The outermost exhaust openings (e.g., the second exhaust openings) can be used as the safety escape passages. The safety escape passages have two functions: if the second precursor used (such as ozone or hydrogen sulfide) is hazardous, it allows the printer to operate under atmospheric conditions; and further improves the local inert atmosphere around the deposition area.

[0126] In one or more examples, the printer head outlet surface is in the form of a disk, square, rectangle, triangle, pentagon or similar shape, wherein each group of openings each forms a disk. Preferably, the printer head outlet surface may be in the form of a disk.

[0127] In one or more embodiments, the printer is adapted to vary the distance between the printer head and the substrate sheet during printing of a three-dimensional structure.

[0128] In one or more embodiments, the printer is adapted to operate at a deposition rate of 1 nm / min or less. The deposition rate is a factor of substrate movement speed, temperature, and the reactivity of the selected first and second precursor fluids. The adaptation is performed by adjusting the movement of the substrate.

[0129] In one or more instances, the printer is adapted to operate at a deposition rate in the range of 0.1 nm / min to 100 nm / min, such as 1 nm / min to 100 nm / min, such as 1 nm / min to 50 nm / min, such as 0.1 nm / min to 10 nm / min, such as 0.5 nm / min to 10 nm / min, such as 1 nm / min to 10 nm / min.

[0130] In one or more examples, the printer is adapted to operate at atmospheric pressure. In other examples, the printer is adapted to operate at vacuum or ultra-high vacuum. The printer operates at a specific pressure meaning that at least the printer head is maintained at atmospheric pressure or maintained at a low vacuum in an open and controlled environment.

[0131] In one or more instances, the printer is adapted to control the temperature of the printer head. The printer may include a heating / cooling source that heats at least the printer head to allow the printer head to operate at a temperature between 10°C and 600°C, such as between 15°C and 450°C, such as between 20°C and 400°C. The printer operating at a certain temperature means that at least the printer head is connected to a heating source for heating the printer head to a specific temperature. In addition, the substrate plate may also be heated to an elevated temperature. All types of tubes / conduits, valves, and precursor and / or inert gas supplies may also be heated / cooled to control the temperature. Therefore, the printer may be adapted to control the temperature of these supply channels. This allows the printer to operate fully at a desired temperature (e.g., a temperature much higher than room temperature).

[0132] In one or more examples, the supply channels are made of stainless steel, polytetrafluoroethylene, fluoroelastomer material (FKM) or perfluoroelastomer compound (FFKM). This provides a control channel that can control temperature.

[0133] The temperature control may extend to all tube channels extending from the container containing the precursor through the valve and supply channel system to the printer head.The temperature may be controlled in different zones, such as for example at least three zones.

[0134] In one or more examples, the printer is adapted to operate in a bottom-up configuration, wherein the printer head is positioned above the substrate sheet.

[0135] In one or more embodiments, the printer head plate further comprises:

[0136] - one or more first distribution channels adapted to direct the first precursor fluid from the first inlet supply channel to the one or more first exit openings;

[0137] - one or more second distribution channels adapted to distribute the second precursor fluid from the second inlet supply channel to the one or more second exit openings;

[0138] - one or more third distribution channels adapted to distribute the inert fluid from the third inlet supply channel to the one or more third exit openings.

[0139] In one or more examples, the printer head plate is removably attached to the printer head such that different printer head plates can be connected to the printer head, the opening diameter of the first exit opening of the different printer head plates having different sizes.

[0140] In one or more examples, the one or more second and third exit openings and the one or more exhaust openings are positioned around the one or more first exit openings.

[0141] In one or more examples, the one or more second and third exit openings and the one or more exhaust openings are circumferentially positioned around each of the one or more first exit openings.

[0142] In one or more examples, the one or more second and third exit openings and the one or more exhaust openings are symmetrically positioned around the one or more first precursor openings. In one or more examples, the one or more first exit openings include a first exit opening positioned in the center of the printer head plate.

[0143] In one or more instances, the discharge opening of a primary set is positioned between each of these first exit openings and a second exit opening of the primary set; and / or the third exit opening of the primary set is positioned between each of these first exit openings and the second exit opening of the primary set.

[0144] In one or more instances, the precursor fluid distance between the one or more first exit openings and the second exit openings of the main group is between 5 μm and 3000 μm, or such as between 5 μm and 500 μm, or such as between 5 μm and 100 μm, or such as between 5 μm and 30 μm, or such as between 10 μm and 20 μm, or such as between 30 μm and 3000 μm, or such as between 50 μm and 2000 μm, or such as between 100 μm and 1000 μm.

[0145] In one or more embodiments, the printer includes a plurality of printer heads. When the printer head has micro-scale openings (i.e., it is a micro-nozzle print head), including a plurality of printer heads is not a simple process. Each micro-nozzle requires a special mounting mechanism and micro-nozzle design. Moreover, it is not simple to successfully connect multiple printer heads to the same gas distribution system.

[0146] In one or more embodiments, the printer head is made of ceramic or a metal such as corrosion resistant steel.

[0147] In one or more examples, the printer is adapted to alternately supply the first precursor fluid, the inert fluid, and the second precursor fluid onto the substrate.

[0148] The printer according to the second aspect and the fifth aspect may further comprise a chamber surrounding the substrate, wherein the chamber is adapted to contain a second precursor fluid. BRIEF DESCRIPTION OF THE DRAWINGS

[0149] Various examples are described below with reference to the figures. Similar reference numbers refer to similar elements throughout the text. Therefore, similar elements will not be described in detail with respect to the description of each figure. It should also be noted that these figures are intended only to facilitate the description of the examples. They are not intended to serve as an exhaustive description of the claimed invention or as a limitation on the scope of the claimed invention. In addition, the illustrated examples do not need to show all aspects or advantages. The aspects or advantages described in conjunction with a specific example are not necessarily limited to that example, and can be practiced in any other example, even if not so illustrated or even if not explicitly described.

[0150] Figure 1A Example time atomic layer deposition, Figure 1B Example of spatial atomic layer deposition.

[0151] Figure 2 An atomic layer processing printer for material deposition, etching and / or cleaning at the atomic scale in selected areas is schematically illustrated.

[0152] Figure 3A , Figure 3B and Figure 3C An example of a printer head is shown in perspective view ( Figure 3A )、Bottom view( Figure 3B ) and exploded view ( Figure 3C ) shows that Figure 3D Shown is an example of distribution channels inside a printer head plate.

[0153] Figure 4 A first example of a printer head plate is shown.

[0154] Figure 5 A second example of a printer head plate is shown.

[0155] Figure 6 A third example of a printer head plate is shown.

[0156] Figure 7 A fourth example of a printer head plate is shown.

[0157] Figure 8 A fifth example of a printer head plate is shown.

[0158] Fig. 9 A sixth example of a printer head plate is shown.

[0159] Fig.10 An example of a printer that can be controlled to switch between a spatial ALD type process and a temporal ALD type process is shown.

[0160] Fig.11Shown is a top SEM image of a TiO2 printed line obtained using the printer.

[0161] Fig.12 Shows the complex printed pattern of amorphous TiO2 deposited using the printer.

[0162] Fig.13A shows the energy dispersive X-ray spectrum of a platinum wire printed using a printer, Fig. 13B The signal intensities shown in FIG. 5 are related to different line thicknesses.

[0163] Fig.14 Shown is a complex printed pattern of amorphous Pt deposited using a printer.

[0164] Fig.15A and Fig. 15B Shown is the X-ray diffraction pattern of material deposited using the printer.

[0165] Fig.16 The temperature dependence of the growth of TiO2 deposited using a printer is shown.

[0166] Fig.17 Atomic force microscopy profiles of TiO2 lines deposited using the printer are shown.

[0167] Fig.18a shows the X-ray photoelectron spectrum of TiO2 deposited using the printer, and Fig.18b Shown is the X-ray photoelectron spectrum of PtO2 deposited using a printer.

[0168] Fig.19a , Fig.19b and Fig.19c Shown are growth curves of platinum measured at different substrate temperatures. DETAILED DESCRIPTION

[0169] Exemplary examples will now be described more fully below with reference to the accompanying drawings. In this regard, examples of the present invention may have different forms and should not be construed as being limited to the descriptions set forth herein. Therefore, examples are described below only by reference to the various figures to illustrate various aspects. As used herein, the term "and / or" includes any and all combinations of one or more items in the relevant listed items. Expressions such as "at least one of" modify the entire list of elements when located in front of the list of elements, rather than modifying individual elements in the list.

[0170] In the drawings, for clarity and ease of description, the thickness of multiple layers and regions is illustrated in an enlarged manner. When a layer, region, element or plate is referred to as "on" another layer, region, element or plate, it can be directly on the other layer, region, element or plate, or an intervening layer, region, element or plate can exist between them. On the contrary, when a layer, region, element or plate is referred to as "directly on" another layer, region, element or plate, there is no intervening layer, region, element or plate between them. In addition, when a layer, region, element or plate is referred to as "below" another layer, region, element or plate, it can be directly below the other layer, region, element or plate, or an intervening layer, region, element or plate can exist between them. On the contrary, when a layer, region, element or plate is referred to as "directly on" another layer, region, element or plate, there is no intervening layer, region, element or plate between them.

[0171] For ease of description, the spatially relative terms "lower" or "bottom" and "upper" or "top", "below", "under", "smaller", "above", etc. may be used herein to describe the relationship between one element or component and another element or component, as illustrated in the various figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, where the device illustrated in the figures is flipped, an element described as being on the "lower" side of other elements or "below" or "under" another element will be oriented as being on the "upper" side of other elements or "above" another element. Therefore, depending on the specific orientation of the figure, the illustrated term "below" or "under" can include two directional positions of "lower" and "upper". Similarly, if the device in one of the figures is flipped, an element described as being "below" or "under" other elements will be oriented as being "above" other elements. Thus, the exemplary terms "below" or "beneath" can encompass both an orientation of above and below, and thus the spatially relative terms may be interpreted differently depending on the orientation being described.

[0172] Throughout the specification, when an element is referred to as being “connected” to another element, the element is “directly connected” to the other element or “electrically connected” to the other element with one or more intervening elements interposed therebetween.

[0173] The terms used herein are only used for the purpose of describing particular examples and are not intended to be limiting. As used herein, unless the content clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include plural forms, including "at least one". "At least one" should not be interpreted as limiting "one". It will be further understood that the terms "include", "comprise", "contain", and / or "have" when used in this specification specify the presence of stated features, wholes, steps, operations, elements and / or parts, without excluding the presence or addition of one or more other features, wholes, steps, operations, elements, parts and / or groups thereof.

[0174] It will be understood that although the terms "first", "second", "third", etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. Thus, the "first element" discussed below may be referred to as the "second element" or the "third element" and the "second element" and the "third element" may be referred to as the "first element" without departing from the teachings herein.

[0175] As used herein, "about" or "approximately" includes stated values ​​and averages within an acceptable range of deviation for a particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of a stated value.

[0176] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. It will be further understood that terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning of these terms in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless so clearly defined in this specification.

[0177] Exemplary examples are described herein with reference to schematically illustrated cross-sectional views as idealized examples, wherein similar reference numbers refer to similar elements throughout the specification. As such, variations in the illustrated shapes due to, for example, manufacturing techniques and / or tolerances can be expected. Therefore, the examples described herein should not be interpreted as being limited to the specific shapes of the zones illustrated herein, but should include shape deviations caused by, for example, manufacturing. For example, a zone illustrated or described as flat may have rough and / or nonlinear features. In addition, the illustrated sharp corners may be rounded. Therefore, the zones illustrated in the figures are schematic in nature, and the shapes of these zones are not intended to illustrate the precise shapes of the zones and are not intended to limit the scope of the claims of the present invention. Some of the components not associated with the description may not be provided in order to specifically describe the exemplary examples of the present disclosure.

[0178] Figure 1A An example of temporal atomic layer deposition (ALD) is shown, where precursor fluids are separated in time and Figure 1B Spatial atomic layer deposition (ALD) is exemplified, where the precursor fluids are spatially separated.

[0179] Time ALD utilizes a chamber in which a functionalized substrate is positioned. The substrate in the chamber is typically subjected to a first precursor gas 132 that is deposited on the functionalized surface, subjected to an inert fluid 136 for cleaning the chamber, subjected to a second precursor gas 134 that is deposited on the surface covered by the deposited first gas, and subjected to an inert gas 136 for cleaning the chamber. This process can be repeated until a desired product, such as a substrate, is obtained. Figure 1A exemplified in .

[0180] Spatial ALD performs the same type of steps as temporal ALD. However, instead of using a larger chamber to deposit material on a surface, spatial ALD uses spatial separation of the precursor fluids 132, 134 and the inert fluid 136 and moves the sample substrate 162 in the X, Y directions, such as Figure 1B exemplified in .

[0181] Figure 2 The atomic layer process printer 100 disclosed herein for material deposition, etching and / or cleaning at the atomic scale in selected areas is illustrated very schematically. The printer 100 includes a substrate plate 160 for holding a substrate 162 and a printer head 101 positioned opposite to the substrate 162 on the substrate plate 160. Figure 2 The upper right corner of the diagram illustrates the X-axis, Y-axis, and Z-axis. Figure 2 The upper right corner of the example defines the first angle of rotation of the X, Y plane around the Z axis and a second angle θ defining the inclination of the X, Y plane about an axis in the X, Y plane. The substrate plate 160 and the printer head 101 may be in one or more of the X, Y, Z planes and / or about two angles. and θ move relative to each other. In this way, a full 3D movement can be obtained.

[0182] The printer 100 will typically be operated in a bottom-up configuration, with the printer head 101 positioned above the substrate plate 160, such as Figure 2 Typically, the substrate sheet 160 will be in the X, Y, Z planes and / or around two angles. and θ, and the printer head 101 will remain fixed. However, it is also conceivable that the printer head 101 moves in the X, Y, Z planes and / or around two angles while the substrate plate 160 remains fixed. Alternatively, it is also possible that both the substrate plate 160 and the printer head 101 move simultaneously.

[0183] like Figure 2 As shown in , the X, Y plane may extend parallel to the substrate plate 160. Therefore, the rotation of the X, Y plane around the Z axis may be the rotation of the substrate plate 160. Typically, the substrate 162 is fixed to the substrate plate 160. The tilt of the X, Y plane may be the tilt of the substrate plate 160 relative to the printer head 101. Therefore, any movement of the substrate plate will be converted into a movement of the substrate 162.

[0184] The Z axis extends between the printer head 101 and the substrate plate 160, thereby defining the distance between the printer head 101 and the substrate plate 160. The distance between the printer head 101 and the substrate plate 160 may be in the range of 0.005 μm to 100 μm, such as 0.005 μm to 50 μm, such as 0.01 μm to 50 μm, such as 0.05 μm to 50 μm, such as 0.1 μm to 50 μm, such as 0.1 μm to 25 μm, or such as 1 μm to 10 μm.

[0185] The distance between the printer head 101 and the substrate plate 160 is variable during printing of the three-dimensional structure. The substrate plate 160 and the printer head 101 can be moved relative to each other in two or more of the following situations: along an axis in the X, Y plane; along the Z axis; at a first angle; Alternatively, the substrate plate 160 and the printer head 101 may be movable relative to each other in three or all of the following situations: along an axis in the X, Y plane; along the Z axis; at a first angle θ. and at a second angle θ. The distance between the printer head 101 and the substrate plate 160 is also variable during printing of the three-dimensional structure.

[0186] The printer 100 will be able to deposit at least one molecular layer per minute. Typically, this will provide a repositioning of up to 100 nm per minute. The printer can therefore operate at a deposition rate in the range of 0.1 nm / min to 100 nm / min, such as 1 nm / min to 100 nm / min, such as 1 nm / min to 50 nm / min, such as 0.1 nm / min to 10 nm / min, such as 0.5 nm / min to 10 nm / min, such as 1 nm / min to 10 nm / min. The printer can typically operate at a deposition rate of 1 nm / min or less.

[0187] The printer 100 is adapted to operate at atmospheric pressure. However, alternatively, the printer 100 may be adapted to operate at vacuum or ultra-high vacuum.

[0188] The printer 100 is typically adapted to operate at temperatures between 10°C and 600°C, such as between 15°C and 450°C, such as between 20°C and 400°C. The printer will typically include a heating source to heat at least the printer head to allow it to operate at the required temperature.

[0189] The printer can also be configured so that it includes not only one printer head 101 but multiple printer heads 101. When the printer head has micro-scale openings (i.e., it is a micro-nozzle print head), it is not a simple process to include multiple printer heads. Each micro-nozzle requires a special mounting mechanism and micro-nozzle design. Moreover, it is not simple to successfully connect multiple printer heads to the same gas distribution system.

[0190] Reference now Figures 3A to 3C , in perspective view ( Figure 3A )、Bottom view( Figure 3B ) and exploded view ( Figure 3C ) is shown in detail in FIG. The printer head 101 includes a printer head body 102 having a plurality of inlet supply / outlet channels 121, a printer head plate 104 having a plurality of openings 111, an additional printer head plate 105, a printer head plate clamp 106 and a clamping nut 107.

[0191] The printer head plate 104 is connected to an additional printer head plate 105, which in turn is releasably fixed to a printer head plate clamp 106 and a clamping nut 107. The clamping nut 107 and the printer head plate clamp 106 can be separated from the printer head 102, which allows the printer head plate 104 to be easily removed and / or replaced. The clamping nut 107 can be fixed to the printer head body 102 by a threaded connection, a bayonet connection, a snap-fit ​​connection, or a similar connection. The printer head plate 104 is removably attached to the printer head 101, so that different printer head plates 104 can be connected to the printer head 101, and the opening diameter of the first exit opening of different printer head plates 104 has different sizes. This allows different atomic resolutions to be obtained using the same printer 100.

[0192] Alternatively, the printer head plate 104 can be simply welded to a piece of metal. In this type of arrangement, no clamps are required.

[0193] The inlet supply / outlet passage 121 includes both inlet supply passages 122 , 124 , 126 and outlet passages 126 , 128 . Figures 4 to 9 Different examples of the location of the opening 111 in the printer head plate 104 are shown, wherein Figure 4 Also shown are examples of how inlet supply channels 122 , 124 , 126 and outlet channels 126 , 128 may be connected to opening 111 in printer head plate 104 .

[0194] exist Figure 4 , the symmetrical printer head plate 104a is shown in close-up and illustrates how the opening 111 connects to the inlet supply channels 122, 124, 126 and the outlet channels 126, 128. Figure 4 The printer head plate 104a in FIG. 1 includes a centrally located first exit opening 112 having a first exit opening diameter of less than 900 microns. The first exit opening 112 is connected to a first inlet supply channel 122 for directing a first precursor fluid 132 onto a substrate 162. The first precursor fluid 132 is shown as Figure 4 The circular container is merely meant as an example of a container for holding the first precursor fluid 132.

[0195] Figure 4 The printer head plate 104a in the embodiment further includes: a plurality of second exit openings 114 connected to the second inlet supply channel 124 for guiding the second precursor fluid 134 onto the substrate 162; and a plurality of third exit openings 116 connected to the third inlet supply channel 126 for guiding the inert fluid 136 onto the substrate 162. Figure 4In the example shown in , both the second exit opening 114 and the third exit opening 116 are concentrically positioned around the first exit opening 112 .

[0196] A ring of several concentrically positioned exhaust openings 118 connected to the first outlet channel 128 is located between the first exit opening 112 and the ring of concentrically positioned third exit openings 116. Undeposited precursor fluid / inert fluid 138 is removed through the several first exhaust openings 118 connected to the first outlet channel 128. Figure 5 In the example shown in FIG. 1 , mainly the undeposited first precursor fluid 132 and the inert fluid 136 are removed through the first exhaust opening 118 .

[0197] A ring with the plurality of concentrically positioned second exit openings 114 is concentrically positioned around the third exit opening 116 through which the second precursor fluid 134 is supplied to the substrate 162. It is found that a plurality of second exhaust openings 120 are circumferentially positioned around the second exit opening 114 for removing undeposited second precursor fluid 134 and possibly some inert fluid 136.

[0198] although Figure 4 Only one example of a printer head plate 104a is shown, but typically the main group of discharge openings 118, 120 will be positioned between each first of the first exit openings 112 and the main group of second exit openings 114; and / or the main group of third exit openings 116 will be positioned between each first of the first exit openings 112 and the main group of second exit openings 114.

[0199] The arrows in the first inlet supply channels 122 , 124 , 126 and the outlet channels 128 , 130 mark the direction of fluid flow through the channels 122 , 124 , 126 , 128 , 130 .

[0200] The precursor fluid distance between the first exit opening 112 and the second exit opening 114 will typically be between 5 μm and 3000 μm, or such as between 5 μm and 500 μm, or such as between 5 μm and 100 μm, or such as between 5 μm and 30 μm, or such as between 10 μm and 20 μm, or such as between 30 μm and 3000 μm, or such as between 50 μm and 2000 μm, or such as between 100 μm and 1000 μm.

[0201] Having a relatively large distance between the first exit opening 112 and the second exit opening 114 prevents the two precursor fluids 132, 134 from mixing simultaneously. Therefore, having an exit opening distance of more than 50 μm between the first exit opening 118 and the second exit opening 120 prevents the two precursor fluids from mixing in the exit openings 118, 120. On the other hand, when there is an exit opening distance of less than 50 μm between the first exit opening 118 and the second exit opening 120, mixing of the two precursor fluids in the exit openings 118, 120 is generally observed.

[0202] like Figure 3C As shown in , the printer head 101 may further include an additional printer head plate 105 positioned between the printer head plate 104 and the inlet channels 122, 124, 126. The additional printer head plate 105 includes a number of openings 122', 124', 126', 128', 130', which are each connected to / are part of the supply channels 122, 124, 126, 128, 130. An O-ring 108 will typically be found between the additional printer head plate 105 and the printer head body 102 for ensuring a tight connection.

[0203] Figure 3D The distribution channels inside the printer head plate 104 are shown. The distribution channels include: one or more first distribution channels 142, which are suitable for guiding the first precursor fluid 132 from the first inlet supply channel 122 to the first exit opening 112. The distribution channels inside the printer head plate 104 also include: one or more second distribution channels 144, which are suitable for distributing the second precursor fluid 134 from the second inlet supply channel 124 to the one or more second exit openings 114; and one or more third distribution channels 146, which are suitable for distributing the inert fluid 136 from the third inlet supply channel 126 to the one or more third exit openings 116. The distribution channels inside the printer head plate 104 further include one or more exhaust distribution channels 147, 147' suitable for removing the precursor fluids 132, 134 and the inert fluid 136.

[0204] Figure 5 Another example of a close-up view of the printer head plate 104b is shown, where there are a plurality of first exit openings 112. In order to provide the viewer with a clearer view of the printer head plate 104b, a small version of the plate without the reference symbol is shown in the upper left corner. Figure 5In the printer head plate 104b shown in FIG. 1 , there are six first exit openings 112 positioned in the center of the printer head plate 104b. Surrounding the first exit openings 112 are a group of first discharge openings 118, which are in turn surrounded by a group of third discharge openings 116, followed by a group of second exit openings 114 and a group of second discharge openings 120. Figure 4 Compared to the printer head plate 104a of FIG. 1 , the circumferential order of the exit openings 112, 114, 116 and the discharge openings 118, 120 is the same. However, the number of exit openings 112, 114, 116 and discharge openings 118, 120 in each ring group is different, and the individual distances between the openings 112, 114, 116, 118, 120 in the same ring are different. Moreover, the sizes of the openings 112, 114, 116, 118, 120 are different. The size of the first exit opening 112 is the same as that of the first exit opening 112. Figure 4 Like the first exit opening shown in , the diameter is less than 900 μm.

[0205] Figure 6 Yet another example of a close-up view of a partially symmetrical printer head plate 104c is shown, where there are square openings 112, 114, 116, 118. In this example, there is only one type of exit opening 118 for removing both the undeposited first precursor fluid 132 and the undeposited second precursor fluid 134, as well as removing the inert fluid 136. Again there is only one first exit opening 112. Surrounding the first exit opening 112 is a group of first exit openings 118, which in turn is surrounded by a group of third exit openings 116, followed by a group of second exit openings 114. Figure 4 and Figure 5 Compared to the printer head plates 104a, 104b of FIG. 1 , the openings 114, 116, 118 are positioned in a square around the first exit opening 112. Figure 6 The shapes of the openings 112, 114, 116, 118, 120 are different from Figure 4 and 5 Although the circular shape in FIG. 1 is shown, the dimension of the first exit opening 112 from one corner to the opposite corner is still less than 900 μm.

[0206] Figure 4 , Figure 5 and Figure 6 The printer head plates 104a, 104b, 104c shown in FIG. 1 all have, at least to some extent, symmetrically positioned openings 112, 114, 116, 118, 120. However, asymmetrical configurations may also be used. Figure 7An example of a close-up view of an asymmetric printer head plate 104d is shown with randomly positioned openings 112, 114, 116, 118, 120. The lack of reference numbers for some openings is meant to illustrate that different choices can be made as to which type of opening 112, 114, 116, 118, 120 different circles are.

[0207] Figure 8 Shown with Figure 4 104e, with the difference being that the third exit opening 116' is angularly offset.

[0208] Fig. 9 An example of a close-up view of the printer head plate 104f is shown, wherein the second exit opening 114", the third exit opening 116", the first exit opening 118", and the second exit opening 120" are annular. Fig. 9 The printer head board 104f and Figure 4 The printer head boards in the Figure 4 A plurality of second exit openings 114, a third exit opening 116, a first discharge opening 118 and a second discharge opening 120 are arranged concentrically around the first exit opening 112 and are combined into a large annular opening, namely, the second exit opening 114", the third exit opening 116", the first discharge opening 118" and the second discharge opening 120".

[0209] exist Figures 4 to 9 The first exit opening diameter of all first exit openings 112 in all the illustrated examples of the printer heads 104a, 104b, 104c, 104d, 104e, 104f in the embodiment is less than 900 μm. In one or more examples, the first exit opening diameter is less than 800 μm, such as less than 700 μm, such as less than 600 μm, such as less than 500 μm, such as less than 400 μm, such as less than 300 μm, such as less than 200 μm, such as less than 100 μm, such as less than 50 μm.

[0210] In one or more instances, the first exit opening diameter is in the range of 0.005μm to 850μm, such as 0.005μm to 750μm, such as 0.005μm to 650μm, such as 0.005μm to 550μm, such as 0.005μm to 450μm, such as 0.005μm to 250μm, such as 0.005μm to 100μm, such as 0.01μm to 50μm, such as 0.01μm to 10μm, such as 0.01μm to 1μm, such as 0.015μm to 0.05μm, such as 0.02μm.

[0211] The printer will typically be able to provide a pattern resolution of 20 nm to 1 mm. The resolution (ie, resolution size) of the printed structure may depend both on the diameter of the one or more first exit openings and on the distance between the printer head and the substrate plate, such as shown below in Table 1.

[0212] Table 1. Selected dimensions of the first exit opening, the distance between the printer head and the substrate plate and the lateral resolution obtained in the printed structures.

[0213]

[0214] The printer head 101 may include an outermost safety escape passage around the openings 112, 114, 116, 118 located on the printer head plates 104a, 104b, 104c, 104d, 104e, 104f. The outermost discharge opening (eg, the second discharge opening 120) may be used as a safety escape passage.

[0215] The form of the outlet surface of the printer head 101 may be a disc, square, rectangular, triangular, pentagonal or similar shape, wherein each set of openings each forms a disc. The outlet surface may refer to both the printer head plate 104 or the printer head plate 105. In general, the shape is not important as long as the printer head plate 104, 110 is easily fixed to the printer 101 and / or released from the printer 101.

[0216] The printer 100 may be used for spatial type ALD as described above in connection with the figures, where there are several exit openings 112, 114, 116 for each of the precursor fluids 132, 134 and the inert fluid 136. This corresponds to the first aspect of the printer 100 as disclosed herein.

[0217] According to a fourth aspect, a method for depositing a material on a substrate 162 in a selected area is also disclosed herein. The method comprises the following steps:

[0218] • providing an atomic layer processing printer having a substrate plate 160 and a printer head 101 positioned opposite each other,

[0219] The substrate plate 160 is movable relative to the printer head 101:

[0220] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0221] ○ Along the Z axis perpendicular to the X, Y plane; and

[0222] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0223] wherein the substrate plate 160 and the printer head 101 are movable relative to each other at a second angle θ, the second angle defining a tilt of the X, Y plane about an axis in the X, Y plane;

[0224] • Positioning the substrate 162 on the substrate plate 160;

[0225] • exposing the substrate 162 to the first precursor fluid 132 through one or more first exit openings 112 each having a diameter of less than 900 microns;

[0226] • removing the first precursor fluid 132 that is not deposited on the substrate 162 via the one or more exhaust openings 118 , 120 in conjunction with exposing the substrate 162 to the inert fluid 136 ;

[0227] • exposing the substrate 162 having the first precursor deposited thereon to the second precursor fluid 134;

[0228] Removing the second precursor fluid 134 that is not deposited on the substrate 162 via the one or more exhaust openings 118 , 120 in conjunction with exposing the substrate 162 to the inert fluid 136 .

[0229] In one or more examples, the substrate plate 160 and the printer head 101 are moved relative to each other between the deposition precursor fluid 132 and the deposition precursor fluid 134 .

[0230] As described in the second and fifth aspects, the printer 100 can be configured to supply the precursor fluids 132, 134 and the inert fluid 136 to the substrate 162 in an alternating manner through the same exit openings 112, 114, 116 (including at least the first exit opening 112). A sequence of the first precursor fluid 132, then the inert fluid 136, and then the second precursor fluid 134 can be used. This corresponds to Figure 1A The time type ALD is shown in FIG. Figures 4 to 9 A printer head plate of can be used for this arrangement. The only difference when using the printer 100 in this mode compared to the space type mode is that the supply channels 122, 124, 126 need to be connected to all openings 112, 114, 116. In addition, in order to obtain high resolution using the printer according to the second aspect, the diameters of the exit openings all need to be less than 900 μm in diameter.

[0231] According to a fifth aspect, a method for vertically depositing a material on a substrate 162 in a selected area is further disclosed herein. The method comprises the following steps:

[0232] ● Providing an atomic layer processing printer having a substrate plate 160 and a printer head 101 positioned relative to each other, wherein the substrate plate 160 and the printer head 101 are movable relative to each other in one or more of the following situations:

[0233] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0234] ○ Along the Z axis perpendicular to the X, Y plane; and

[0235] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0236] wherein the substrate plate 160 and the printer head 101 are movable relative to each other at a second angle θ, the second angle defining a tilt of the X, Y plane about an axis in the X, Y plane;

[0237] • Positioning the substrate 162 on the substrate plate 160;

[0238] • exposing the substrate 162 to the first precursor fluid 132 through one or more first exit openings 112 each having a diameter of less than 900 microns;

[0239] Removing the first precursor fluid 132 that is not deposited on the substrate 162 by means of the one or more exhaust openings 118 , 120 in combination with exposing the substrate 162 to the inert fluid 136 through the one or more first exit openings 112 ;

[0240] • exposing the substrate 162 having the first precursor deposited thereon to the second precursor fluid 134 through the one or more first exit openings 112;

[0241] Removing the second precursor fluid 134 that is not deposited on the substrate 162 by means of the one or more exhaust openings 118 , 120 in conjunction with exposing the substrate 162 to the inert fluid 136 through the one or more first exit openings 112 .

[0242] Furthermore, by having a chamber surrounding the substrate 162, it may not be necessary to use the second inlet supply channel 124 to supply the second precursor fluid 134 to the substrate 162 through the second exit opening 114. This corresponds to the third aspect as described above.

[0243] Alternatively, the precursor fluids 132, 134 may be mixed before being supplied to the substrate 162. This aspect is based on the third aspect. Therefore, in a sixth aspect, a method for rapid material deposition on a substrate 162 in a selected area is also disclosed herein, wherein the method comprises the following steps:

[0244] • providing an atomic layer processing printer having a substrate plate 160 and a printer head 101 positioned opposite each other,

[0245] The substrate plate 160 is movable relative to the printer head 101:

[0246] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0247] ○ Along the Z axis perpendicular to the X, Y plane; and

[0248] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0249] wherein the substrate plate 160 and the printer head 101 are movable relative to each other at a second angle θ, the second angle defining a tilt of the X, Y plane about an axis in the X, Y plane;

[0250] • Positioning the substrate 162 on the substrate plate 160;

[0251] ● mixing the first precursor fluid 132 with the second precursor fluid 134;

[0252] • Exposing the substrate 162 to the mixture of the first precursor fluid 132 and the second precursor fluid 134 through one or more first exit openings 112 each having a diameter of less than 900 microns.

[0253] The printer 100 can be used not only for rapid material deposition on the substrate 162 in a selected area, but also for etching. A method for etching material on the substrate 162 in a selected area is also disclosed herein in a seventh aspect, wherein the method comprises the following steps:

[0254] • providing an atomic layer processing printer having a substrate plate 160 and a printer head 101 positioned opposite each other,

[0255] The substrate plate 160 is movable relative to the printer head 101:

[0256] o along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular to each other;

[0257] ○ Along the Z axis perpendicular to the X, Y plane;

[0258] ○ To define a first angle of rotation of the X, Y plane around the Z axis

[0259] wherein the substrate plate 160 and the printer head 101 are movable relative to each other at a second angle θ, the second angle defining a tilt of the X, Y plane about an axis in the X, Y plane;

[0260] • Positioning the substrate 162 on the substrate plate 160;

[0261] • exposing the substrate 162 to a first etchant through one or more first exit openings 112 each having a diameter of less than 900 microns;

[0262] removing the first etchant not deposited on the substrate 162 by means of the one or more exhaust openings 118 , 120 in combination with exposing the substrate 162 to the inert fluid 136 through the one or more first exit openings 112 ;

[0263] • exposing the substrate 162 having the first precursor deposited thereon to a second etchant through the one or more first exit openings 112;

[0264] Removing the second etchant not deposited on the substrate 162 by means of the one or more exhaust openings 118 , 120 in combination with exposing the substrate 162 to the inert fluid 136 through the one or more first exit openings 112 .

[0265] In the printer according to the method of the fourth to seventh aspects, the one or more discharge openings may include:

[0266] o one or more first exhaust openings 118 connected to the first outlet channel 128 for removing undeposited first precursor fluid 132 and possibly the inert fluid 136 from the substrate 162; and

[0267] o One or more second exhaust openings 120 connected to the second outlet channel 130 for removing undeposited second precursor fluid 134 and possibly the inert fluid 136 from the substrate 162 .

[0268] exist Fig.10 An example of a printer 100 is shown in FIG. 1 , which can be controlled so as to switch between a spatial ALD type process and a temporal ALD type process, each of which includes material deposition, etching and cleaning.

[0269] Precursor fluids 132, 134 and inert fluid 136 are Fig.101 and 1 , are shown as gases controlled by flow controllers 155, which can open proportionally, measure flow, and provide feedback signals. Controller 155 is typically computer controlled. Inert gas 136 from container 156 is bubbled through first precursor solution 172 and second precursor solution 174 to obtain first precursor gas 132 and second precursor gas 134, respectively, to obtain precursor fluids 132, 134.

[0270] The supply channels 122 , 124 , 126 for supplying the first precursor fluid 132 , the second precursor fluid 134 , and the inert fluid 136 to the substrate 162 are controlled by a first set of a plurality of valves 148 .

[0271] The printer 100 also includes a second set of valves 149 for cleaning the supply channels 122, 124, 126 with the inert fluid 136. The printer 100 additionally includes a third valve 150, which allows the printer 100 to be used in a temporal ALD mode, because the third valve can deliver the second precursor fluid 134 to the substrate 162 through the first supply channel 122, and likewise deliver the first precursor fluid 132 to the substrate 162 through the second supply channel 124. Thus, by individually controlling the valves 148, 149, 150, for example, by opening these valves and closing these valves, the precursor fluids 132, 134 and the inert fluid 136 can be supplied to the printer head 101 and to the substrate 162, as described above for all aspects of the printer 100. The valves 148, 149, 150 will typically be diaphragm vacuum valves. These valves can be controlled in several different ways, for example, pneumatically.

[0272] The inert gas 136 is supplied to the first precursor solution 172 and the second precursor solution 174 through the fourth set of valves 151. The valves 151 may be needle valves that regulate bubblers.

[0273] The printer further includes a fifth valve 152, which is a pressure reducing valve for controlling the supply of the inert fluid 136. The fifth valve 152 is an inert fluid 136 dispenser, and it allows the printer 100 to operate in both the spatial ALD mode and the temporal ALD mode.

[0274] Exhaust channels 128 , 130 are controlled by a standard vacuum system that includes a sixth set of valves 153 , a pressure sensor 154 , a connector 157 (eg, a T-connector), a trap 158 that acts as a filter for a pump 159 , and a pump 159 .

[0275] An example of a printed structure obtained using the printer according to the first aspect is described below.

[0276] exist Fig.11. The printed material is TiO2. The lateral resolution is approximately 320 microns and the thickness is approximately 30 nanometers. The diameter of the first existing opening is 80 μm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C, the temperature of the substrate is 150°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0277] Fig.12 A complex printed pattern of amorphous TiO2 deposited at the printer head is shown, where the diameter of the first existing opening is 80 μm. The printed pattern shows a resolution of 15 nm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C, the temperature of the substrate is 150°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0278] Fig.13A An energy dispersive X-ray spectrum of a platinum wire printed using a printer is shown. The signal clearly indicates the presence of platinum. Fig. 13B The signal intensity shown in is related to different line thicknesses. Three different thicknesses were intentionally produced (thinnest, thickest and between thinnest and thickest). The diameter of the first existing opening was 80 μm. The distance between the printer head and the sample was 50 μm. The temperature of the printer head was 100°C, the temperature of the substrate was 250°C, the temperature of the tube was 90°C, and the precursor source was set at a temperature of 60°C.

[0279] Fig.14 is a complex printed pattern of platinum. The diameter of the first existing opening is 80 μm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C, the temperature of the substrate is 250°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0280] Fig.15A and 15B The X-ray diffraction pattern of the deposited material is shown, where Fig.15A is a de-titaniumized TiO2 line pattern deposited using a printer head at a temperature of 275 degrees Celsius, and Fig. 15B is a platinum line pattern. The diameter of the first presence opening is 80 μm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C, the temperature of the substrate is 250°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0281] Fig.16The dependence of the growth of TiO2 deposited using TTIP and H2O on temperature is shown. Within the error range, there is no temperature dependence indicating that the deposition is stable as expected in this temperature region. The diameter of the first existing opening is 80μm. The distance between the printer head and the sample is 50μm. The temperature of the printer head is 100°C, the temperature of the substrate is varied, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0282] Fig.17 Atomic force microscopy profiles of deposited TiO2 wires are shown. Fig.17 The three profiles shown in show the geometry of the edge of the printed line. The diameter of the first existing opening is 80 μm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C, the temperature of the substrate is 150°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C.

[0283] Fig.18a Shown is an X-ray photoelectron spectrum of TiO2 deposited using a printer, where the temperature of the printer head is 100°C, the temperature of the substrate is 150°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C. The peak corresponds to visible TiO2. The diameter of the first presence opening is 80 μm. The distance between the printer head and the sample is 50 μm.

[0284] Fig.18b The X-ray photoelectron spectrum of PtO2 deposited using a printer is shown, where the temperature of the printer head is 100°C, the temperature of the substrate is 150°C, the temperature of the tube is 90°C, and the precursor source is set at a temperature of 60°C. The peak corresponds to the visible PtO2. The diameter of the first presence opening is 80 μm. The distance between the printer head and the sample is 50 μm.

[0285] Figure 19a to Figure 19c The growth curve of platinum measured using a printer is shown, where the diameter of the first existing opening is 80 μm. The distance between the printer head and the sample is 50 μm. The temperature of the printer head is 100°C and the temperature of the substrate is Fig.19a The temperature is 200℃, Fig.19b is 225°C and Fig.19c The temperature of the tube was 90°C and the precursor source was set at a temperature of 60°C.

[0286] Reference Number

[0287] 100 Printers

[0288] 101 Printer Head

[0289] 102 Printer head body

[0290] 104 Printer head board

[0291] 104a First Example of Printer Head Plate

[0292] 104b Second Example of Printer Head Plate

[0293] 104c Third Example of Printer Head Plate

[0294] 104d Fourth Example of Printer Head Plate

[0295] 104e Fifth instance of printer head plate

[0296] 105 Additional Printer Head Board

[0297] 106 Printer head plate fixture

[0298] 107 Clamping nut

[0299] 108 O-ring

[0300] 111 Opening in the printer head plate

[0301] 112 First Leaving Opening

[0302] 114 Second exit opening

[0303] 114" annular second exit opening

[0304] 116 The third leaving opening

[0305] 116' has a third exit opening with an angle offset

[0306] 116” annular third exit opening

[0307] 118 first discharge opening

[0308] 118" annular first discharge opening

[0309] 120 second discharge opening

[0310] 120" annular second discharge opening

[0311] 121 Inlet supply / exit channel

[0312] 122 First inlet supply channel

[0313] 122' An opening connected to / part of the first inlet supply channel

[0314] 124 Second inlet supply channel

[0315] 124' An opening connected to / part of a second inlet supply channel

[0316] 126 Third Entrance Supply Channel

[0317] 126' An opening connected to / part of a third inlet supply channel

[0318] 128 First Exit Channel

[0319] 128' An opening connected to / part of the first outlet channel

[0320] 130 Second Exit Channel

[0321] 130' An opening connected to / part of a second outlet channel

[0322] 132 First precursor fluid

[0323] 134 Second precursor fluid

[0324] 136 Inert fluid

[0325] 138 Undeposited precursor fluid / inert gas

[0326] 140 Undeposited precursor fluid / inert gas

[0327] 142 First distribution channel

[0328] 144 Second distribution channel

[0329] 146 Third distribution channel

[0330] 147 Exhaust distribution channel

[0331] 147' discharge distribution channel

[0332] 148 Valve of the first group

[0333] 149 Valve of the second group

[0334] 150 Third valve

[0335] 151 Valve of the fourth group

[0336] 152 Fifth Valve

[0337] 153 Valve of group 6

[0338] 154 Pressure Sensor

[0339] 155 Controller

[0340] 156 Container with inert gas

[0341] 157 Connectors

[0342] 158 Traps used as filters

[0343] 159 Pump

[0344] 160 substrate board

[0345] 162 Substrate on substrate board

[0346] 172 first precursor solution

[0347] 174 Second precursor solution

[0348] X axis in the XX, Y plane

[0349] Y axis in YX, Y plane

[0350] Z is the axis perpendicular to the X and Y planes. Limit the rotation angle of the X and Y planes around the Z axis θ defines the angle of inclination of the X, Y plane about an axis in the X, Y plane

Claims

1. An atomic layer processing printer (100) for material deposition, etching and / or cleaning at the atomic scale in selected areas, the printer (100) comprising: o a substrate plate (160) for holding a substrate (162) onto which one or more fluids (132, 134) can be deposited using the printer (100); o a printer head (101) positioned opposite the substrate (162) on the substrate plate (160), wherein the printer head (101) comprises a printer head plate (104) having a plurality of openings, the openings comprising: - one or more first exit openings (112); - one or more second exit openings (114); - one or more third exit openings (116); - one or more discharge openings (118, 120); The printer head (101) further comprises a printer head body (102), the printer head body having: o a first inlet supply channel (122) connected to the one or more first exit openings (112) for directing a first precursor fluid (132) onto the substrate (162) through the one or more first exit openings (112); o a second inlet supply channel (124) connected to the one or more second exit openings (114) for directing a second precursor fluid (134) onto the substrate (162) through the one or more second exit openings (114); o a third inlet supply channel (126) connected to the one or more third exit openings (116) for directing an inert fluid (136) onto the substrate (162) through the one or more third exit openings (116); o one or more outlet channels (128, 130) connected to the one or more exhaust openings (118, 120) for removing undeposited first precursor fluid (132), undeposited second precursor fluid (134), and an inert fluid (136) from the substrate (162); wherein the printer head plate (104) is removably attached to the printer head body (102); The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; - movement along a Z axis perpendicular to said X, Y plane; and - a first angle to define the rotation of the X, Y plane around the Z axis move; wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ), the second angle (θ) defining a tilt of the X, Y plane about an axis in the X, Y plane, wherein the one or more discharge openings include: o one or more first exhaust openings (118) connected to a first outlet channel (128) for removing undeposited first precursor fluid (132) and possibly an inert fluid (136) from the substrate (162); and o One or more second exhaust openings (120) connected to a second outlet channel (130) for removing undeposited second precursor fluid (134) and possibly inert fluid (136) from the substrate (162).

2. The printer according to claim 1, wherein the printer head (101) is fixed in the X, Y plane and is fixed along the Z axis.

3. A printer according to any preceding claim, wherein the X, Y plane extends parallel to the substrate plate (160).

4. A printer according to any preceding claim, wherein the rotation of the X, Y plane about the Z axis is a rotation of the substrate plate (160).

5. A printer according to any preceding claim, wherein the tilt of the X, Y plane is a tilt of the substrate plate (160) relative to the printer head (101).

6. A printer according to any preceding claim, wherein the Z-axis extends between the printer head (101) and the substrate plate (160) thereby defining a distance between the printer head (101) and the substrate plate (160).

7. A printer according to any preceding claim, wherein the exit surface of the printer head (101) further comprises a safety escape passage positioned at the outermost sides around the first, second and third exit openings (112, 114, 116) and the discharge openings (118, 120).

8. A printer according to any preceding claim, wherein the printer is adapted to vary the distance between the printer head (101) and the substrate sheet (160) during printing of a three-dimensional structure.

9. A printer according to any preceding claim, wherein the printer is adapted to control the temperature of the printer head (101).

10. A printer according to any preceding claim, wherein the printer is adapted to control the temperature of the supply channel (122, 124, 126).

11. A printer according to any preceding claim, wherein the printer comprises a heating / cooling source which heats at least the printer head (101) to allow the printer head to operate at a temperature between 10°C and 600°C, such as between 15°C and 450°C, such as between 20°C and 400°C.

12. A printer according to any preceding claim, wherein the printer is adapted to operate in a bottom-up arrangement, wherein the printer head (101) is positioned above the substrate plate (160).

13. A printer according to any preceding claim, wherein the printer head plate (104) further comprises: - one or more first distribution channels (142) adapted to guide the first precursor fluid (132) from the first inlet supply channel (122) to the one or more first exit openings (112); - one or more second distribution channels (144) adapted to distribute the second precursor fluid (134) from the second inlet supply channel (124) to the one or more second exit openings (114); - one or more third distribution channels (146) adapted to distribute the inert fluid (136) from the third inlet supply channel (126) to the one or more third exit openings (116).

14. The printer according to any preceding claim, wherein the one or more second and third exit openings (114, 116) and the one or more exhaust openings (118, 120) are positioned around the one or more first exit openings (112).

15. The printer according to any preceding claim, wherein the one or more second and third exit openings (114, 116) and the one or more exhaust openings (118, 120) are positioned circumferentially around each of the one or more first exit openings (112).

16. The printer according to any preceding claim, wherein the one or more second and third exit openings (114, 116) and the one or more discharge openings (118, 120) are symmetrically positioned around the one or more first exit openings (112).

17. The printer of any preceding claim, wherein the one or more first exit openings (112) comprises a first exit opening (112) centrally located in the printer head plate (104).

18. A printer according to any preceding claim, wherein: o a main set of discharge openings (118, 120) is positioned between each of said first exit openings (112) and a main second exit opening (114); and / or o The third exit openings (116) of the main group are positioned between each of the first exit openings (112) and the second exit openings (114) of the main group.

19. A printer according to any preceding claim, wherein the printer comprises a plurality of printer heads (101).

20. An atomic layer processing printer for depositing, etching and / or cleaning materials at the atomic scale in selected areas, the printer comprising: o a substrate plate (160) for holding a substrate (162) onto which one or more fluids (132, 134) can be deposited using the printer; o a printer head (101) positioned opposite the substrate (162) on the substrate plate (160), wherein the printer head (101) comprises a printer head plate (104) having a plurality of exit openings (111), the exit openings comprising one or more first exit openings (112); The printer head (101) further comprises a printer head body (102) having a plurality of inlet supply channels connected to the one or more first exit openings (112), the plurality of inlet supply channels comprising: o a first inlet supply channel (122) for directing a first precursor fluid (132) onto the substrate (162); o a second inlet supply channel (124) for directing a second precursor fluid (134) onto the substrate (162); o a third inlet supply channel (126) for directing an inert fluid (136) onto the substrate (162); wherein the printer further comprises one or more outlet channels (128, 130) connected to one or more exhaust openings (118, 120) for removing undeposited first precursor fluid (132), undeposited second precursor fluid (134), and inert fluid (136) from the substrate (162); wherein the printer head plate (104) is removably attached to the printer head body (102); The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; - movement along a Z axis perpendicular to said X, Y plane; and - a first angle to define the rotation of the X, Y plane around the Z axis move; wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ), the second angle (θ) defining a tilt of the X, Y plane about an axis in the X, Y plane, wherein the one or more discharge openings include: o one or more first exhaust openings (118) connected to a first outlet channel (128) for removing undeposited first precursor fluid (132) and possibly an inert fluid (136) from the substrate (162); and o One or more second exhaust openings (120) connected to a second outlet channel (130) for removing undeposited second precursor fluid (134) and possibly inert fluid (136) from the substrate (162).

21. A method for depositing material on a substrate (162) in selected areas, the method comprising the steps of: o providing an atomic layer processing printer having a substrate plate (160) and a printer head (101) positioned opposite to each other, The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; - movement along a Z axis perpendicular to said X, Y plane; and - a first angle to define the rotation of the X, Y plane around the Z axis Move; and wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ), the second angle (θ) defining a tilt of the X, Y plane about an axis in the X, Y plane; o positioning a substrate (162) on the substrate plate (160); o exposing the substrate (162) to a first precursor fluid (132) through one or more first exit openings (112); o removing the first precursor fluid (132) not deposited on the substrate (162) via one or more exhaust openings (118, 120) in conjunction with exposing the substrate (162) to an inert fluid (136); o exposing the substrate (162) having the first precursor deposited thereon to a second precursor fluid (134); o Removing the second precursor fluid (134) not deposited on the substrate (162) via the one or more exhaust openings (118, 120) in conjunction with exposing the substrate (162) to an inert fluid (136).

22. The method of claim 21, further comprising the step of moving the substrate plate (160) and the printer head (101) relative to each other between depositing the first precursor fluid (132) and depositing the second precursor fluid (134).

23. A method for vertically depositing material on a substrate (162) in selected areas, the method comprising the steps of: o providing an atomic layer processing printer having a substrate plate (160) and a printer head (101) positioned opposite to each other, The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; -Move along the Z axis perpendicular to the X, Y plane; - a first angle to define the rotation of the X, Y plane around the Z axis Move; and wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ) defining an inclination of the X, Y plane about an axis in the X, Y plane; o positioning a substrate (162) on the substrate plate (160); o exposing the substrate (162) to a first precursor fluid (132) through one or more first exit openings (112) each having a diameter in the range of 0.005 to 900 microns; o removing the first precursor fluid (132) not deposited on the substrate (162) by means of one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136) through the one or more first exit openings (112); o exposing the substrate (162) having the first precursor deposited thereon to a second precursor fluid (134) through the one or more first exit openings (112); o Removing the second precursor fluid (134) not deposited on the substrate (162) via the one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136) through the one or more first exit openings (112).

24. A method for rapid material deposition on a substrate (162) in selected areas, the method comprising the steps of: o providing an atomic layer processing printer having a substrate plate (160) and a printer head (101) positioned opposite to each other, The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; -Move along the Z axis perpendicular to the X, Y plane; - a first angle to define the rotation of the X, Y plane around the Z axis Move; and wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ), the second angle (θ) defining a tilt of the X, Y plane about an axis in the X, Y plane; o positioning a substrate (162) on the substrate plate (160); ○ mixing the first precursor fluid (132) and the second precursor fluid (134); o Exposing the substrate (162) to a mixture of the first precursor fluid (132) and the second precursor fluid (134) through one or more first exit openings (112).

25. A method for etching material on a substrate (162) in selected areas, the method comprising the steps of: o providing an atomic layer processing printer having a substrate plate (160) and a printer head (101) positioned opposite to each other, The substrate plate (160) is movable relative to the printer head (101): - move along an axis in an X, Y plane defined by an X-axis and a Y-axis that are perpendicular relative to each other; -Move along the Z axis perpendicular to the X, Y plane; - a first angle to define the rotation of the X, Y plane around the Z axis Move; and wherein the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ), the second angle (θ) defining a tilt of the X, Y plane about an axis in the X, Y plane; o positioning a substrate (162) on the substrate plate (160); o exposing the substrate (162) to a first etchant through one or more first exit openings (112); o removing the first etchant not deposited on the substrate (162) by means of one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136) through the one or more first exit openings (112); o exposing the substrate (162) having the first precursor deposited thereon to a second etchant through the one or more first exit openings (112); o Removing the second etchant not deposited on the substrate (162) by means of the one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136) through the one or more first exit openings (112).

26. The method of any one of claims 21 to 25, wherein the printer head (101) comprises a printer head plate (104) having a plurality of openings, the openings comprising: - the one or more first exit openings (112), each of the first exit openings having a first exit opening diameter of less than 500 micrometers; - one or more second exit openings (114); - one or more third exit openings (116); - One or more discharge openings (118, 120).

27. The method of claim 26, wherein the printer head (101) further comprises a printer head body (102), wherein the printer head plate (104) is removably attached to the printer head body (102), the printer head body (102) comprising: o a first inlet supply channel (122) connected to the first exit opening (112) for directing the first precursor fluid (132) / the first etchant onto the substrate (162) through the one or more first exit openings (112); o a second inlet supply channel (124) connected to the one or more second exit openings (114) for directing the second precursor fluid (134) / the second etchant onto the substrate (162) through the one or more second exit openings (114); o a third inlet supply channel (126) connected to the one or more third exit openings (116) for directing the inert fluid (136) onto the substrate (162) through the one or more third exit openings (116); o One or more outlet channels (128, 130) connected to the one or more exhaust openings (118, 120) for removing undeposited first precursor fluid (132) / first etchant, undeposited second precursor fluid (134) / second etchant, and an inert fluid (136) from the substrate (162).

Images