Atomic layer process printer

Abstract

The present invention relates to an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area. The present invention also relates to a method for material deposition, etching, and / or cleaning at an atomic scale in a selected area using an atomic layer process printer.

Description

Technology Field

[0001] The present invention relates to an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area. The present invention also relates to a method for material deposition, etching, and / or cleaning at an atomic scale in a selected area using an atomic layer process printer. Background Technology

[0002] There are many prototyping and additive nanoscale manufacturing tools. However, they often present challenges, including low processing speeds, issues with operating under atmospheric conditions, excessive material usage, and the complexity of processing different materials simultaneously. Furthermore, many existing methods require expensive tools.

[0003] Atomic Layer Deposition (ALD) is an example of a method used as a nanoscale manufacturing tool for printing continuous films on flat surfaces. The principle of ALD is that the surface is affected by a first precursor gas adsorbed onto the surface, followed by vacuum treatment of an excess of the first precursor gas, and then complete reaction on the surface after the introduction of a complete vacuum treatment of an excess of the second precursor gas. Generally, ALD relies on two-stage or multi-stage reactions to control the deposition process. ALD can operate in two ways: temporal ALD and spatial ALD. Total spatial ALD separates different gases in space, whereas temporal ALD separates gases over time.

[0004] Temporal ALD utilizes a chamber in which a substrate is placed. The substrate within the chamber is typically exposed to a first precursor gas adsorbed on the surface, to an inert gas for cleaning the chamber, to a second precursor gas that reacts with the first precursor gas on the surface, and to an inert gas for cleaning the chamber. This process can be repeated or combined with other processes until the desired product is obtained. Temporal ALD is often considered a slow method and requires a large amount of gas because the entire chamber is filled at each stage. Spatial selectivity is not inherently possible.

[0005] Spatial ALD performs the same type of steps as temporal ALD. However, instead of using a chamber to deposit material on a surface, spatial ALD uses spatial separation of gases and moves the sample relative to the printer head in the X and Y directions. Depending on the settings, either the printer head moves or the sample moves.

[0006] Using spatial ALD enables faster deposition compared to temporal ALD, and generally reduces the amount of gas used because deposition occurs locally instead of in a single larger chamber. With spatial ALD, the need to evacuate the chamber between each gas volume is further eliminated.

[0007] Whether temporal or spatial ALD is used, it is impossible to provide three-dimensional structures. Therefore, a three-dimensional structuring system is required to provide high-resolution nanoscale three-dimensional structures.

[0008] In a first embodiment, an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area is disclosed in the present invention. The printer may include a substrate plate for holding a substrate on which one or more fluids can be deposited using the printer, and a printer head positioned to face the substrate on the substrate plate.

[0009] The above printer head is generally:

[0010] - One or more first exit openings, each having a first exit opening diameter smaller than 900 micrometers;

[0011] - One or more second exit openings;

[0012] - One or more third exit openings;

[0013] - Includes a printer head plate having a plurality of openings including one or more exhaust openings.

[0014] The above printer is:

[0015] o A first inlet supply channel connected to one or more first outlet openings to guide a first precursor fluid onto the substrate through one or more first outlet openings;

[0016] o A second inlet supply channel connected to one or more second outlet openings to guide a second precursor fluid onto the substrate through one or more second outlet openings;

[0017] o A third inlet supply channel connected to one or more third outlet openings to guide an inert fluid onto the substrate through one or more third outlet openings;

[0018] o further includes one or more exhaust channels connected to one or more exhaust openings to remove the undeposited first precursor fluid, the undeposited second precursor fluid, and the inert fluid from the substrate.

[0019] The above substrate plate is generally in relation to the above printer head:

[0020] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0021] o along the Z-axis perpendicular to the X,Y plane; and

[0022] o It is possible to move by a first angle (φ) that defines the rotation of the X,Y plane around the Z-axis.

[0023] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the tilting of the X,Y plane around an axis in the X,Y plane.

[0024] The above one or more exhaust openings may include one or more first exhaust openings connected to a first exhaust channel to remove an undeposited first precursor fluid and possibly an inert fluid from the substrate; and one or more second exhaust openings connected to a second exhaust channel to remove an undeposited second precursor fluid and possibly an inert fluid from the substrate.

[0025] In a second aspect, the present invention discloses an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area. The printer may include a substrate plate for holding a substrate that can be deposited using the printer with one or more fluids, and a printer head positioned to face the substrate on the substrate plate. The printer head generally comprises:

[0026] - One or more first outlet openings, each having a first outlet opening diameter smaller than 900 micrometers;

[0027] - One or more third exit openings;

[0028] - Includes a printer head plate having a plurality of openings including one or more exhaust openings.

[0029] The above printer is:

[0030] o A first inlet supply channel connected to one or more first outlet openings to guide a first precursor fluid onto the substrate through one or more first outlet openings;

[0031] o A third inlet supply channel connected to one or more third outlet openings to guide an inert fluid onto the substrate through one or more third outlet openings;

[0032] o It may further include one or more exhaust channels connected to one or more exhaust openings to remove the undeposited first precursor fluid, the undeposited second precursor fluid, and the inert fluid from the substrate.

[0033] The above substrate plate is generally in relation to the above printer head:

[0034] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0035] o along the Z-axis perpendicular to the X,Y plane; and

[0036] o It is possible to move by a first angle (φ) that defines rotation in the X,Y plane around the Z-axis.

[0037] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0038] The above one or more exhaust openings may include one or more first exhaust openings connected to a first exhaust channel to remove an undeposited first precursor fluid and possibly an inert fluid from the substrate; and one or more second exhaust openings connected to a second exhaust channel to remove an undeposited second precursor fluid and possibly an inert fluid from the substrate.

[0039] The second inlet supply channel and the second outlet opening may be omitted in the second embodiment compared to the first embodiment by having a second precursor fluid in a chamber surrounding the substrate.

[0040] In a third embodiment, an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area is disclosed in the present invention. The printer may include a substrate plate for holding a substrate on which one or more fluids can be deposited using the printer, and a printer head positioned to face the substrate on the substrate plate.

[0041] The printer head may include a printer head plate having a plurality of outlet openings, each having one or more first outlet openings having a first outlet opening diameter smaller than 900 micrometers.

[0042] The printer may further include a plurality of inlet supply channels connected to one or more first outlet openings, and the plurality of inlet supply channels are:

[0043] o A first inlet supply channel for guiding a first precursor fluid onto the substrate;

[0044] o A second inlet supply channel for guiding a second precursor fluid onto the substrate;

[0045] o Includes a third inlet supply channel for guiding an inert fluid onto the substrate.

[0046] The printer may further include one or more exhaust channels connected to one or more exhaust openings for removing an undeposited first precursor fluid, an undeposited second precursor fluid, and an inert fluid from a substrate.

[0047] The above substrate plate is generally in relation to the above printer head:

[0048] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0049] o along the Z-axis perpendicular to the X,Y plane; and

[0050] o It is possible to move by a first angle (φ) that defines rotation in the X,Y plane around the Z-axis.

[0051] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0052] The above one or more exhaust openings may include one or more first exhaust openings connected to a first exhaust channel to remove an undeposited first precursor fluid and possibly an inert fluid from the substrate; and one or more second exhaust openings connected to a second exhaust channel to remove an undeposited second precursor fluid and possibly an inert fluid from the substrate.

[0053] In the third embodiment, the precursor fluid and the inert fluid will generally be alternately supplied to the substrate through one or more outlet openings. This is similar to a temporal ALD type process, whereas the first and second embodiments are similar to a spatial ALD type process.

[0054] In a fourth aspect, a method for depositing a material on a substrate in a selected area is disclosed in the present invention. The method is:

[0055] o The method may include the step of providing an atomic layer process printer having a substrate plate and a printer head positioned toward the substrate plate, and

[0056] The above substrate plate is in relation to the printer head:

[0057] - Along the axes in the X,Y plane defined by the X and Y axes perpendicular to each other;

[0058] - Along the Z-axis perpendicular to the X,Y plane; and

[0059] - It can be moved by the first angle (φ) that defines the rotation of the X,Y plane around the Z-axis.

[0060] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0061] The method according to the fourth mode is:

[0062] o A step of positioning a substrate on the above substrate plate;

[0063] o A step of exposing the substrate to a first precursor fluid through one or more first outlet openings, each having a diameter smaller than 900 micrometers;

[0064] o A step of removing the first precursor fluid that is not deposited on the substrate by means of one or more exhaust openings in combination with exposing the substrate to an inert fluid;

[0065] o A step of exposing the substrate on which the first precursor is deposited to a second precursor fluid;

[0066] o The method further includes the step of removing the second precursor fluid not deposited on the substrate by means of the one or more exhaust openings in combination with exposing the substrate to an inert fluid.

[0067] In a fifth aspect, a method for vertically depositing a material onto a substrate in a selected area is disclosed in the present invention, the method comprising the step of providing an atomic layer process printer having a substrate plate and a printer head positioned toward the substrate plate, wherein the substrate plate is in relation to the printer head:

[0068] - Along the axes in the X,Y plane defined by the X and Y axes perpendicular to each other;

[0069] - Along the Z-axis perpendicular to the X,Y plane; and

[0070] - It can be moved by the first angle (φ) that defines the rotation of the X,Y plane around the Z-axis.

[0071] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0072] The method according to the fifth mode is:

[0073] o A step of positioning a substrate on the above substrate plate;

[0074] o A step of exposing the substrate to a first precursor fluid through one or more first outlet openings, each having a diameter smaller than 900 micrometers;

[0075] o A step of removing a first precursor fluid not deposited on the substrate by one or more exhaust openings in combination with exposing the substrate to an inert fluid through one or more first outlet openings;

[0076] o A step of exposing the substrate on which the first precursor is deposited to a second precursor fluid through one or more first outlet openings;

[0077] o The method further includes the step of removing the second precursor fluid not deposited on the substrate by the one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first outlet openings.

[0078] A method for rapid material deposition on a substrate in a selected area in a sixth aspect is disclosed in the present invention, the method comprising the step of providing an atomic layer process printer having a substrate plate and a print head positioned toward the substrate plate, wherein the substrate plate is in relation to the print head:

[0079] - Along the axes in the X,Y plane defined by the X and Y axes perpendicular to each other;

[0080] - Along the Z-axis perpendicular to the X,Y plane; and

[0081] - It can be rotated by a first angle (φ) that defines the rotation of the X,Y plane around the Z-axis.

[0082] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0083] The method according to the sixth mode is:

[0084] o A step of positioning a substrate on the above substrate plate;

[0085] o A step of mixing the first precursor fluid and the second precursor fluid;

[0086] o Further includes the step of exposing the substrate to a mixture of the first precursor fluid and the second precursor fluid through one or more first outlet openings, each having a diameter smaller than 900 micrometers.

[0087] In a seventh aspect, a method for material etching on a substrate in a selected area is disclosed in the present invention, the method comprising the step of providing an atomic layer process printer having a substrate plate and a printer head positioned toward the substrate plate, wherein the substrate plate is with respect to the printer head:

[0088] - Along the axes in the X,Y plane defined by the X and Y axes perpendicular to each other;

[0089] - Along the Z-axis perpendicular to the X,Y plane; and

[0090] - It can be moved by the first angle (φ) that defines the rotation of the X,Y plane around the Z-axis.

[0091] The above substrate plate and the printer head can also generally move relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane.

[0092] The method according to the seventh mode is:

[0093] o A step of positioning a substrate on the above substrate plate;

[0094] o A step of exposing the substrate to a first etching agent through one or more first exit openings, each having a diameter smaller than 900 micrometers;

[0095] o A step of removing the first etching agent not deposited on the substrate by one or more exhaust openings in combination with exposing the substrate to an inert fluid through one or more first outlet openings;

[0096] o A step of exposing the substrate on which the first precursor is deposited to a second etching agent through one or more first exit openings;

[0097] o Further includes the step of removing a second etchant not deposited on the substrate by the one or more exhaust openings in combination with exposing the substrate to an inert fluid through the one or more first outlet openings.

[0098] The term fluid also includes gases. Examples of precursor fluids may include, for instance, organic, inorganic, and metal-based precursor fluids.

[0099] One or more exhaust openings include different types of exhaust openings, for example, one or more first exhaust openings for removing an excess amount of first precursor fluid, and one for a second exhaust opening for removing an excess amount of second precursor fluid.

[0100] A printer and a method are obtained by means of a printer according to the first, second, and / or third embodiment and a method according to the fourth, fifth, sixth, and / or seventh embodiment, which involves washing, depositing, and etching a material from a fluid or gaseous phase to obtain a film, pattern, and 3D structure having atomic-scale resolution in the traverse direction and nanometer resolution in the lateral direction. The traverse direction means a direction parallel to the Z-axis. The lateral direction means a direction parallel to the X,Y plane.

[0101] Compared to conventional ALD technology, the ability to move the substrate plate and the printer head relative to each other in all 3D directions provides very high atomic-scale resolution in the lateral direction and nanometer resolution in the lateral direction, while simultaneously opening up the possibility of creating 3D structures in an easy manner. This consequently enables state-of-the-art printers based on the principles of spatial ALD technology.

[0102] Enhanced control of the 3D geometric shape of the printed structure can be obtained by enabling the substrate plate to move in relation to the printer head in the X, Y, Z planes and by a first angle (φ) that defines the rotation of the X, Y planes around the Z-axis.

[0103] US2013012029A1 discloses an ALD printer having a printer head that can move in the XYZ plane. The distribution of the exit / exhaust channels differs from the aforementioned embodiment and provides only area deposition in the XY plane, i.e., a single plane, providing only 2D resolution rather than 3D resolution. It is not possible to obtain a 3D structure directly from printing using the ALD printer of US2013 / 012029A1.

[0104] Atomic-scale thickness resolution (digital growth control) and pattern resolution up to 12 nm can be obtained by a printer according to the first, second and / or third embodiment and a method according to the fourth, fifth, sixth and / or seventh embodiment.

[0105] Having one or more first exit openings, each having a diameter smaller than 900 micrometers, is essential for obtaining the low resolution obtainable by the printer according to the first, second and / or third embodiment and the method according to the fourth, fifth, sixth, and / or seventh embodiment.

[0106] In one or more embodiments, the first outlet opening diameter is less than 800 μm, for example, less than 700 μm, for example, less than 600 μm, for example, less than 500 μm, for example, less than 400 μm, for example, less than 300 μm, for example, less than 200 μm, for example, less than 100 μm, for example, less than 50 μm.

[0107] Separate channels and apertures further enable the printing of precise micro / nano-scale features. This prevents cross-contamination of the material, providing high-purity printed material. Therefore, multi-material printing can be utilized with rapid switching between different materials, characterized by short pulse valves and a short distance between the gas source and the print head.

[0108] Conversely, having an ejection aperture in the range of 1-12 mm in an ALD printer is disclosed in US2015086716A1, and such resolution cannot be achieved. Millimeter apertures entail the fact that the process and printer of US2015086716A1 rely on the Bernoulli principle, in which the highest velocity occurs at the lowest pressure and the lowest velocity occurs at the highest pressure within a horizontally flowing fluid. When working with micro-sized apertures of less than 100 micrometers, as in the case of the printer according to the first, second, and / or third embodiments and the method according to the fourth, fifth, sixth, and / or seventh embodiments, the Bernoulli principle is expected to begin to fail due to rapid molecular scattering caused by the increase in the relevant velocity and impact. More generally, the Bernoulli principle is applicable only to isentropic flow, without considering turbulent and high Mach number flows.

[0109] In US2015086716A1, the printer head moves relative to a fixed substrate plate. In the printer according to the first, second and / or third embodiment and the method according to the fourth, fifth, sixth and / or seventh embodiment, the substrate plate is instead moved in the XYZ plane relative to the printer head. These differences provide differences in rigidity and possible speeds and facilitate the maintenance of plan-parallelism required for the printer to operate.

[0110] A printer according to the first, second, and / or third embodiment and a method according to the fourth, fifth, sixth, and / or seventh embodiment can be used for both cleaning, deposition, and / or etching of fluids / materials having inorganic, organic, and metal compositions. When the printer is used for etching, the term precursor fluid means comprising an etching fluid / agent.

[0111] The printer according to the first, second, and / or third embodiments and the method according to the fourth, fifth, sixth, and / or seventh embodiments can operate without plasma and, for example, can process titanium isopropoxide (TTIP) with water to obtain titanium dioxide (TiO2). Additionally, the printer can process the printing of sulfides, oxides, nitrides, and pure metals, as well as the printing of core composite 3 and 4-element composite materials. Thus, in one or more embodiments, when printed, the precursor fluid forms sulfide, oxide, nitride, pure metal, and core composite 3 and 4-element compound materials.

[0112] A printer according to the first, second, and / or third embodiments and a method according to the fourth, fifth, sixth, and / or seventh embodiments also allow for the formation of continuous films and patterns. By using a printer according to the first, second, and third embodiments, high conformality for material multilayering and any surface shape can be obtained.

[0113] Higher deposition rates can be further obtained by using a printer according to the first, second, and / or third embodiments and a method according to the fourth, fifth, sixth, and / or seventh embodiments. The printer can operate at room temperature and at higher temperatures, such as 400 degrees Celsius. A printer operating at a temperature means that at least the printer head is connected to a heating source to heat it to a specific temperature. Additionally, the substrate plate can also be heated to an elevated temperature.

[0114] The printer can operate at atmospheric pressure or at low vacuum pressure in an open and controlled environment. Operating the printer at a specific pressure means that, at a minimum, the printer head is maintained at atmospheric pressure or at low vacuum pressure in an open and controlled environment. Advantageously, it offers low consumption of reactive fluids and provides material versatility. Furthermore, it enables additive processing, high resolution of selected areas, and adaptive processing for various planar and wavy inorganic and organic substrates.

[0115] In one or more examples, one or more exhaust openings include: one or more first exhaust openings connected to a first exhaust channel to remove a first precursor fluid (and possibly an inert fluid) that has not been deposited from the substrate; and one or more second exhaust openings connected to a second exhaust channel to remove a second precursor fluid (and possibly an inert fluid) that has not been deposited from the substrate.

[0116] By having separate exhaust openings for each precursor fluid, chemical clogging in the exhaust channels and any potential damage to the printer are prevented. If the two exhaust channels are merged into one, the fluids react in the merged channel and block it, leading to operational failure.

[0117] One or more exhaust channels can be driven by a vacuum pump to a pressure of at least about 20 mbar. The pressure will generally be measured at the inlet.

[0118] In one or more embodiments, the X,Y plane extends parallel to the substrate plate. Similarly, the rotation of the X,Y plane around the Z-axis may be a rotation of the substrate plate. Additionally, the inclination of the X,Y plane may be an inclination of the substrate plate relative to the printer head. In one or more embodiments, the printer head may be tilted. The second angle (θ) may be in the range of 0.5 to 10 degrees, e.g. 1 to 5 degrees, e.g. 2 to 4 degrees, or e.g. 2.5 to 3.5 degrees.

[0119] The Z-axis extends between the print head and the substrate plate, defining the distance between the print head and the substrate plate. The distance between the print head and the substrate plate is in the range of 0.005-100 μm, e.g. 0.005-50 μm, e.g. 0.01-50 μm, e.g. 0.05-50 μm, e.g. 0.1-50 μm, e.g. 0.1-25 μm, or e.g. 1-10 μm.

[0120] In one or more embodiments, the first outlet opening diameter is less than 800 μm, for example, less than 700 μm, for example, less than 600 μm, for example, less than 500 μm, for example, less than 400 μm, for example, less than 300 μm, for example, less than 200 μm, for example, less than 100 μm, for example, less than 50 μm.

[0121] In one or more embodiments, the first outlet opening diameter is in the range of 0.005-850 μm, e.g. 0.005-750 μm, e.g. 0.005-650 μm, e.g. 0.005-550 μm, e.g. 0.005-450 μm, e.g. 0.005-250 μm, e.g. 0.005-100 μm, e.g. 0.01-50 μm, e.g. 0.01-10 μm, e.g. 0.01-1 μm, e.g. 0.015-0.05 μm, e.g. 0.02 μm.

[0122] In one or more embodiments, the printer is applied to provide a pattern resolution of 20 nm to 1 mm. To achieve a specific resolution, the size of the first exit aperture should be about 0.625 to 1.25 times the desired resolution.

[0123] The resolution of the printed structure, that is, the resolution size, depends on the diameter of one or more first exit openings and the distance between the printer head and the substrate plate.

[0124] In one or more embodiments, the discharge surface of the printer head further includes a safety evacuation channel located at the outermost edge around the first, second, and third outlet openings and the exhaust opening. The outermost exhaust opening, e.g., the second exhaust opening, may serve as a safety evacuation channel. The safety evacuation channel has two functions: it enables the printer to operate under atmospheric conditions when the used second precursor is hazardous, such as ozone or hydrogen sulfide, and further improves the local inert atmosphere around the deposition area.

[0125] In one or more embodiments, the printer head ejection surface is a disc, a square, a rectangle, a triangle, a pentagon, or a set of openings each forming a circular disc. The printer head ejection surface may preferably be in the shape of a disc.

[0126] In one or more embodiments, the printer is applied to change the distance between the printer head and the substrate plate during printing of a three-dimensional structure.

[0127] In one or more embodiments, the printer is applied to operate at a deposition rate of 1 nm / min or less. The deposition rate is a factor of the substrate movement speed, temperature, and the reactivity of the selected first and second precursor fluids. Application is performed by adjusting the movement of the substrate.

[0128] In one or more embodiments, the printer is applied to operate at a deposition rate in the range of 0.1-100 nm / min, e.g. 0.1-100 nm / min, e.g. 1-50 nm / min, e.g. 0.1-10 nm / min, e.g. 0.5-10 nm / min, e.g. 1-10 nm / min.

[0129] In one or more embodiments, the printer is adapted to operate at atmospheric pressure. In other embodiments, the printer is adapted to operate in a vacuum or ultra-high vacuum. That the printer operates at a specific pressure means that, at a minimum, the printer head is maintained at atmospheric pressure or in a low vacuum state in an open and controlled ambient environment.

[0130] In one or more embodiments, the printer is applied 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 operation at a temperature between 10 and 600°C, for example, between 15 and 450°C, for example, between 20 and 400°C. A printer operating at a specific temperature means that at least the printer head is connected to a heating source to heat it to a specific temperature. Additionally, the substrate plate may be heated to an elevated temperature. All types of piping / conduits, valves, precursors, and / or inert gas supply devices may also be heated / cooled to control the temperature. Thus, the printer may be applied to control the temperature of the supply channels. This allows the printer to operate fully at a desired temperature, for example, a temperature much higher than room temperature.

[0131] In one or more embodiments, the supply channel is made of stainless steel, Teflon, a fluoroelastomer material (FKM), or a perfluoroelastomer compound (FFKM). This provides a control channel in which the temperature can be controlled.

[0132] Temperature control can be extended through a valve and supply channel system to the entire piping channel extending from a container containing a precursor to the printer head. The temperature can be controlled, for example, in different zones, for example, at least three zones.

[0133] In one or more embodiments, the printer is adapted to operate as a bottom-up set in which the printer head is positioned on the substrate plate.

[0134] In one or more embodiments, the printer head plate is:

[0135] - One or more first distribution channels applied to guide a first precursor fluid from a first inlet supply channel to one or more first outlet openings;

[0136] - One or more second distribution channels applied to distribute a second precursor fluid from a second inlet supply channel to one or more second outlet openings;

[0137] - Includes one or more third distribution channels applied to distribute an inert fluid from a third inlet supply channel to one or more third outlet openings.

[0138] In one or more embodiments, the printer head plate is removablely attached to the printer head so that different printer head plates can be connected to the printer head, and the different printer head plates have opening diameters of various sizes of the first exit opening.

[0139] In one or more embodiments, the one or more second and third outlet openings and the one or more exhaust openings are located around the one or more first outlet openings.

[0140] In one or more embodiments, the one or more second and third outlet openings and the one or more exhaust openings are positioned circumferentially around each of the one or more first outlet openings.

[0141] In one or more embodiments, the one or more second and third outlet openings and the one or more exhaust openings are symmetrically positioned around the one or more first precursor openings. In one or more embodiments, the one or more first outlet openings include a first outlet opening located at the center of the printer head plate.

[0142] In one or more embodiments, a main set of exhaust openings is located between each of the first outlet openings and a main set of the second outlet openings; and / or a main set of the third outlet openings is located between each of the first outlet openings and a main set of the second outlet openings.

[0143] In one or more embodiments, the precursor fluid distance between the main set of the one or more first outlet openings and the second outlet opening is between 5 μm and 3,000 μm, or for example between 5 μm and 500 μm, or for example between 5 μm and 100 μm, or for example between 5 μm and 30 μm, or for example between 10 μm and 20 μm, or for example between 30 μm and 3,000 μm, or for example between 50 μm and 2,000 μm, or for example between 100 μm and 1,000 μm.

[0144] In one or more embodiments, the printer includes multiple printer heads. Including multiple printer heads is not a simple process when the printer heads have micro-scale openings, i.e., micro-nozzle print heads. Each micro-nozzle requires a special mounting mechanism and micro-nozzle design. Furthermore, successfully connecting multiple printer heads to the same gas distribution system is not simple.

[0145] In one or more embodiments, the printer head is made of a metal such as corrosion-resistant steel or ceramic.

[0146] In one or more embodiments, the printer is applied to alternately supply a first precursor fluid, an inert fluid, and a second precursor fluid onto the substrate.

[0147] A printer according to the second and fifth embodiments may further include a chamber surrounding the substrate, wherein the chamber is configured to contain a second precursor fluid. Brief explanation of the drawing

[0148] Various examples are described below with reference to the drawings. Identical reference numbers refer to identical elements throughout. Accordingly, detailed descriptions of similar elements are omitted in relation to the description of each drawing. Furthermore, it should be noted that the drawings are intended only to facilitate the description of examples. They are not intended to be a complete description of the claimed invention or a limitation on the scope of the claimed invention. Additionally, the examples illustrated are not required to possess all the embodiments or advantages depicted. The embodiments or advantages described in relation to a particular example are not necessarily limited to that example and may be practiced in any other examples even if they are not so illustrated or explicitly described. Figure 1a illustrates temporal atomic layer deposition and Figure 1b illustrates spatial atomic layer deposition. FIG. 2 schematically illustrates an atomic layer process printer for material deposition, etching, and / or cleaning at an atomic scale in a selected area. FIGS. 3a-c shows an embodiment of a printer head illustrated in a perspective view (Fig. 3a), an upward view (Fig. 3b), and an exploded view (Fig. 3c). FIG. 3d shows an example of a distribution channel inside a printer head plate. FIG. 4 shows a first embodiment of a printer head plate. Figure 5 shows a second embodiment of a printer head plate. FIG. 6 shows a third embodiment of a printer head plate. FIG. 7 shows a fourth embodiment of a printer head plate. FIG. 8 shows a fifth embodiment of a printer head plate. FIG. 9 shows a sixth embodiment of a printer head plate. FIG. 10 shows an example of a printer that can be controlled for switching between spatial and temporal ALD type processes. Figure 11 shows an SEM plan view of a TiO2 print line obtained using a printer. Figure 12 shows a complex printed pattern of amorphous TiO2 deposited using a printer. Figure 13a shows energy-dispersive X-ray spectroscopy of platinum lines printed using a printer. Figure 14 shows a complex printed pattern of amorphous Pt deposited using a printer. Figures 15a and 15b show the X-ray diffraction patterns of the material deposited using a printer. Figure 16 shows the growth dependence on temperature for TiO2 deposition using a printer. Figure 17 shows the atomic force microscope profile of a TiO2 line deposited using a printer. Figure 18a shows the X-ray photoelectron spectrum of TiO2 deposited using a printer, and Figure 18b shows the X-ray photoelectron spectrum of PtO2 deposited using a printer. Figures 19a-c show platinum growth curves measured at various substrate temperatures. Specific details for implementing the invention

[0149] Exemplary embodiments will be described more fully below with reference to the accompanying drawings. In this regard, the embodiments may take different forms and should not be interpreted as being limited to the description provided herein. Accordingly, the embodiments below are intended to describe aspects with reference to the drawings. As used herein, the term "and / or" includes all combinations of one or more of the related and listed items. Expressions such as "at least one of the following" modify the entire list of elements when preceding a list of elements, but do not modify the individual elements of the list.

[0150] In the drawings, for convenience and clarity of explanation, the thicknesses of multiple layers and regions are depicted in an enlarged manner. When a layer, region, element, or plate is referred to as being "above" another layer, region, element, or plate, the other layer, region, element, or plate, or an interposed layer, region, element, or plate may exist between them. Conversely, when a layer, region, element, or plate is referred to as being "directly above" another layer, region, element, or plate, there is no interposed layer, region, element, or plate between them. Additionally, when a layer, region, element, or plate is referred to as being "below" another layer, region, element, or plate, it may be directly below the other layer, region, element, or plate, or an interposed layer, region, element, or plate may exist between them. Conversely, when a layer, region, element, or plate is referred to as being "directly below" another layer, region, element, or plate, there is no interposed layer, region, element, or plate between them.

[0151] Spatially relative terms such as "lower" or "bottom," and "upper" or "top," "below," "beneath," "less," "above," etc., may be used in the present invention to facilitate the description of the relationship between one element or component and another element or component as described in the drawings. Spatially relative terms are to be understood as intended to include other directions of the device in use or operation in addition to the directions depicted in the drawings. For example, if the device depicted in the drawings is inverted, it may be described as being on the "lower" side of another element, or the "below" or "beneath" of another element may be directed toward the "upper" side of another element, or toward the "above" of another element. Accordingly, the exemplary terms "below" or "beneath" may include both "lower" and "upper" directional positions depending on the specific direction of the drawings. Similarly, if one of the devices in the drawings is inverted, the element described as "below" or "bottom" will face "above" the other element. Therefore, the exemplary terms "below" or "bottom" may include both upward and downward directions, and thus spatially relative terms may be interpreted differently depending on the described direction.

[0152] Throughout the specification, where an element is referred to as being "connected" to another element, the element is "directly connected" to another configuration or is "electrically connected" to another component through one or more intervening elements sandwiched between them.

[0153] The terms used in this invention are used merely to describe specific examples and are not intended to be limiting. As used in this invention, the singular forms “one,” “one,” and “above” are intended to include the plural form including “at least one” unless the content otherwise clearly indicates. “At least one” should not be interpreted as limiting “one” or “one.” As used herein, the terms “constitute,” “constitute,” “include,” and / or “include” specify a stated feature, integer, step, operation, element, and / or component, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0154] It will be understood that while terms such as "first," "second," and "third" may be used in the present invention to describe various elements, these elements should not be limited by these terms. These terms are used solely to distinguish one element from another. Accordingly, the "first element" described below may be named the "second element" or the "third element," and the "second element" and the "third element" may also be named similarly without departing from the teachings of the present invention.

[0155] The terms “about” or “approximately” as used in the present invention mean that the stated value is within an acceptable range of deviation for a specific value as determined by a person skilled in the art, taking into account errors associated with uncertain measurements and the measurement of a specific quantity (i.e., the limits of the measurement system). For example, “about” may mean within one or more standard deviations, or within ± 30%, 20%, 10%, or 5% of the stated value.

[0156] Unless otherwise defined, all terms used in this invention (including technical and scientific terms) have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with such meaning in the context of the relevant technology, and should not be interpreted in an idealized or overly formal sense unless explicitly defined in this specification.

[0157] Exemplary examples are described in the present invention with reference to cross-sectional views, which are schematic diagrams of idealized examples, wherein similar reference numbers refer to similar elements throughout the specification. Thus, variations from the shapes of the examples are expected, for example, as a result of manufacturing techniques and / or tolerances. Accordingly, the examples described in the present invention should not be interpreted as being limited to the specific shapes of the regions as described in the present invention, and should include, for example, deviations in shape that occur during the manufacturing process. For example, regions depicted or described as flat may have rough and / or non-linear features. Also, exemplified acute angles may be rounded. Thus, regions depicted in the drawings are essentially schematic, and these shapes are not intended to represent the exact shape of the regions or to limit the scope of the claims. Some parts not related to the specification may not be provided to specifically describe the exemplary examples of the present disclosure.

[0158] Figure 1a illustrates temporal atomic layer deposition (ALD) in which precursor fluids are separated over time, and Figure 1b illustrates spatial atomic layer deposition (ALD) in which precursor fluids are separated in space.

[0159] Temporal ALD utilizes a chamber in which a functionalized substrate is placed. The substrate in the chamber is generally exposed to a first precursor fluid (132) that is deposited on the functionalized surface, exposed to an inert fluid (136) for cleaning the chamber, exposed to a second precursor fluid (134) that is deposited on the surface covered by a first gas, and exposed to an inert fluid (136) for cleaning the chamber. This process can be repeated until a desired product is obtained, as illustrated in FIG. 1a.

[0160] 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 precursor fluids (132, 134) and inert fluids (136) and instead moves the sample substrate (162) in the X,Y direction as shown in FIG. 1b.

[0161] FIG. 2 schematically illustrates an atomic layer process printer (100) as disclosed in the present invention for material deposition, etching, and / or cleaning at an atomic scale in a selected area. The printer (100) includes a substrate plate (160) for holding a substrate (162) and a printer head (101) positioned to face the substrate (162) on the substrate plate (160). The X, Y, and Z axes are illustrated in the upper right corner of FIG. 2. Additionally, a first angle (φ) defining the rotation of the X,Y plane around the Z axis and a second angle (θ) defining the inclination of the X,Y plane around the axis in the X,Y plane are illustrated in the upper right corner of FIG. 2. The substrate plate (160) and the printer head (101) are movable relative to one or more of the X, Y, Z planes and / or the two angles (φ and θ). In this way, a complete 3D movement can be achieved.

[0162] The printer (100) will operate normally in an upward set in which the printer head (101) is positioned over the substrate plate (160) as illustrated in FIG. 2. Generally, the substrate plate (160) will be moved around the X, Y, Z planes and / or two angles (φ and θ) and the printer head (101) will remain stationary. However, movement of the printer head (101) in the X, Y, Z planes and / or around two angles (φ and θ) can also be expected while the substrate plate (160) remains stationary. Alternatively, movement of both the substrate plate (160) and the printer head (101) may be possible simultaneously.

[0163] As illustrated in FIG. 2, the X,Y plane may extend parallel to the substrate plate (160). Thus, rotation of the X,Y plane around the Z-axis may be rotation of the substrate plate (160). Generally, the substrate (162) is fixed to the substrate plate (160). The inclination of the X,Y plane may be the inclination of the substrate plate (160) relative to the printer head (101). Thus, any movement of the substrate plate will be converted into movement of the substrate (162).

[0164] The Z-axis extends between the printer head (101) and the substrate plate (160) and defines 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 0.005-100 μm, e.g. 0.005-50 μm, e.g. 0.01-50 μm, e.g. 0.05-50 μm, e.g. 0.1-50 μm, e.g. 0.1-25 μm, or e.g. 1-10 μm.

[0165] 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) may be moved relative to each other along the axis in the X,Y plane; along the Z axis; by two or more of a first angle (φ); and a second angle (θ). Alternatively, the substrate plate (160) and the printer head (101) may be moved relative to each other along the axis in the X,Y plane; along the Z axis; by three or all of the first angle (φ); and the second angle (θ). The distance between the printer head (101) and the substrate plate (160) may also be variable during printing of the three-dimensional structure.

[0166] The printer (100) will be able to deposit at least one molecular layer per minute. Generally, this will provide a maximum of 100 nm per minute. Thus, the printer can operate at a deposition rate in the range of 0.1-100 nm / min, e.g. 1-100 nm / min, e.g. 1-50 nm / min, e.g. 0.1-10 nm / min, e.g. 0.5-10 nm / min, e.g. 1-10 nm / min. The printer can generally operate normally at a deposition rate of 1 nm / min or less.

[0167] The printer (100) is configured to operate at atmospheric pressure. However, the printer (100) can alternatively be configured to operate in a vacuum or ultra-high vacuum.

[0168] The printer (100) is generally adapted to operate at a temperature between 10-600°C, for example between 15-450°C, for example between 20-400°C. The printer will generally include a heating source that heats at least the printer head so as to be able to operate at the requested temperature.

[0169] The printer may also be configured to include multiple printer heads (101) rather than a single printer head (101). Including multiple print heads is not a simple process if the print heads are micro-scale apertures, i.e., micro-nozzle print heads. Each micro-nozzle requires a special mounting mechanism and micro-nozzle design. Furthermore, successfully connecting multiple printer heads to the same gas distribution system is not simple.

[0170] Now, referring to FIGS. 3a-c, an example of a printer head (101) is shown in more detail in a perspective view (Fig. 3a), an upward view (Fig. 3b), and an exploded view (Fig. 3c). 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).

[0171] A printer head plate (104) is connected to an additional printer head plate (105), which is in turn releasedly secured 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 detached from the printer head (102) to allow for easy removal and / or change of the printer head plate (104). The clamping nut (107) can be secured to the printer head body (102) by a screw connection, a bayonet connection, a snap-fit ​​connection, etc. The printer head plate (104) is removablely attached to the printer head (101), so that different printer head plates (104) can be connected to the printer head (101), and the different printer head plates (104) have different opening diameters of the first exit opening. This makes it possible to obtain different atomic resolutions using the same printer (100).

[0172] Alternatively, the printer head plate (104) can be simply soldered to a piece of metal. In this type of setup, a clamp is not required.

[0173] The inlet supply / outlet channel (121) includes both the inlet supply channels (122, 124, 126) and the discharge channels (126, 128). FIG. 4-9 shows another example of the location of the opening (111) in the printer head plate (104), together with FIG. 4, which shows an example of a method in which the inlet supply channels (122, 124, 126) and the discharge channels (126, 128) can be connected to the opening (111) in the printer head plate (104).

[0174] In FIG. 4, a symmetric printer head plate (104a) is shown in close-up with an example of how an opening (111) is connected to an inlet supply channel (122, 124, 126) and an outlet channel (126, 128). The printer head plate (104a) in FIG. 4 includes a centrally located first outlet opening (112), which has a first outlet opening diameter smaller than 900 micrometers. The first outlet opening (112) is connected to a first inlet supply channel (122) for guiding a first precursor fluid (132) onto a substrate (162). The first precursor fluid (132) is shown in FIG. 4 as being inside a circular container. This is merely an example of a container for holding the first precursor fluid (132).

[0175] The printer head plate (104a) in FIG. 4 also includes a plurality of second outlet openings (114) connected to a second inlet supply channel (124) to guide a second precursor fluid (134) onto a substrate (162); and a plurality of third outlet openings (116) connected to a third inlet supply channel (126) to guide an inert fluid (136) onto a substrate (162). Both the second outlet openings (114) and the third outlet openings (116) are shown in FIG. 4 as being centrally located around the first outlet opening (112) in the embodiment.

[0176] It is a ring having a plurality of concentrically positioned discharge openings (118) connected to a first discharge channel (128) between a ring concentrically positioned between a first discharge opening (112) and a third discharge opening (116). Undeposited precursor fluid / inert fluid (138) is removed through a plurality of first exhaust openings (118) connected to the first discharge channel (128). In the example illustrated in FIG. 5, the undeposited first precursor fluid (132) and inert fluid (136) are mainly removed through the first exhaust openings (118).

[0177] A ring positioned concentrically around a third outlet opening (116) has a plurality of second outlet openings (114) positioned concentrically to supply the second precursor fluid (134) to the substrate (162). A plurality of second exhaust openings (120) for removing the un-deposited second precursor fluid (134) and possibly a portion of the inert fluid (136) are made to be positioned circumferentially around the second outlet opening (114).

[0178] FIG. 4 illustrates only one embodiment of the printer head plate (104a), but often the main set of first exhaust openings (118, 120) will be located between each of the first exit openings (112) and the main set of second exit openings (114) and / or between each of the first exit openings (112) and the main set of second exit openings (114).

[0179] Arrows in the first inlet supply channel (122, 124, 126) and discharge channel (128, 130) indicate the direction in which the fluid flows through the channels (122, 124, 126, 128, 130).

[0180] The precursor fluid distance between the first outlet opening (112) and the second outlet opening (114) will generally be between 5 μm and 3,000 μm, or for example between 5 μm and 500 μm, or for example between 5 μm and 100 μm, or for example between 5 μm and 30 μm, or for example between 10 μm and 20 μm, or for example between 30 μm and 3,000 μm, or for example between 50 μm and 2,000 μm, or for example between 100 μm and 1,000 μm.

[0181] Having a relatively large distance between the first outlet opening (112) and the second outlet opening (114) prevents the two precursor fluids (132, 134) from mixing simultaneously. Thus, having an exhaust opening distance of 50 μm or more between the first exhaust opening (118) and the second exhaust opening (120) prevents the mixing of the two precursor fluids at the exhaust openings (118, 120). On the other hand, when the exhaust opening distance between the first exhaust opening (118) and the second exhaust opening (120) is less than 50 μm, the mixing of the two precursor fluids at the exhaust openings (118, 120) is generally observed.

[0182] As illustrated in FIG. 3c, 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 plurality of openings (122', 124', 126', 128, 130'), each of which is connected to the supply channels (122, 124, 126, 128, 130). An O-ring (108) will generally be made between the additional printer head plate (105) and the printer head body (102) to ensure a hermetic connection.

[0183] FIG. 3d illustrates a distribution channel within a printer head plate (104). The distribution channel includes one or more first distribution channels (142) applied to guide a first precursor fluid (132) from a first inlet supply channel (122) to a first outlet opening (112). The distribution channel within the printer head plate (104) also includes one or more second distribution channels (144) applied to distribute a second precursor fluid (134) from a second inlet supply channel (124) to one or more second outlet openings (114), and one or more third distribution channels (146) applied to distribute an inert fluid (136) from a third inlet supply channel (126) to one or more third outlet openings (116). The distribution channel within the printer head plate (104) further includes one or more exhaust distribution channels (147, 147') applied to remove the precursor fluid (132, 134) and the inert fluid (136).

[0184] FIG. 5 shows another embodiment of an enlarged view of a printer head plate (104b) having a plurality of first exit openings (112). To provide the viewer with a clearer drawing of the printer head plate (104b), a smaller version of the plate is shown in the upper left corner without a reference symbol. In the printer head plate (104b) shown in FIG. 5, there are six first exit openings (112) located in the center of the printer head plate (104b). Surrounding the first exit openings (112) is a set of first exhaust openings (118), which is again surrounded by a set of third exit openings (116), and then by a set of second exit openings (114) and a set of second exhaust openings (120). Compared to the printer head plate (104a) of FIG. 4, the circumferential order of the exit openings (112, 114, 116) and exhaust openings (118, 120) is the same. However, the number of exit openings (112, 114, 116) and exhaust openings (118, 120) in each set of rings is different, and the individual distances between the openings (112, 114, 116, 118, 120) in the same ring are different. Additionally, the sizes of the openings (112, 114, 116, 118, 120) are different. The size of the first exit opening (112) is similar to that shown in FIG. 4, with a diameter smaller than 900 μm.

[0185] FIG. 6 shows another embodiment of an enlarged view of a partially symmetrical printer head plate (104c), in which square-shaped openings (112, 114, 116, 118) are present. In this embodiment, only one type of exhaust opening (118) is present for removing the inert fluid (136) as well as the undeposited first precursor fluid (132) and the undeposited second precursor fluid (134). Again, only one first outlet opening (112) is present. Surrounding the first outlet opening (112) is one set of first exhaust openings (118), which is then surrounded by one set of third outlet openings (116), and subsequently by one set of second outlet openings (114). Compared to the printer head plates (104a, 104b) of FIGS. 4 and 5, the openings (114, 116, 118) are positioned in a square around the first exit opening (112). Although the shape of the openings (112, 114, 116, 118, 120) in FIG. 6 is different from the circular shape in FIGS. 4 and 5, the size of the first exit opening (112) is still smaller than 900 μm from one corner to the opposite corner.

[0186] The printer head plates (104a, 104b, 104c) illustrated in FIGS. 4, 5, and 6 all have symmetrical positions of openings (112, 114, 116, 118, 120) at least to some extent. However, an asymmetric configuration may also be used. FIG. 7 shows an example of an enlarged view of an asymmetric printer head plate (104d), in which the openings (112, 114, 116, 118, 120) are positioned randomly. The absence of reference numbers for some of the openings is intended to illustrate other options, such as the possibility of different circles depending on the type of opening (112, 114, 116, 118, 120).

[0187] FIG. 8 shows an example of an enlarged view of a printer head plate (104e) somewhat similar to FIG. 4, with the difference that the third exit opening (116') has an offset angle.

[0188] FIG. 9 shows an example of an enlarged view of a printer head plate (104f) in which the second exit opening (114''), the third exit opening (116''), the first exhaust opening (118''), and the second exhaust opening (120'') form a ring. The printer head plate (104f) in FIG. 9 is somewhat similar to that in FIG. 4, except for the difference that a plurality of the second exit opening (114), the third exit opening (116), the first exhaust opening (118), and the second exhaust opening (120), which are respectively arranged in a concentric circle configuration around the first exit opening (112) in FIG. 4, are combined into one larger ring-shaped opening for each of the second exit opening (114''), the third exit opening (116''), the first exhaust opening (118''), and the second exhaust opening (120'').

[0189] In all illustrated embodiments of the printer head (104a, 104b, 104c, 104d, 104e, 104f) in FIG. 4-9, the first exit opening diameter of all first exit openings (112) is less than 900 μm. In one or more embodiments, the first exit opening diameter is less than 800 μm, e.g., less than 700 μm, e.g., less than 600 μm, e.g., less than 500 μm, e.g., less than 400 μm, e.g., less than 300 μm, e.g., less than 200 μm, e.g., less than 100 μm, e.g., less than 50 μm.

[0190] In one or more embodiments, the first outlet opening diameter is 0.005-850 μm, for example 0.005-750 μm, for example 0.005-650 μm, for example 0.005-550 μm, for example 0.005-450 μm, for example 0.005-250 μm, for example 0.005-100 μm, for example 0.01-50 μm, for example 0.01-10 μm, for example 0.01-1 μm, for example 0.015-0.05 μm, for example 0.02 μm.

[0191] Printers can generally provide pattern resolutions of 20 nm to 1 mm. The resolution of the printed structure, i.e., the resolution size, can vary depending on both the diameter of one or more first exit openings and the distance between the printer head and the substrate plate, as shown in Table 1 below.

[0192] Table 1. Selected size of the first exit opening, distance between the printer head and the substrate plate, and lateral resolution obtained from the printed structure.

[0193] Side resolution Diameter of the first opening The distance between the sample and the print head 100 µm - 1 mm 80 - 800 ㎛ 100 ㎛ 10 - 100 ㎛ 8 - 80 ㎛ 10 - 100 ㎛ 1 - 10 ㎛ 800 nm - 8 µm 1 - 10 ㎛ 100 nm -1 µm 80 nm - 800 nm 100 - 1000 nm

[0194] The printer head (101) may include a safety escape channel located at the outermost edge around the openings (112, 114, 116, 118) in the printer head plates (104a, 104b, 104c, 104d, 104e, 104f). The outermost exhaust opening, for example, the second exhaust opening (120), may serve as a safety escape channel.

[0195] The discharge surface of the printer head (101) may be in a shape similar to a set of openings forming a square, rectangular, triangular, pentagonal, or circular disc, respectively. The discharge surface may refer to either the printer head plate (104) or an additional printer head plate (105). Overall, the shape is not relevant as long as the printer head plate(s) (104, 110) are easily attached to and / or released from the printer (101).

[0196] The printer (100) can be used for a spatial type of ALD as described above in relation to the drawing, wherein there are a plurality of outlet openings (112, 114, 116) for each of the precursor fluid (132, 134) and the inert fluid (136). This corresponds to a first embodiment of the printer (100) as described in the present invention.

[0197] According to a fourth aspect of the present invention, a method for depositing material on a substrate (162) in a selected area is also disclosed. The method is:

[0198] · A step of providing an atomic layer process printer having a substrate plate (160) and a printer head (101) positioned toward the substrate plate,

[0199] Here, the substrate plate (160) is in relation to the printer head (101):

[0200] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0201] o along the Z-axis perpendicular to the above X,Y plane; and

[0202] o It is movable by a first angle (φ) defining rotation in the X,Y plane around the above Z-axis;

[0203] Here, the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane;

[0204] · A step of positioning a substrate (162) on the substrate plate (160);

[0205] · A step of exposing a substrate (162) to a first precursor fluid (132) through one or more first outlet openings (112), each having a diameter smaller than 900 micrometers;

[0206] · A step of removing a first precursor fluid (132) that is 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);

[0207] · A step of exposing a substrate (162) on which a first precursor is deposited to a second precursor fluid (134);

[0208] · Includes a step of removing a second precursor fluid (134) that is not deposited on the substrate (162) by one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136).

[0209] In one or more embodiments, the substrate plate (160) and the printer head (101) are moved relative to each other between the deposition of the precursor fluid (132, 134).

[0210] As described in the second and fifth embodiments, the printer (100) may be configured to alternately supply precursor fluids (132, 134) and inert fluids (136) to a substrate (162) through the same outlet openings (112, 114, 116) including at least the first outlet opening(s) (112). A sequence of the first precursor fluid (132), then the inert fluid (136), and then the second precursor fluid (134) may be used. This corresponds to a temporal type ALD as illustrated in FIG. 1a. The printer head plate of FIG. 4-9 may be used for this setup. The only difference when using the printer (100) in this mode compared to the spatial type mode is that the supply channels (122, 124, 126) must be connected to all openings (112, 114, 116). In addition, to obtain high resolution using the printer according to the second embodiment, the exit aperture diameters all need to be smaller than 900 μm.

[0211] According to a fifth aspect of the present invention, a method for vertically depositing material on a substrate (162) in a selected area is further disclosed. The method is:

[0212] · A step of providing an atomic layer process printer having a substrate plate (160) and a printer head (101) positioned toward the substrate plate, wherein the substrate plate (160) and the printer head (101) are:

[0213] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0214] o along the Z-axis perpendicular to the X,Y plane; and

[0215] o Moveable to one or more of the following by a first angle (φ) defining rotation in the X,Y plane around the Z-axis;

[0216] Here, the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around an axis in the X,Y plane;

[0217] · A step of positioning a substrate (162) on a substrate plate (160);

[0218] · A step of exposing a substrate (162) to a first precursor fluid (132) through one or more first outlet openings (112), each having a diameter smaller than 900 micrometers;

[0219] · A step of removing a first precursor fluid (132) that is 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 one or more first outlet openings (112);

[0220] · A step of exposing a substrate (162) on which a first precursor is deposited to a second precursor fluid (134) through one or more first outlet openings (112);

[0221] · Includes the step of removing a second precursor fluid (134) that is 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 one or more first outlet openings (112).

[0222] Additionally, by having a chamber surrounding the substrate (162), it may not be necessary to supply the second precursor fluid (134) to the substrate (162) through the second outlet opening (114) using the second inlet supply channel (124). This corresponds to the third embodiment described above.

[0223] Alternatively, the precursor fluid (132, 134) may be mixed before being supplied to the substrate (162). This embodiment is designed in the third embodiment. Accordingly, the present invention discloses a method for rapid material deposition on a substrate (162) in a selected area in the sixth embodiment, wherein the method comprises:

[0224] · A step of providing an atomic layer process printer having a substrate plate (160) and a printer head (101) positioned toward the substrate plate,

[0225] Here, the substrate plate (160) is in relation to the printer head (101):

[0226] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0227] o along the Z-axis perpendicular to the X,Y plane; and

[0228] o Moveable by a first angle (φ) defining rotation in the X,Y plane around the Z-axis;

[0229] Here, the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane;

[0230] · A step of positioning a substrate (162) on a substrate plate (160);

[0231] · A step of mixing the first precursor fluid (132) and the second precursor fluid (134);

[0232] · Includes the step of exposing a substrate (162) to a mixture of a first precursor fluid (132) and a second precursor fluid (134) through one or more first outlet openings (112), each having a diameter smaller than 900 micrometers.

[0233] The printer (100) can be used for rapid material deposition as well as etching on the substrate (162) in a selected area. Accordingly, the present invention discloses a method for material etching on the substrate (162) in a selected area in a seventh aspect, said method comprising:

[0234] · A step of providing an atomic layer process printer having a substrate plate (160) and a printer head (101) positioned toward the substrate plate,

[0235] Here, the substrate plate (160) is in relation to the printer head (101):

[0236] o Along the axes in the X,Y plane defined by the X-axis and Y-axis perpendicular to each other;

[0237] o Along the Z-axis perpendicular to the X,Y plane;

[0238] o It is movable by a first angle (φ) that defines rotation in the X,Y plane around the Z-axis;

[0239] Here, the substrate plate (160) and the printer head (101) are movable relative to each other at a second angle (θ) that defines the inclination of the X,Y plane around the axis in the X,Y plane;

[0240] · A step of positioning a substrate (162) on a substrate plate (160);

[0241] · A step of exposing a substrate (162) to a first etching agent through one or more first exit openings (112), each having a diameter smaller than 900 micrometers;

[0242] · A step of removing a first etching agent not deposited on the substrate (162) by one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136) through one or more first outlet openings (112);

[0243] · A step of exposing a substrate (162) on which a first precursor is deposited to a second etching agent through one or more first exit openings (112);

[0244] · Includes the step of removing a second 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 one or more first outlet openings (112).

[0245] In a printer according to the method of the 4th-7th embodiment, one or more exhaust openings:

[0246] o One or more first exhaust openings (118) connected to a first exhaust channel (128) to remove a first precursor fluid (132) that is not deposited and possibly an inert fluid (136) from the substrate (162); and

[0247] o It may include one or more second exhaust openings (120) connected to a second exhaust channel (130) to remove the undeposited second precursor fluid (134) and possibly an inert fluid (136) from the substrate (162).

[0248] An embodiment of a printer (100) in which the transition between spatial and temporal ALD type processes can be controlled to include material deposition, etching, and cleaning is shown in FIG. 10.

[0249] The precursor fluids (132, 134) and the inert fluid (136) are represented as gases in FIG. 10, controlled by a flow controller (155) that can be proportionally opened, measure flow, and provide feedback signals. The controller (155) is typically computer-controlled. The precursor fluids (132, 134) are obtained by bubbling an inert gas from a container (156) through a first precursor solution (172) and a second precursor solution (174) to obtain the first precursor fluid (132) and the second precursor fluid (134), respectively.

[0250] 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 plurality of first valve sets (148).

[0251] The printer (100) also includes a second set of valves (149) for flushing supply channels (122, 124, 126) with an inert fluid (136). Since the second precursor fluid (134) can be sent onto the substrate (162) through the first supply channel (122) and likewise the first precursor fluid (132) can be sent onto the substrate (162) through the second supply channel (124), the printer (100) further includes a third valve (150) that allows the printer (100) to be used in a temporal ALD mode. Thus, by controlling the valves (148, 149, 150) individually, for example by turning them on and off, the precursor fluid (132, 134) and the inert fluid (136) can be supplied to the printer head (101) and the substrate (162) as described above for all modes of the printer (100). The valves (148, 149, 150) are generally diaphragm vacuum valves. The valves can be controlled in a number of different ways, for example, pneumatically.

[0252] The inert fluid (136) is supplied to the first precursor solution (172) and the second precursor solution (174) through the fourth valve set (151). The valve (151) can be a needle valve that controls the bubbler.

[0253] The printer further includes a fifth valve (152) which is a pressure reducing valve for controlling the supply of inert fluid (136). The fifth valve (152) is an inert fluid (136) distributor, which enables the printer (100) to operate spatial ALD mode and temporal ALD mode.

[0254] The exhaust channels (128, 130) are controlled by a standard vacuum system comprising a sixth set of valves (153), a pressure sensor (154), a connector (157) (e.g., a T-type connector), a trap (158) that acts as a filter for the pump (159), and the pump (159).

[0255] Examples of printed structures obtained using a printer according to the first embodiment are described below.

[0256] Figure 11 shows an SEM top view of the printed line. The printed material is TiO2. The lateral resolution is about 320 micrometers and the thickness is about 30 nanometers. The diameter of the first exit aperture 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 temperature of the precursor source is set to 60 °C.

[0257] FIG. 12 shows a complex printed pattern of amorphous TiO2 deposited on a printer head, where the diameter of the first exit opening is 80 μm. The printed pattern has 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 temperature of the precursor source is set to 60 °C.

[0258] Figure 13a shows energy-dispersive X-ray spectroscopy of a platinum line printed using a printer. The signal clearly shows the presence of platinum. The signal intensity shown in Figure 13b is related to different line thicknesses. Three different thicknesses are intentionally created (thinnest, thickest, and in between). The diameter of the first exit aperture 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 temperature of the precursor source is set to 60 °C.

[0259] FIG. 14 is a complex printed pattern of platinum. The diameter of the first exit 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 temperature of the precursor source is set to 60 °C.

[0260] Figures 15a and 15b show the X-ray diffraction patterns of the deposited material, where Figure 15a is an anatase TiO2 line pattern deposited using a printer head temperature of 275 °C, and Figure 15b is a platinum line pattern. The diameter of the first exit aperture is 80 μm. The distance between the printer head and the sample is 50 μm. The printer head temperature is 100 °C, the substrate temperature is 250 °C, the tube temperature is 90 °C, and the precursor source is set to a temperature of 60 °C.

[0261] Figure 16 shows the dependence of growth on temperature for TiO2 deposition using TTIP and H2O. Within the limits of error, there is no temperature dependence indicating that deposition is stable in this temperature range, as expected. The diameter of the first exit 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 variable, the temperature of the tube is 90 °C, and the temperature of the precursor source is set to 60 °C.

[0262] Figure 17 shows an atomic force microscope profile of a deposited TiO2 line. The three profiles shown in Figure 17 represent the geometric shape of the edges of the printed line. The diameter of the first exit 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 temperature of the precursor source is set to 60 °C.

[0263] FIG. 18a shows the X-ray photoelectron spectrum of TiO2 deposited using a printer, where the printer head temperature is set to 100 °C, the substrate temperature to 150 °C, the tube temperature to 90 °C, and the precursor source temperature to 60 °C. The peak corresponds to the visible TiO2. The diameter of the first exit aperture is 80 μm. The distance between the printer head and the sample is 50 μm.

[0264] FIG. 18b shows the X-ray photoelectron spectrum of PtO2 deposited using a printer, where the printer head temperature is 100 °C, the substrate temperature is 150 °C, the tube temperature is 90 °C, and the precursor source is set to a temperature of 60 °C. The peak corresponds to the visible PtO2. The diameter of the first exit aperture is 80 μm. The distance between the printer head and the sample is 50 μm.

[0265] Figures 19a-c show platinum growth curves measured using a printer, where the diameter of the first exit 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 200 °C in Figure 19a, 225 °C in Figure 19b, and 250 °C in Figure 19c. The temperature of the tube is 90 °C, and the precursor source is set to a temperature of 60 °C. Explanation of the symbols

[0266] 100: Printer 101: Printer head 102: Printer head body 104: Printer head plate 104a: First embodiment of the printer head plate 104b: Second embodiment of the printer head plate 104c: Third embodiment of the printer head plate 104d: Fourth embodiment of the printer head plate 104e: Fourth embodiment of the printer head plate 105: Additional printer head plate 106: Printer head plate clamp 107: Clamping nut 108: O-ring 111: Openings in the printer head plate 112: First outlet opening 114: Second outlet opening 114'': Ring-shaped second outlet opening 116: Third outlet opening 116': Third outlet opening with an offset angle 116'': Ring-shaped third outlet opening 118: First exhaust opening 118'': Ring-shaped first exhaust opening 120: Second exhaust opening 120'': Ring-shaped exhaust opening 121: Inlet Supply / Discharge Channel 122: First inlet supply channel 122': Opening 124 connected to the first inlet supply channel / part: Second inlet supply channel 124': Opening 126 connected to the second inlet supply channel / part: Third inlet supply channel 126': Opening 128 connected to the third inlet supply channel / part: First discharge channel 128': Opening 130 connected to the first discharge channel / part: Second discharge channel 130': Opening 132 connected to the second discharge channel / part: First precursor fluid 134: Second precursor fluid 136: Inert fluid 138: Undeposited precursor fluid / inert fluid 140: Undeposited precursor fluid / inert fluid 142: First distribution channel 144: Second distribution channel 146: Third distribution channel 147: Exhaust distribution channel 147': Exhaust distribution channel 148: Valve of the first valve 149: Valve of the second valve 150: Third Valve 151: Set of 4 valves 152: 5th valve 153: Set of 6 valves 154: Pressure sensor 155: Controller 156: Vessel with inert fluid 157: Connector 158: Trap acting as filler 159: Pump 160: Substrate plate 162: Substrate on substrate plate 172: 1st precursor solution 174: 2Precursor Solution X: X-axis in the X,Y plane Y: Y-axis in the X,Y plane Z: Z-axis perpendicular to the X,Y plane φ: Angle defining the rotation of the X,Y plane around the Z-axis θ: Angle defining the inclination of the X,Y plane around the axis in the X,Y plane

Claims

Claim 1 As an atomic layer process printer (100) for material deposition, etching, and / or cleaning at an atomic scale in a selected area, the printer (100) is configured to operate at atmospheric pressure, and the printer (100) comprises: o a substrate plate (160) for holding a substrate (162) on which one or more fluids (132, 134) can be deposited using the printer (100); o a printer head (101) positioned toward the substrate (162) on the substrate plate (160), the printer head (101) comprises: - one or more first exit openings (112), each having a first exit opening diameter smaller than 900 micrometers; - one or more second exit openings (114); - one or more third exit openings (116); - A printer head plate (104) having a plurality of openings including one or more exhaust openings (118, 120); and the printer comprises: o a first inlet supply channel (122) connected to the one or more first outlet openings (112) to guide a first precursor fluid (132) onto the substrate (162) through the one or more first outlet openings (112); o a second inlet supply channel (124) connected to the one or more second outlet openings (114) to guide a second precursor fluid (134) onto the substrate (162) through the one or more second outlet openings (114); o a third inlet supply channel (126) connected to the one or more third outlet openings (116) to guide an inert fluid (136) onto the substrate (162) through the one or more third outlet openings (116); o an undeposited first precursor fluid (132), an undeposited second One or more exhaust channels (128, 130) connected to one or more exhaust openings (118, 120) to remove a precursor fluid (134) and an inert fluid (136) from the substrate (162);The substrate plate (160) is movable with respect to the printer head (101): - along an axis in the X,Y plane defined by an X-axis and a Y-axis perpendicular to each other; - along a Z-axis perpendicular to the X,Y plane; and - at a first angle (φ) defining a rotation of the X,Y plane around the Z-axis; and the substrate plate (160) and the printer head (101) are movable with respect to each other at a second angle (θ) defining an inclination of the X,Y plane around an axis in the X,Y plane; and the one or more exhaust openings include: o one or more first exhaust openings (118) connected to a first exhaust channel (128) to remove an undeposited first precursor fluid (132) and possibly an inert fluid (136) from the substrate (162); A printer characterized by including one or more second exhaust openings (120) connected to a second exhaust channel (130) to remove a second precursor fluid (134) that is not deposited and possibly an inert fluid (136) from the substrate (162). Claim 2 A printer according to claim 1, characterized in that the printer head (101) is fixed in the X and Y planes and along the Z axis. Claim 3 A printer characterized in that, in claim 1 or 2, the X,Y plane extends parallel to the substrate plate (160). Claim 4 A printer characterized in that, in claim 1 or 2, the rotation of the X and Y planes around the Z axis is the rotation of the substrate plate (160). Claim 5 A printer characterized in that, in claim 1 or 2, the slope of the X,Y plane is the slope of the substrate plate (160) with respect to the printer head (101). Claim 6 A printer characterized in that, in claim 1 or 2, the printer head (101) can be tilted. Claim 7 A printer according to claim 1 or 2, characterized in that the second angle (θ) is in the range of 0.5 to 10 degrees. Claim 8 A printer characterized in that, in claim 1 or 2, the Z-axis extends between the printer head (101) and the substrate plate (160) to define the distance between the printer head (101) and the substrate plate (160). Claim 9 A printer according to claim 8, characterized in that the distance between the printer head (101) and the substrate plate (160) is in the range of 0.005 to 100 μm. Claim 10 A printer according to claim 1 or 2, characterized in that the discharge surface of the printer head (101) further includes a safety evacuation channel located at the outermost edge around the first, second, and third outlet openings (112, 114, 116) and the exhaust opening (118, 120). Claim 11 A printer according to claim 1 or 2, characterized in that the discharge surface of the printer head (101) is in the shape of a disk, square, rectangle, triangle, or pentagon. Claim 12 A printer according to claim 1 or 2, characterized in that the discharge surface of the printer head (101) is in the form of a disc. Claim 13 A printer according to claim 1 or 2, characterized in that the printer is applied to change the distance between the printer head (101) and the substrate plate (160) during printing of a three-dimensional structure. Claim 14 A printer according to claim 1 or 2, characterized in that the printer is applied to operate at a deposition rate of 1 nm / min or less. Claim 15 A printer according to claim 1 or 2, characterized in that the printer is applied to operate at a deposition rate in the range of 0.1-100 nm / min. Claim 16 A printer according to claim 1 or 2, characterized in that the printer is applied to control the temperature of the printer head (101). Claim 17 A printer according to claim 1 or 2, characterized in that the printer is applied to control the temperature of the supply channels (122, 124, 126). Claim 18 A printer according to claim 1 or 2, characterized in that the printer includes a heating / cooling source that heats at least one printer head (101) so as to be operated at a temperature between 10 and 600 ℃. Claim 19 A printer according to claim 1 or 2, characterized in that the supply channels (122, 124, 126) are made of stainless steel, Teflon, a fluoroelastomer material (FKM), or a perfluoroelastomer compound (FFKM). Claim 20 A printer according to claim 1 or 2, characterized in that the diameter of the first exit opening is less than 800 μm. Claim 21 A printer according to claim 1 or 2, characterized in that the first outlet opening diameter is in the range of 0.005 to 850 μm. Claim 22 A printer according to claim 1 or 2, characterized in that the printer is applied to provide a pattern resolution of 20 nm to 1 mm. Claim 23 A printer according to claim 1 or 2, characterized in that the printer is applied to operate in an upward set in which the printer head (101) is positioned on the substrate plate (160). Claim 24 A printer according to claim 1 or 2, wherein the printer head plate (104) further comprises: - one or more first distribution channels (142) applied to guide the first precursor fluid (132) from the first inlet supply channel (122) to the one or more first outlet openings (112); - one or more second distribution channels (144) applied to distribute the second precursor fluid (134) from the second inlet supply channel (124) to the one or more second outlet openings (114); - one or more third distribution channels (146) applied to distribute the inert fluid (136) from the third inlet supply channel (126) to the one or more third outlet openings (116). Claim 25 A printer according to claim 1 or 2, wherein the printer head plate (104) is removablely attached to the printer head (101), so that different printer head plates (104) can be connected to the printer head (101), and the different printer head plates (104) have various sizes of opening diameters of the first outlet opening. Claim 26 A printer according to claim 1 or 2, characterized in that the one or more second and third outlet openings (114, 116) and the one or more exhaust openings (118, 120) are located around the one or more first outlet openings (112). Claim 27 A printer according to claim 1 or 2, characterized in that the one or more second and third outlet openings (114, 116) and the one or more exhaust openings (118, 120) are positioned circumferentially around each of the one or more first outlet openings (112). Claim 28 A printer according to claim 1 or 2, characterized in that the one or more second and third outlet openings (114, 116) and the one or more exhaust openings (118, 120) are symmetrically positioned around the one or more first precursor openings. Claim 29 A printer according to claim 1 or 2, wherein the one or more first exit openings (112) include a first exit opening (112) located in the center of the printer head plate (104). Claim 30 A printer according to claim 1 or 2, characterized in that the printer comprises a plurality of printer heads (101). Claim 31 A printer according to claim 1 or 2, wherein the printer head (101) is made of ceramic or metal. Claim 32 A method for depositing material on a substrate (162) in a selected area, wherein the method is performed at atmospheric pressure, and the method comprises the step of providing an atomic layer process printer having a substrate plate (160) and a printer head (101) positioned toward the substrate plate (160), wherein the substrate plate (160) with respect to the printer head (101) comprises: - along an axis in the X,Y plane defined by an X-axis and a Y-axis perpendicular to each other; - along a Z-axis perpendicular to the X,Y plane; and - at a first angle (φ) defining a rotation of the X,Y plane around the Z-axis; The substrate plate (160) and the printer head (101) are movable and are movable relative to each other at a second angle (θ) defining the inclination of the X,Y plane around an axis in the X,Y plane; o a step of positioning a substrate (162) on the substrate plate (160); o a step of exposing the substrate (162) to a first precursor fluid (132) through one or more first outlet openings (112), each having a diameter smaller than 900 micrometers; o a step of removing the first precursor fluid (132) that is not deposited on the substrate (162) by one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136); o a step of exposing the substrate (162) on which the first precursor is deposited to a second precursor fluid (134); o a step of removing the first precursor fluid (132) that is not deposited on the substrate (162) by one or more exhaust openings (118, 120) in combination with exposing the substrate (162) to an inert fluid (136). A method characterized by including the step of removing the second precursor fluid (134) that is not deposited on the substrate (162) by one or more exhaust openings (118, 120). Claim 33 A method according to claim 32, further comprising the step of moving the substrate plate (160) and the printer head (101) relative to each other between the deposition of the precursor fluids (132, 134). Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete

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