Multiple flow nozzle for direct atomic layer deposition and uses thereof

Abstract

The disclosure relates to devices, systems and methods for directly forming multilayer films. Specifically, the disclosure relates to devices, systems and methods for directly forming multi-layered film having at least one dimension that is not the film thickness, smaller than the diameter of a precursor outlet aperture, and / or a reactant outlet aperture, thereby allowing controlling line width during deposition, and higher deposition rates when arrays / multiple nozzles are used.

Description

MULTIPLE FLOW NOZZLE FOR DIRECT ATOMIC LAYER DEPOSITION AND USES THEREOFBACKGROUND

[0001] The disclosure is directed to devices, systems and methods for forming multi-layer films. Specifically, the disclosure is directed to devices, systems and methods for forming multilayered film having at least one dimension smaller than the diameter of a precursor outlet, and / or a reactant outlet.

[0002] Typically (see e.g., FIG. 1A) Direct Atomic Layer Processing (DALP) nozzle employs a precursor (P) channel outlet concentric with the nozzle concentrically surrounded by a reactant (R) annulus. When coupled to the proper drivetrain, this configuration allows printing a line in any direction simply by moving the nozzle in a reciprocating manner in any direction (see e.g., FIG. 1C), whereby the film grows (in the Z direction) from a repeatedly altering between the precursor and the reactant over the same deposition area (see e.g., FIG. ID), with any line width being equal to (or greater) than the diameter of the precursor outlet aperture (see e.g., FIG. 1A, 2-Pr, FIG. IB).

[0003] In DALP, the geometry of the nozzle creates a condition whereby in using reciprocal motion during depositions with certain shapes such as lines, the reactant passes over the precursor line only half of the time in certain areas, such as the line edges, thereby inducing an “edge effect” (see e.g., FIG. IE), where the thickness is half that of the thickness of the reacted line, because the reactant there passes only half of the times.

[0004] The width (lateral resolution) has limitations as well. Typical precursor orifice diameter varies depending on the nozzle design and final purpose of the DALP process, and can be between about 20pm, and about 5mm However, to achieve smaller feature sizes, it is necessary to reduce the thickness of the nozzle walls, which complicates the fabrication process making it challenging to reach higher resolution with the same design or fabrication process.

[0005] Other issues associated with nozzle design for DALP are, for example; precursor scalability (the scale-up from benchtop to commercial applications), compatibility (with various precursor / reactant chemistries, to prevent corrosion or degradation, ensuring long-term reliability), and cost (commercially feasible).

[0006] To provide better resolution throughout the printing process, and address the edge effects, there is therefore a need an improved nozzle design.SUMMARY

[0007] Disclosed, in various exemplary implementations, are devices, systems and methods for forming multi-layered film having at least one dimension, other than the trace thickness, that is smaller than the diameter of a precursor outlet, and / or a reactant outlet.

[0008] In an exemplary implementation provided herein is a deposition method for forming a film having at least one dimension, other than the film thickness - smaller than a diameter of a precursor outlet, and / or a reactant outlet, the method implemented in a deposition system comprising: a nozzle operable for direct atomic layer processing (DALP), the nozzle comprising: a first precursor outlet port having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port, a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and / or a first reactant outlet port having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet; and a substrate operable to move reciprocally in a X axis, and / or a Y axis, and / or a Z axis: rotating the nozzle relative to the X-axis at a first predetermined angle configured to only partially overlap the material deposited by the first precursor; moving the substrate along the X-axis under the rotated nozzle in a first direction for a first predetermined distance; and moving the substrate along the X-axis and Y-axis at the same time under the nozzle in a first direction for a first predetermined distance, depositing the first precursor and the first reactant , wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension other than the film thickness - smaller than the diameter of the first precursor outlet, and / or the first reactant outlet,

[0009] In another exemplary implementation, provided herein is a method of preventing edge effect in direct atomic layer processing (DALP), the method comprising providing a direct atomic layer processing system comprising: a nozzle comprising: a first precursor outlet port having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port, a first inert gas outlet arranged in a concentric annulusaround the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet port having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet are coplanar; and a substrate operable to move reciprocally in a X axis, a Y axis, a Z axis, or a combination thereof: using the first precursor outlet, and the first reactant outlet, depositing the first precursor and the first reactant while moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance; and while moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, using the first and second inert gas outlets and the first and second exhaust ports, or first and second vacuum ports, removing unreacted precursor and unreacted reactant.

[0010] In yet another exemplary implementation, provided herein is a nozzle operable for direct atomic layer deposition comprising: a first precursor outlet port with an aperture having a predetermined diameter, the precursor outlet further comprising: a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port; a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port; and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet port an aperture having a predetermined diameter, the reactant outlet further comprising: a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet port; a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port; and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet are arranged coplanar on the nozzle at a predetermined distance.

[0011] The nozzle further comprises: a second precursor outlet port having a predetermined diameter, with: a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port; a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port: and a sixth exhaust port, or a sixth vacuumport, each arranged in a concentric annulus around the third inert gas outlet; and a second reactant outlet port having a predetermined diameter, with a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet port; a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet.

[0012] These and other features of the devices, systems and methods for forming multilayered film having at least one dimension, other than the thickness, smaller than the diameter of a precursor outlet, and / or a reactant outlet, will become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.BRIEF DESCRIPTION OF THE FIGURES

[0013] For a better understanding of devices, systems and methods for forming multi-layered film having at least one dimension smaller than the diameter of a precursor outlet, and / or a reactant outlet, with regard to the exemplary implementations thereof, reference is made to the accompanying examples and figures, in which:

[0014] FIG. 1A illustrates a bottom plan view of a typical DALP nozzle, with FIG. IB, illustrating the film formation, while FIG. 1C illustrates the line formed in simultaneous deposition, FIG. ID illustrating the film building process, and FIG IE illustrating the edge effects created on reciprocal motion of the nozzle or substrate stage;

[0015] FIG. 2A, illustrates a schematic of an exemplary implementation of the redesigned nozzle, with the coplanar outlet apertures of precursor (right) and reactant (left), with FIG. 2B, depicting an exemplary implementation of the nozzle with coplanar apertures of precursor and reactant, having equal or different diameters;

[0016] FIG. 3 A, is a schematic illustration of simultaneous in-phase deposition (and film formation) of precursor and reactant along a single direction, with FIG. 3B illustrating schematically, the effect of rotation angle relative to the print direction on the formed film width;

[0017] FIG.s 4A-4C, is a schematic illustrating an exemplary implementation of the system, for an alternative method of forming films having width that is smaller than the diameter of the outlet apertures of precursor and reactant;

[0018] FIG. 5 illustrate schematically, another exemplary implementation nozzle having additional precursor and reactants;

[0019] FIG.s 6A, 6B, depicting actual film deposited using the nozzle disclosed; and

[0020] FIG. 7A illustrates traces formed using an exemplary implementation of the nozzle, detailing the degree of overlap in percentages between 10% and 75%, where FIG. 7B is a graph showing the effect of the degree of overlap, on line length.DETAILED DESCRIPTION

[0021] Provided herein are exemplary implementations of devices, systems and methods for forming multi-layered film having at least one dimension smaller than the diameter of a precursor outlet, and / or a reactant outlet.

[0022] Direct Atomic Layer Processing (DALP) refers to a precise thin film deposition technique enabling the growth of uniform and conformal films at the atomic scale. Using DALP film growth is done in a controlled, layer-by-layer fashion beginning with a substrate surface (see e.g., FIG.s ID, IE, 6A, 6B) that is chemically prepared, typically cleaned to remove any contaminants or oxides. The deposition starts with an initial reactant, called the precursor, being introduced onto the substrate. The precursor is selected based on the desired film composition and properties. It is typically a vapor or gas-phase fluid that can react with, or preferentially adhere to the substrate surface. To achieve atomic-level control, the precursor is introduced in a controlled pulse or brief exposure over the substrate, or alternatively, the substrate (which can be rotatable) can be maneuvered below the nozzle. Substrate exposure to the precursor is precisely controlled in term of timing and amounts, to ensure they interact with the substrate surface for a defined period. This process can take place after surface treatment of the substrate, or independently. During this exposure, a self-limiting reaction occurs (meaning that it stops once a full monolayer is formed) at the surface, resulting in the formation of a monolayer or sub-monolayer of the desired material. Excess precursor, unreacted byproducts, and any adsorbed impurities are then purged from the chamber using an inert gas (see e.g., FIG. 1A, FIG. 2A, 401) such as nitrogen or argon. The cycle is then repeated, alternating between precursor / reactant exposure and purge steps, gradually building up the film layer by layer. The number of cycles is carefully controlled to achieve the desired film thickness, which can range from a few nanometers to several micrometers. Success of ALD will hinge on the ability to precisely control the number of atomic layers deposited during each cycle. This control is achieved by accurately controlling theexposure parameters, for example; precursor pulse time, the reactant pulse times, temperature, pressure, substrate (and / or conveyor) speed and other process parameters.Definitions:

[0023] In the context of the disclosure, the term "operable" means the system and / or the device and / or the program, or a certain element or step is fully functional, sized, adapted, and calibrated, comprises elements for. and meets applicable operability requirements to perform a recited function when activated, coupled, implemented, actuated, effected, realized, or when an executable program is executed by at least one processor associated with the system and / or the device. In relation to systems and circuits, the term "operable" means the system and / or the circuit is fully functional and calibrated, comprises logic for, having the hardware and firmware necessary, as well as the circuitry for, and meets applicable operability requirements to perform a recited function when executed by at least one processor.

[0024] The term "fluid communication" or refers to any area, a structure, or communication that allows for fluid communication between at least two fluid retaining regions, for example, a tube, duct, conduit or the like connecting two regions. One or more fluid communication can be configured or adapted to provide for example, vacuum driven flow, electrokinetic driven flow, control the rate and timing of fluid flow by varying the dimensions of the fluid communication passageway, rate of circulation or a combination comprising one or more of the foregoing. Alternatively, and in another exemplary implementation, the term “in communication” can also refer to gaseous and / or vapor communication, i.e. that gas and / or vapor may be transferred from one volume to another volume since these volumes are in communication. This term does not exclude the presence of a gas shutter or valve between the volumes that may be used to interrupt the gas communication between the volumes.

[0025] The terms “first,” “second,” and the like, when used herein do not denote any order, quantity, or importance, but rather are used to denote one element from another. The terms “a”, “an” and “the” herein do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the duct(s) includes one or more ducts). Reference throughout the specification to “one exemplary implementation”, “another exemplary implementation”, “an exemplary implementation”, and so forth, means that a particular element (e.g.,feature, structure, and / or characteristic) described in connection with the exemplary implementation is included in at least one exemplary implementation described herein, and may or may not be present in other exemplary implementations. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various exemplary implementations.

[0026] In addition, for the purposes of the present disclosure, directional or positional terms such as "top", “apical”, “basal”, “proximal”, “distal”, "bottom", "upper," "lower," "side." "front," "frontal," "forward," "rear," "rearward," "back," "trailing," "above," "below," "left," "right," "radial ." "vertical," "upward," "downward," "outer," "inner," "exterior," "interior," "intermediate," etc., are merely used for convenience in describing the various exemplary implementations of the present disclosure. The term “coplanar” as used in this application is defined as a plane in the same plane as the conventional plane or working surface of a layer, regardless of orientation.

[0027] The term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and / or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives.

[0028] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Furthermore, the terms “first,” “second,” and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another.

[0029] Likewise, the term "about" means that amounts, ranges, sizes, formulations, parameters, and other quantities and characteristics are not and do not need be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, ranges, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such and is intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing the application. For example, “about” can include a range of + / - 15% or 10%, or 5% of a given value.

[0030] A more complete understanding of the components, processes, assemblies, and devices disclosed herein can be obtained by reference to the accompanying drawings. These figures (alsoreferred to herein as "FIG.") are merely schematic representations (e.g.. illustrations) based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and / or to define or limit the scope of the exemplary implementations. Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the exemplary implementations selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.

[0031] Turning to FIG.s 2A, and in an exemplary implementation, provided herein is nozzle 10 operable for direct Atomic layer processing (DALP) comprising: first precursor outlet port 200 with aperture 201 having predetermined diameter ODi, precursor outlet port 200 further comprising: first exhaust port, or first vacuum port 501, each arranged in concentric annulus around first precursor outlet aperture 201; first inert gas outlet 401 arranged in concentric annulus around first exhaust port, or first vacuum inlet port 501; and second exhaust port, or second vacuum port 502, each arranged in concentric annulus around first inert gas outlet 401; and first reactant outlet port 300 aperture 301 having predetermined diameter OD2, reactant outlet 300 further comprising: third exhaust port, or third vacuum port 503, each arranged in concentric annulus around first reactant outlet port 300 aperture 301; second inert gas outlet 402 arranged in concentric annulus around third exhaust port, or third vacuum inlet port 503; and fourth exhaust port, or fourth vacuum port 504, each arranged in concentric annulus around second inert gas outlet 402, wherein first precursor outlet aperture 201 and first reactant outlet aperture 301 are arranged coplanar to each other on nozzle 100 at predetermined distance Wl.

[0032] As illustrated in FIG. 2A schematically, and depicted in FIG. 2B, the design incorporates two separate injection zones — one for the precursor 200 and one for the reactant 300. Both zones also have a vacuum channel 501, 503, an inert gas curtain 401, 402, and another vacuum channel 502, 504. The two zones (interchangeable with outlet port) are separated by a certain distance (Wi), enabling different deposition modes with higher line resolution (in other words, line width that is smaller than the diameter of the precursor aperture 201, and / or the reactant aperture 301) and / or no edge effect following removal of unreacted precursor or reactant (see e.g., also FIG. 6A). It is noted, that this channel configuration is an example only, and the order and number of channels can differ depending on the chosen design / application.

[0033] In another exemplary implementation, the nozzles disclosed are implemented as part of DALP system used to carry out the methods provided. Accordingly, provided herein is deposition method for forming film having at least one dimension (in other words, width, or length (not height)) that is smaller than diameter of precursor outlet aperture 201, and / or reactant outlet aperture 301, the method implemented in deposition system comprising: nozzle 10 operable for Direct Atomic Layer Processing (DALP) comprising: first precursor outlet port 200 with aperture 201 having predetermined diameter ODi, precursor outlet port 200 further comprising: first exhaust port, or first vacuum port 501, each arranged in concentric annulus around first precursor outlet aperture 201; first inert gas outlet 401 arranged in concentric annulus around first exhaust port, or first vacuum inlet port 501; and second exhaust port, or second vacuum port 502, each arranged in concentric annulus around first inert gas outlet 401 ; and first reactant outlet port 300 aperture 301 having predetermined diameter OD2, reactant outlet 300 further comprising: third exhaust port, or third vacuum port 503, each arranged in concentric annulus around first reactant outlet port 300 aperture 301; second inert gas outlet 402 arranged in concentric annulus around third exhaust port, or third vacuum inlet port 503; and fourth exhaust port, or fourth vacuum port 504, each arranged in concentric annulus around second inert gas outlet 402, wherein first precursor outlet aperture 201 and first reactant outlet aperture 301 are arranged coplanar to each other on nozzle 100 at predetermined distance Wl and substrate operable to move reciprocally in at least X-axis, Y-axis, and Z-axis: the method comprising: rotating nozzle 100 relative to the X-axis at first predetermined angle (see e.g., FIG. 3B, Oi, Oi), whereby the reactant deposited is configured to only partially overlap the material deposited by the first reactant 300; moving the substrate along the X-axis under the potentially rotated nozzle 100 in a first direction for a first predetermined distance; and moving the substrate along the X-axis and Y-axis at the same time under the nozzle in a first direction for a first predetermined distance, depositing the first precursor 200 and the first reactant 300, wherein the first direction along the X-axis is configured for depositing the first precursor 200 first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture.

[0034] To achieve the desired line thickness, the process can be repeated, by rotating the nozzle or the substrate up to 180° from the predetermined angle (in other words, where a cord passing through the centers of apertures 201, 301 of first precursor 200 and first reactant 300 respectively, is parallel with the printing direction, to a desired angle 0), or returning the substrate to its original position see e.g., FIG. 3B, Oi, O2), or by rotating the substrate (or rotating the nozzle AND the substrate)and so on. Accordingly, the method further comprising: moving the substrate along the Z-axis; rotating the nozzle, and / or the substrate relative to the X-axis at a second predetermined angle configured to only partially overlap the material deposited by the first reactant moving the substrate along the X-axis under the rotated nozzle and / or the rotated substrate in a direction opposite the first direction for the first predetermined distance; and depositing the first precursor and the first reactant, wherein the first precursor is configured for deposition first. It is noted, that the rotation of the nozzle and / or substrate is done manually in certain configurations, or automatically in other configurations of the system.

[0035] As illustrated in FIG.s 3A, 3B, operating in phase, in other words, when the coplanar apertures are parallel with the printing direction, while being similar to the standard deposition process, substantially eliminate edge effects. The left edge (see e.g., FIG. 3A) is an area covered only by the reactant, which doesn't produce any film, while the right edge is an area covered only by the precursor, only capable of producing a single (monoatomic) layer of deposition, negligible and usually undetectable, and which can be removed. Furthermore, and as illustrated in FIG. 3B, depending on the angle of diagonal deposition (see e.g., FIG. 3B, ft, ft), the area covered by both precursor and reactant can be fine-tuned, and so can the line width.

[0036] As depicted in FIG. 2B, first precursor outlet port 200 with aperture 201, and first reactant outlet port 300 aperture 301, are coplanar and can have diameters (ODi, Ol ). that are the same or different.

[0037] Turning now to FIG. 4A-4C, illustrating an alternative method for forming a film using ALD, where the film has line width (in other words, at least one dimension) that is smaller than first precursor outlet port 200 aperture 201, and / or first reactant outlet port 300 aperture 301. In the alternative method, the step of rotating the nozzle relative to the X-axis is eliminated (see e.g., FIG. 4A), the method further comprising, following the step of simultaneously depositing the first precursor and the first reactant, forming a first precursor strip 2000 and a first reactant strip 3000 of the first predetermined distance along the X-axis: while depositing the first precursor 200 and the first reactant 300, moving the substrate along the Y-axis (see e.g., FIG. 4B) to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant 3001 (in the Y- axis direction) with the strip formed by the first precursor 2000; and while depositing the first precursor 200 and the first reactant 300, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance (see e.g., FIG. 4C), forminga film having a first thickness, the film has line width (in other words, at least one dimension that is NOT in the Z-axis) that is smaller than first precursor outlet port 200 aperture 201, and / or first reactant outlet port 300 aperture 301. In the alternative method, the lateral shift can be used to fine-tune the desired line width, and again, the unreacted reactant can be removed using the inert gas and the vacuum lines, while the initial precursor will only form monoatomic layer. It is noted, that following the last step of deposition, the substrate and the nozzle are transitioned each to their original position.

[0038] In certain exemplary implementations, using valve control, the initial reactant strip 3000 will not be formed, and deposition will occur only on the transverse motion of the nozzle (or the substrate). In certain exemplary implementation, the substrate is operable to move in four (4) dimensions (in other words, X-axis, Y-axis, Z-axis, and 360° rotation relative to the Z-axis). Similarly, the nozzle is operable to move in four (4) dimensions (in other words, X-axis, Y-axis, Z-axis, and 360° rotation relative to the Z-axis).

[0039] Similar to the optional partial rotation of the nozzle (and / or the substrate) relative to the deposition direction, here too, to build more film layers (see e.g., FIG. ID), the method further comprises: moving the substrate or the nozzle along the Z-axis; either rotating the nozzle 180° relative to the Z-axis, or returning the nozzle to its original position and while depositing the first precursor 200, moving the substrate and / or the nozzle, and / oe along the X-axis under the nozzle in a direction opposite the first direction (if the nozzles are rotated), or in the same first direction, if the nozzle is positioned in its original position for the first predetermined distance, the first precursor 200 configured to be deposited over the reacted film having the first thickness; then, moving the substrate and / or the nozzle along the Y-axis to the second predetermined distance opposite the second direction; and depositing the first reactant 300, moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, the first reactant 300 configured to only be deposited partially over the deposited precursor, forming a film having a second thickness.

[0040] Here too. in certain circumstances, the first reactant 300 is not deposited simultaneously, the method comprising, following the step of moving the substrate and / or the nozzle along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip 3001 formed by the reactant with the strip formed by the first precursor 2000, while depositing the first reactant 300, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.Furthermore, following the step of depositing the first precursor and the first reactant: while moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, using the first inert gas outlet and the first and second exhaust ports, or vacuum ports, removing unreacted precursor and unreacted reactant.

[0041] Turning now to FIG. 5, illustrating additional injection zones with the same or different precursors and / or same or different reactants, enabling more complex structures and materials with varying fine line width being possible. Accordingly, the rotatable nozzle further comprises: a second precursor outlet port aperture having a predetermined diameter, with: a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture 202; a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and a second reactant outlet aperture 302 port having a predetermined diameter, with a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet. Using the twin nozzles, it is additionally possible to pre-treat the substrate (or a deposited precursor) through one of the nozzles or through the added nozzles as well as adjust the line width with nozzle without exchanging nozzles.

[0042] It is noted that other ports for each of the precursors, reactants, and inert gasses can be added and further used to achieve complex structures while simultaneously controlling all dimensions, with at least one dimension other than line width, which is smaller than the aperture diameter. The multiple flow nozzles disclosed can have triple, quadruple apertures, providing further flexibility and narrower / smaller line features These ports can be coupled to the same or other compounds used to form different films with different physico-chemical characteristics.

[0043] Turning now to FIG.s 2A, 6A, and 6B, where FIG. 6A shows the top view of the line corresponding to the precursor only area, referring to the area where only the precursor port reaches. The figure depicts the absence of a film formation (compared to the film in FIG 6B, which is precursor + reactant). FIG. 6A shows that using the methods disclosed, the films do not grow in areas with unreacted precursor. As shown, first precursor outlet port 200 with aperture 201 had diameter ODi of 193 pm, and first reactant outlet port 300 aperture 301 had diameter OD2 of 198 pm, with IF; being1.54mm, an elongated film (trace) was formed having length of 4.5 mm, and width of less than third (54.84 m) the diameters of first precursor outlet port 200 aperture 201, or first reactant outlet port 300 aperture 301.

[0044] Turning now to FIG.s 7A, 7B, illustrating an example of the effect of the degree of overlap between the nozzles as illustrated in FIG.s 4A-4C, on the line width dimensions width, formed by shifting laterally the substrate (nozzle) after the first film deposition, resulting in different trace dimensions using nozzles where the aperture diameter of the precursor port was 50 pm and the aperture diameter of the reactant was similarly, 50 pm. As illustrated in FIG. 7B, the smaller the overlap percentage, the narrower the line.

[0045] In an exemplary implementation, the precursor, or reactant used in the ALD, film forming methods disclosed can be, for example, at least one of: Trimethylaluminum (TMA), Tetrakis(dimethylamino)titanium (TDMAT), Bis(cyclopentadienyl)zirconium(IV) dichloride (Cp2ZrC12), Tetrakis(ethylmethylamino)hafnium (TEMAH), andBis(ethylcyclopentadienyl)ruthenium(II) (Ru(EtCp)2), Titanium tetrachloride (TiC14), Tungsten hexafluoride (WF6). Hafnium tetrachloride (HfC14), Ruthenium trichloride (RuC13), and Molybdenum hexacarbonyl (Mo(CO)6), Diethyl zinc (DEZ), Dimethylamino magnesium (DMAMg), Bis(cyclopentadienyl)iron(II) (Cp2Fe), Triisobutylaluminum (TIBA),Tetrakis(trimethylsilyl)hafnium (TTHf), Aluminum isopropoxide (Al(O-iPr)3), Titanium isopropoxide (Ti(O-iPr)4), Zirconium n-propoxide (Zr(O-nPr)4), Hafnium ethoxide (Hf(OEt)4), Tantalum ethoxide (Ta(OEt)5). Bis(t-butylamino)silane (BTBAS), Bis(t-butylamino)zinc (BTBAS2), Bis(t-butylamino)titanium (BTBAT), Bis(t-butylamino)zirconium (BTBZ), Bis(t- butylamino)hafnium (BTBAH), Dimethylcyclopentadienyl platinum (MeCpPtMe3), Bis(methylcyclopentadienyl)nickel (Ni(MeCp)2), Cyclopentadienyltungsten tricarbonyl (CpW(CO)3), Dimethylcyclopentadienyl manganese tricarbonyl (MeCpMn(CO)3), and Iron pentacarbonyl (Fe(CO)5).

[0046] In another exemplary implementation, the inert gas can be at least one of: Nitrogen, Argon, Helium, and Neon. It is noted that the choice of inert gas depends on factors such as process requirements, film properties, equipment capabilities, and cost considerations. Additionally, specific applications or variations within ALD techniques may call for the use of other inert gases or gas mixtures.

[0047] Surface treatment of the substrate used in the methods described herein can be at least one of: solvent (e.g., acetone, isopropyl alcohol (IPA), or ultrasonic cleaning to remove organic contaminants and particles) or acid (e.g., sulfuric acid (H2SO4) or hydrochloric acid (HC1)), cleaning; plasma (e.g.. using reactive gases like oxygen (02), hydrogen (H2), or fluorine-based gases (CF4, SFe), is done to remove native oxide layers or to pattern the substrate surface), and / or wet (e.g., to remove unwanted layers or roughen the surface for improved film adhesion for example, for SIS) etching; and surface functionalization (e.g.. silane coupling agents, such as APTES (aminopropyltriethoxy silane) or HMDS (hexamethyldisilazane), by introducing specific chemical groups that enhance film bonding or modify surface energy).

[0048] Accordingly and in an exemplary implementation, provided herein is deposition method for forming a film having at least one dimension smaller than a diameter of a precursor outlet, and / or a reactant outlet aperture other than line thickness, the method implemented in a deposition system comprising: a nozzle operable for Direct Atomic Layer Processing (DALP), the nozzle comprising: a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet port aperture having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet; and a substrate operable to move reciprocally in at least a X-axis, a Y-axis, and a Z-axis: rotating the nozzle and / or the substrate such that a cord passing through a center of the first precursor outlet port aperture and the first reactant outlet port aperture is tilted relative to the X-axis at a first predetermined angle configured to only partially overlap the material deposited by the first precursor; moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture, wherein (i) the substrate is rotatable, (ii) the method further comprising rotating the substrateat a predetermined angle relative to the X-axis, and (iii) further comprising: moving the substrate along the Z-axis; rotating the nozzle, and / or the substrate relative to the X-axis at a second predetermined angle configured to only partially overlap the material deposited by the first reactant moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance; and depositing the first precursor and the first reactant, wherein the first precursor is configured for deposition first, as well as (iv) repositioning the nozzle in a position at an initial point relative to the predetermined distance; and repeating the steps of moving the substrate, to the step of depositing the first precursor and the first reactant, wherein (v) the first precursor outlet and the first reactant outlet aperture are coplanar, (vi) the diameter of the first precursor outlet is identical to the diameter of the first reactant outlet aperture, (vii) is different from the diameter of the first reactant outlet aperture, (viii), wherein the step of rotating the nozzle relative to the X-axis is eliminated, the method further comprising, following the step of simultaneously depositing the first precursor and the first reactant, forming a first precursor strip and a first reactant strip of the first predetermined distance along the X-axis: while depositing the first precursor and the first reactant, moving the substrate along the Y-axis to a second predetermined distance in a second direction configured to only partially overlap the strip formed by the reactant with the strip formed by the first precursor; and while depositing the first precursor and the first reactant, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness, the method further comprising (ix): moving the substrate along the Z-axis; rotating the nozzle, or the substrate 180°, or rotating the nozzle 90° and the substrate 90°. while depositing the first precursor, moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, the first precursor configured to be deposited over the film having the first thickness; moving the substrate along the Y-axis to the second predetermined distance opposite the second direction; and depositing the first reactant, moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, the first reactant configured to only be deposited partially over the deposited precursor, forming a film having a second thickness, (x) repositioning the nozzle in the initial point relative to the predetermined distance; and repeating the steps of moving the substrate along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, and while depositing the first precursor and the first reactant, moving the substrate along the X-axis under thenozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness, (xi) wherein the first reactant is not deposited simultaneously, the method comprising, following the step of moving the substrate along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, while depositing the first reactant, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness, (xii). the method further comprising, following the step of depositing the first precursor and the first reactant: while moving the substrate along the X- axis under the nozzle in a direction opposite the first direction for the first predetermined distance, using the first inert gas outlet and the first and second exhaust ports, or vacuum ports, removing unreacted precursor and unreacted reactant, wherein (xiii) the step of rotating the nozzle and / or the substrate is eliminated, and wherein the step of moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance comprises moving the substrate diagonally relative to the X-axis; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture, wherein (xiv) the nozzle further comprises: a second precursor outlet port aperture having a predetermined diameter, with: a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture ; a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and a second reactant outlet aperture port having a predetermined diameter, with a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet, (xv) the first precursor is different from the second precursor, or (xvi) is different from the second reactant.

[0049] In another exemplary implementation, provided herein is a method of preventing edge effect in Direct Atomic Layer Processing (DALP), the method comprising providing an atomic layer deposition system comprising: a nozzle comprising: a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentricannulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet aperture port having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet aperture are coplanar; and a substrate operable to move reciprocally in at least a X axis, a Y axis, and a Z axis, wherein the nozzle, or the substrate or both the nozzle and the substrate are rotatable: using the first precursor outlet, and the first reactant outlet aperture, depositing the first precursor and the first reactant while moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance; and while moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, using the first and second inert gas outlets and the first and second exhaust ports, or first and second vacuum ports, removing unreacted precursor and unreacted reactant.

[0050] In yet another exemplary implementation, provided herein is a nozzle operable for atomic layer deposition comprising: a first precursor outlet port aperture with an aperture having a predetermined diameter, the precursor outlet further comprising: a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet aperture; a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port; and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet aperture port an aperture having a predetermined diameter, the reactant outlet aperture further comprising: a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port; a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port; and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet aperture are arranged coplanar on the nozzle at a predetermined distance, the nozzle further comprising (xvii): a second precursor outlet port aperture having a predetermined diameter, with: a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet portaperture ; a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and a second reactant outlet aperture port having a predetermined diameter, with a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet.

[0051] In an exemplary implementation, provided herein is a system for direct Atomic layer processing (DALP)Direct Atomic Layer Processing (DALP) comprising: a nozzle having a plurality of functional ports; and a substrate operable to move relative to the nozzle, the system being operable to form a film having at least one dimension that is not thickness, which smaller than a diameter of at least one functional port aperture diameter, wherein (xviii) the nozzle comprises: at least one precursor outlet port aperture having a predetermined diameter, with an exhaust port, or a vacuum port, each arranged in a concentric annulus around the at least one precursor outlet port aperture, an inert gas outlet arranged in a concentric annulus around the exhaust port, or the vacuum inlet port, and another exhaust port, or another vacuum port, each arranged in a concentric annulus around the inert gas outlet; and at least one reactant outlet port aperture having a predetermined diameter, with an exhaust port, or a vacuum port, each arranged in a concentric annulus around the reactant outlet port aperture, an inert gas outlet arranged in a concentric annulus around the exhaust port, or third vacuum inlet port, and another exhaust port, or another vacuum port, each arranged in a concentric annulus around the inert gas outlet, wherein (xix) the substrate operable to move reciprocally in at least a X-axis, a Y- axis, and a Z-axis. (xx) and is operable to move diagonally relative to the nozzle.

[0052] In another exemplary implementation, provided herein is a deposition method for forming a film having at least one dimension other than the film thickness - smaller than a diameter of a precursor outlet, and / or a reactant outlet aperture , the method implemented in a deposition system comprising: a nozzle operable for Direct Atomic Layer Processing (DALP), the nozzle comprising: a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulusaround the first inert gas outlet; and a first reactant outlet port aperture having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet; and a substrate, wherein the nozzle is operable to move reciprocally in a X-axis, a Y-axis, a Z-axis or a combination thereof: rotating the nozzle and / or the substrate such that a cord passing through a center of the first precursor outlet port aperture and the first reactant outlet port aperture is tilted relative to the X-axis at a first predetermined angle configured to only partially overlap the material deposited by the first precursor; moving the nozzle along the X-axis over the substrate in a first direction for a first predetermined distance; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture (xxi), wherein the nozzle is rotatable, the method further comprising (xxii) rotating the nozzle at a predetermined angle relative to the X-axis, (xxiii) moving the nozzle along the Z-axis; rotating the nozzle, and / or the substrate relative to the X-axis at a second predetermined angle configured to only partially overlap the material deposited by the first reactant moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance; and depositing the first precursor and the first reactant, wherein the first precursor is configured for deposition first (xxiv), further comprising: returning the nozzle to its initial position at an initial point relative to the predetermined distance; and repeating the steps of moving the nozzle, to the step of depositing the first precursor and the first reactant, (xxv) wherein the first precursor outlet and the first reactant outlet aperture are coplanar (xxvi) wherein the diameter of the first precursor outlet is identical to the diameter of the first reactant outlet aperture (xxvii) or is different from the diameter of the first reactant outlet aperture (xxviii), wherein the step of rotating the substrate relative to the X-axis is eliminated, the method further comprising, following the step of simultaneously depositing the first precursor and the first reactant, forming a first precursor strip and a first reactant strip of the first predetermined distance along the X-axis: while depositing the first precursor and the first reactant, moving the nozzle along the Y-axis to a second predetermined distance in a second direction configured to only partially overlap the strip formed by the reactant with the strip formed by the first precursor; and while depositing the first precursor and the first reactant,moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness (xxix), the method further comprising: moving the nozzle along the Z-axis; rotating the nozzle, or the substrate 180°, or rotating the nozzle 90° and the substrate 90°, or repositioning the nozzle in its original position; while depositing the first precursor, moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance, the first precursor configured to be deposited over the film having the first thickness; moving the nozzle along the Y-axis to the second predetermined distance opposite the second direction; and depositing the first reactant, moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance, the first reactant configured to only be deposited partially over the deposited precursor, forming a film having a second thickness (xxx), and further comprising repositioning the nozzle in the initial point relative to the predetermined distance; and repeating the steps of moving the nozzle along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, and while depositing the first precursor and the first reactant, moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness (xxxi), wherein the first reactant is not deposited simultaneously, the method comprising, following the step of moving the nozzle along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, while depositing the first reactant, moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness (xxxii), the method further comprising, following the step of depositing the first precursor and the first reactant: while moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, using the first inert gas outlet and the first and second exhaust ports, or vacuum ports, removing unreacted precursor and unreacted reactant (xxxiii), wherein the step of rotating the nozzle and / or the substrate is eliminated, and wherein the step of moving the nozzle along the X-axis over the substrate in a first direction for a first predetermined distance comprises moving the nozzle diagonally relative to the X-axis; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet,and / or the first reactant outlet aperture (xxxiv) the nozzle further comprises: a second precursor outlet port aperture having a predetermined diameter, with: a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture ; a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and a second reactant outlet aperture port having a predetermined diameter, with a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet (xxxv), wherein the first precursor is different from the second precursor (xxxvi), wherein the first reactant is different from the second reactant, and (xxxvi), wherein the nozzle, and / or the substrate is each coupled to a rotating platform, capable of rotating between 10and 180°.

[0053] While in the foregoing specification the devices, systems and methods for forming multi-layered film having at least one dimension smaller than the diameter of a precursor outlet, and / or a reactant outlet, have been described in relation to certain preferred exemplary implementations, and many details are set forth for purpose of illustration, it will be apparent to those skilled in the art that the disclosure of the devices, systems and methods for forming multi-layered film having at least one dimension smaller than the diameter of a precursor outlet, and / or a reactant outlet is susceptible to additional exemplary implementations and that certain of the details described in this specification and as are more fully delineated in the following claims can be varied considerably without departing from the basic principles of this disclosure.

Claims

What is claimed is1. A deposition method for forming a film having at least one dimension smaller than a diameter of a precursor outlet, and / or a reactant outlet aperture other than line thickness, the method implemented in a deposition system comprising: a nozzle operable for Direct Atomic Layer Processing (DALP), the nozzle comprising: a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet port aperture having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet; and a substrate operable to move reciprocally in at least a X-axis, a Y-axis, and a Z-axis: a) rotating the nozzle and / or the substrate such that a cord passing through a center of the first precursor outlet port aperture and the first reactant outlet port aperture is tilted relative to the X- axis at a first predetermined angle configured to only partially overlap the material deposited by the first precursor; b) moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance; and c) depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture.2 The method of claim 1, wherein the substrate is rotatable.3 The method of claim 2, further comprising rotating the substrate at a predetermined angle relative to the X-axis.4 The method of claim 1, further comprising:a) moving the substrate along the Z-axis; b) rotating the nozzle, and / or the substrate relative to the X-axis at a second predetermined angle configured to only partially overlap the material deposited by the first reactant c) moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance; and d) depositing the first precursor and the first reactant, wherein the first precursor is configured for deposition first.5 The method of claim 1, further comprising: a) repositioning the nozzle in a position at an initial point relative to the predetermined distance; and b) repeating the steps of moving the substrate, to the step of depositing the first precursor and the first reactant.6 The method of claim 1, wherein the first precursor outlet and the first reactant outlet aperture are coplanar.7 The method of claim 1, wherein the diameter of the first precursor outlet is identical to the diameter of the first reactant outlet aperture.8 The method of claim 1, wherein the diameter of the first precursor outlet is different from the diameter of the first reactant outlet aperture.9 The method of claim 6, wherein the step of rotating the nozzle relative to the X-axis is eliminated, the method further comprising, following the step of simultaneously depositing the first precursor and the first reactant, forming a first precursor strip and a first reactant strip of the first predetermined distance along the X-axis: a) while depositing the first precursor and the first reactant, moving the substrate along the Y-axis to a second predetermined distance in a second direction configured to only partially overlap the strip formed by the reactant with the strip formed by the first precursor; and b) while depositing the first precursor and the first reactant, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.10 The method of claim 9, further comprising: a) moving the substrate along the Z-axis;b) rotating the nozzle, or the substrate 180°, or rotating the nozzle 90° and the substrate 90°; c) while depositing the first precursor, moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, the first precursor configured to be deposited over the film having the first thickness; d) moving the substrate along the Y-axis to the second predetermined distance opposite the second direction; and e) depositing the first reactant, moving the substrate along the X-axis under the rotated nozzle in a direction opposite the first direction for the first predetermined distance, the first reactant configured to only be deposited partially over the deposited precursor, forming a film having a second thickness.

11. The method of claim 9, further comprising a) repositioning the nozzle in the initial point relative to the predetermined distance; and b) repeating the steps of moving the substrate along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, and while depositing the first precursor and the first reactant, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.

12. The method of claim 10, wherein the first reactant is not deposited simultaneously, the method comprising, following the step of moving the substrate along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, while depositing the first reactant, moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.

13. The method of claim 1, further comprising, following the step of depositing the first precursor and the first reactant: while moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, using the first inert gas outlet and the first and second exhaust ports, or vacuum ports, removing unreacted precursor and unreacted reactant.

14. The method of claim 1, wherein the step of rotating the nozzle and / or the substrate is eliminated, and wherein the step of moving the substrate along the X-axis under the nozzle in a firstdirection for a first predetermined distance comprises moving the substrate diagonally relative to the X-axis; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture.

15. The method of claim 1, wherein the nozzle further comprises: a) a second precursor outlet port aperture having a predetermined diameter, with: i. a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture ; ii. a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and b) a second reactant outlet aperture port having a predetermined diameter, with i. a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; ii. a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and iii. an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet.

16. The method of claim 15, wherein the first precursor is different from the second precursor.

17. The method of claim 15, wherein the first reactant is different from the second reactant.

18. A method of preventing edge effect in Direct Atomic Layer Processing (DALP), the method comprising a) providing an atomic layer deposition system comprising: i. a nozzle comprising:• a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and• a first reactant outlet aperture port having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet aperture are coplanar; and ii. a substrate operable to move reciprocally in at least a X axis, a Y axis, and a Z axis, wherein the nozzle, or the substrate or both the nozzle and the substrate are rotatable: b) using the first precursor outlet, and the first reactant outlet aperture, depositing the first precursor and the first reactant while moving the substrate along the X-axis under the nozzle in a first direction for a first predetermined distance; and c) while moving the substrate along the X-axis under the nozzle in a direction opposite the first direction for the first predetermined distance, using the first and second inert gas outlets and the first and second exhaust ports, or first and second vacuum ports, removing unreacted precursor and unreacted reactant.

19. A nozzle operable for atomic layer deposition comprising: a) a first precursor outlet port aperture with an aperture having a predetermined diameter, the precursor outlet further comprising: i. a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet aperture; ii. a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port; and iii. a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and b) a first reactant outlet aperture port an aperture having a predetermined diameter, the reactant outlet aperture further comprising: i. a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port; ii. a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port; andiii. a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet, wherein the first precursor outlet and the first reactant outlet aperture are arranged coplanar on the nozzle at a predetermined distance.

20. The nozzle of claim 18. further comprising: a) a second precursor outlet port aperture having a predetermined diameter, with: i. a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture ; ii. a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and b) a second reactant outlet aperture port having a predetermined diameter, with i. a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; ii. a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and c) an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet.

21. A system for direct Atomic layer processing (DALP)Direct Atomic Layer Processing (DALP) comprising: a) a nozzle having a plurality of functional ports; and b) a substrate operable to move relative to the nozzle, the system being operable to form a film having at least one dimension that is not thickness, which smaller than a diameter of at least one functional port aperture diameter.

22. The system of claim 21, wherein the nozzle comprises: a) at least one precursor outlet port aperture having a predetermined diameter, with an exhaust port, or a vacuum port, each arranged in a concentric annulus around the at least one precursor outlet port aperture, an inert gas outlet arranged in a concentric annulus around the exhaust port, or the vacuum inlet port, and another exhaust port, or another vacuum port, each arranged in a concentric annulus around the inert gas outlet; andb) at least one reactant outlet port aperture having a predetermined diameter, with an exhaust port, or a vacuum port, each arranged in a concentric annulus around the reactant outlet port aperture, an inert gas outlet arranged in a concentric annulus around the exhaust port, or third vacuum inlet port, and another exhaust port, or another vacuum port, each arranged in a concentric annulus around the inert gas outlet.

23. The system of claim 21, wherein the substrate operable to move reciprocally in at least a X- axis, a Y-axis, and a Z-axis.

24. The system of claim 23, wherein the substrate is operable to move diagonally relative to the nozzle.

25. A deposition method for forming a film having at least one dimension other than the film thickness - smaller than a diameter of a precursor outlet, and / or a reactant outlet aperture , the method implemented in a deposition system comprising: a nozzle operable for Direct Atomic Layer Processing (DALP), the nozzle comprising: a first precursor outlet port aperture having a predetermined diameter, with a first exhaust port, or a first vacuum port, each arranged in a concentric annulus around the first precursor outlet port aperture , a first inert gas outlet arranged in a concentric annulus around the first exhaust port, or the first vacuum inlet port, and a second exhaust port, or a second vacuum port, each arranged in a concentric annulus around the first inert gas outlet; and a first reactant outlet port aperture having a predetermined diameter, with a third exhaust port, or a third vacuum port, each arranged in a concentric annulus around the first reactant outlet aperture port, a second inert gas outlet arranged in a concentric annulus around the third exhaust port, or the third vacuum inlet port, and a fourth exhaust port, or a fourth vacuum port, each arranged in a concentric annulus around the second inert gas outlet; and a substrate, wherein the nozzle is operable to move reciprocally in a X-axis, a Y-axis, a Z-axis or a combination thereof: a) rotating the nozzle and / or the substrate such that a cord passing through a center of the first precursor outlet port aperture and the first reactant outlet port aperture is tilted relative to the X- axis at a first predetermined angle configured to only partially overlap the material deposited by the first precursor; b) moving the nozzle along the X-axis over the substrate in a first direction for a first predetermined distance; and c) depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at leastone dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture.

26. The method of claim 25, wherein the nozzle is rotatable.

27. The method of claim 26, further comprising rotating the nozzle at a predetermined angle relative to the X-axis.

28. The method of claim 25, further comprising: a) moving the nozzle along the Z-axis; b) rotating the nozzle, and / or the substrate relative to the X-axis at a second predetermined angle configured to only partially overlap the material deposited by the first reactant c) moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance; and d) depositing the first precursor and the first reactant, wherein the first precursor is configured for deposition first.

29. The method of claim 25, further comprising: a) returning the nozzle to its initial position at an initial point relative to the predetermined distance; and b) repeating the steps of moving the nozzle, to the step of depositing the first precursor and the first reactant,30. The method of claim 25, wherein the first precursor outlet and the first reactant outlet aperture are coplanar.

31. The method of claim 25, wherein the diameter of the first precursor outlet is identical to the diameter of the first reactant outlet aperture.

32. The method of claim 25, wherein the diameter of the first precursor outlet is different from the diameter of the first reactant outlet aperture.

33. The method of claim 30, wherein the step of rotating the substrate relative to the X-axis is eliminated, the method further comprising, following the step of simultaneously depositing the first precursor and the first reactant, forming a first precursor strip and a first reactant strip of the first predetermined distance along the X-axis: a) while depositing the first precursor and the first reactant, moving the nozzle along the Y-axis to a second predetermined distance in a second direction configured to only partially overlap the strip formed by the reactant with the strip formed by the first precursor; andb) while depositing the first precursor and the first reactant, moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.

34. The method of claim 33, further comprising: a) moving the nozzle along the Z-axis; b) rotating the nozzle, or the substrate 180°, or rotating the nozzle 90° and the substrate 90°, or repositioning the nozzle in its original position. c) while depositing the first precursor, moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance, the first precursor configured to be deposited over the film having the first thickness; d) moving the nozzle along the Y-axis to the second predetermined distance opposite the second direction; and e) depositing the first reactant, moving the nozzle along the X-axis over the rotated substrate in a direction opposite the first direction for the first predetermined distance, the first reactant configured to only be deposited partially over the deposited precursor, forming a film having a second thickness.

35. The method of claim 33, further comprising a) repositioning the nozzle in the initial point relative to the predetermined distance; and b) repeating the steps of moving the nozzle along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, and while depositing the first precursor and the first reactant, moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.

36. The method of claim 34, wherein the first reactant is not deposited simultaneously, the method comprising, following the step of moving the nozzle along the Y-axis to a second predetermined distance in a second direction configure to only partially overlap the strip formed by the reactant with the strip formed by the first precursor, while depositing the first reactant, moving the nozzle along the X-axis over the substrate in a direction opposite the first direction for the first predetermined distance, forming a film having a first thickness.

37. The method of claim 25, further comprising, following the step of depositing the first precursor and the first reactant: while moving the nozzle along the X-axis over the substrate in adirection opposite the first direction for the first predetermined distance, using the first inert gas outlet and the first and second exhaust ports, or vacuum ports, removing unreacted precursor and unreacted reactant.

38. The method of claim 25, wherein the step of rotating the nozzle and / or the substrate is eliminated, and wherein the step of moving the nozzle along the X-axis over the substrate in a first direction for a first predetermined distance comprises moving the nozzle diagonally relative to the X-axis; and depositing the first precursor and the first reactant, wherein the first direction along the X-axis is configured for depositing the first precursor first, thereby forming the film having at least one dimension smaller than the diameter of the first precursor outlet, and / or the first reactant outlet aperture.

39. The method of claim 25, wherein the nozzle further comprises: a) a second precursor outlet port aperture having a predetermined diameter, with: i. a fifth exhaust port, or a fifth vacuum port, each arranged in a concentric annulus around the second precursor outlet port aperture ; ii. a third inert gas outlet arranged in a concentric annulus around the fifth exhaust port, or the fifth vacuum inlet port; and a sixth exhaust port, or a sixth vacuum port, each arranged in a concentric annulus around the third inert gas outlet; and b) a second reactant outlet aperture port having a predetermined diameter, with i. a seventh exhaust port, or a seventh vacuum port, each arranged in a concentric annulus around the second reactant outlet aperture port; ii. a fourth inert gas outlet arranged in a concentric annulus around the seventh exhaust port, or the seventh vacuum inlet port; and iii. an eighth exhaust port, or an eighth vacuum port, each arranged in a concentric annulus around the fourth inert gas outlet.

40. The method of claim 39, wherein the first precursor is different from the second precursor.

41. The method of claim 36, wherein the first reactant is different from the second reactant.

42. The method of claim 25, wherein the nozzle, and / or the substrate is each coupled to a rotating platform, capable of rotating between 10and 180°.

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