Apparatus and methods for thin-film deposition

Abstract

A thin film deposition system includes a modular reactor head, a substrate stage, and a modular reactor head positioning system that positions the modular reactor head relative to a substrate to deliver precursor gases to the substrate positioned on the substrate stage. The modular reactor head includes sets of modular components that perform different functions and can be arranged in different configurations.

Description

Technical Field

[0001] Cross - reference to Related Applications This disclosure claims priority from U.S. Provisional Application No. 62 / 949,798, filed on December 18, 2019, which is hereby incorporated by reference herein.

[0002] This disclosure generally relates to thin - film deposition, and more specifically, to apparatus and methods for thin - film deposition.

Background Art

[0003] Techniques such as sputtering, evaporation, and chemical vapor deposition are used to deposit films for many applications (e.g., modern electronic devices, optical components, display technology, food packaging, etc.). For these applications, improved control over film thickness is required. Atomic layer deposition (ALD) is the best technique for producing films with nanometer - scale thickness control because it deposits the film one atomic layer at a time. As feature sizes continue to decrease in applications such as integrated circuits and memory devices, ALD is becoming the preferred (and in some cases the only) option for depositing several film components. Weaknesses associated with conventional time - based ALD include its speed (a relatively slow batch process) and the need for its vacuum chamber (which hinders its scalability).

[0004] Conventional time - based ALD operates by sequentially inserting two or more chemical precursor gases into a vacuum chamber and having evacuation and purge steps during the exposure. When suitable experimental conditions are used, a single atomic layer of material is formed after each sequence, and the sequence is repeated many times to build the film. Thus, conventional time - based ALD separates the two precursor gases temporally. In contrast, spatial atomic layer deposition (SALD) techniques have been developed that separate the two precursors spatially rather than temporally. The substrate moves between the two precursor gases to replicate continuous exposure. This eliminates or reduces the evacuation and purge steps that slow down time - based ALD.

Summary of the Invention

[0005] Atmospheric pressure SALD (AP-SALD) can produce thin film layers of materials (e.g., metal oxides) that are compact, conformal, and pinhole-free, and can deposit thin films at approximately room temperature. This is one to two orders of magnitude faster and more scalable than conventional ALD. In particular, AP-SALD is also compatible with roll-to-roll manufacturing and has been demonstrated to work on eyeglasses, eyeglasses coated with transparent conductive oxides, semiconductor wafers, foils, fabrics, and plastic surfaces. These advantages make AP-SALD very attractive for high-throughput manufacturing of large-area, low-cost electronic devices such as solar cells, batteries, and microelectronics, as well as functional coatings such as barrier films and antimicrobial coatings.

[0006] Therefore, novel apparatus and methods for thin-film deposition are provided. [Means for solving the problem]

[0007] Summary of the Invention This disclosure includes novel thin film, film, or thin layer deposition methods, generally comprising at least one reactor head that is modular and configurable for functional flexibility and scalability for producing thin films. Thin layer deposition may include spatial atomic layer deposition and / or chemical vapor deposition. The reactor head may include, but is not limited to, different types of components such as precursor gas slits, plasma sources, exhaust slits, heating channels, and / or cooling channels for different types of deposition. The spaced elevation and width of each component may be adjusted to facilitate and control gas flow. A positioning system having mounting elements for the reactor head is configured to maintain adjustable orientation and position of the reactor head relative to the substrate. The positioning system may comprise at least one displacement measuring device and at least one actuator. A heating stage with suction may be used to heat the substrate and hold substrates of different sizes, geometric shapes, and thicknesses. The heating stage may be configured with zone-controlled heating to provide different temperatures at different locations. A linear motor positioning system may be used to vibrate the substrate relative to the modular reactor head. The system can deposit thin films by spatial atomic layer deposition or chemical vapor deposition to produce films with uniform thickness and / or composition, or films with varying thickness and / or composition.

[0008] One aspect of the present disclosure provides a modular reactor head for use with a thin film deposition system, comprising a set of modular components, wherein the set of modular components are adjacent to one another in a first direction within the reactor head, the set of modular components may be positioned relative to one another in a second direction, the second direction being substantially perpendicular to the first direction, and the set of modular components comprises at least one precursor gas modular component for depositing at least two precursor gases onto a substrate.

[0009] In another embodiment, the set of modular components includes at least two precursor gas modular components. In yet another embodiment, at least two precursors include a reactor channel and a reactor channel opening. In yet another embodiment, the reactor channel opening delivers a gaseous or liquid material having a higher outlet velocity at one end of the reactor channel opening than at the opposite end of the reactor channel opening. In one embodiment, the set of modular components includes at least one of a precursor fluid component, an exhaust modular component, an inert gas modular component, a temperature control modular component, a chemical modular component, a cleaning modular component, and a plasma source modular component. In yet another embodiment, the temperature control modular component includes a metal plate for controlling the temperature of a modular component adjacent to the temperature control modular component. In yet another embodiment, the temperature control modular component includes a reactor channel for receiving either a coolant for cooling the metal plate or a heatant for heating the metal plate. In yet another embodiment, the set of modular components are mounted at a predetermined height relative to each other. In yet another embodiment, the precursor fluid modular component includes an actuator for controlling the deposition of the precursor fluid.

[0010] Another aspect of the present disclosure provides a thin film deposition system comprising: a substrate stage for supporting a substrate; a modular reactor head for depositing a thin film on the substrate, the modular reactor head comprising a set of modular components, the set of modular components being adjacent to one another in a first direction within the reactor head, the set of modular components being oriented in a second direction relative to one another, the second direction being substantially perpendicular to the first direction, and the set of modular components comprising at least one precursor gas modular component for depositing at least two precursor gases on the substrate; and a modular reactor head positioning system for positioning the modular reactor head relative to a substrate on the substrate stage.

[0011] In a further aspect, the modular reactor head positioning system includes a linear displacement system. In another aspect, the linear displacement system includes a set of displacement measurement devices and a set of linear actuators. In yet another aspect, the modular reactor head positioning system includes a leveling system for gap control between the modular reactor head and the substrate stage. In one aspect, the substrate stage includes a vacuum system for holding the substrate relative to the substrate stage. In another aspect, the substrate stage includes an upper plate for supporting the substrate and a heating component for heating the upper plate. In yet another aspect, the substrate stage includes a linear motor system. The present invention provides, for example, the following: (Item 1) A modular reactor head for use with a thin film deposition system, A set of modular components comprising a set of modular components that are adjacent to each other in a first direction within the reactor head, The set of modular components may be positioned relative to each other in a second direction, the second direction being substantially perpendicular to the first direction. A modular reactor head, wherein the set of modular components includes at least one precursor gas modular component for depositing at least two precursor gases onto a substrate. (Item 2) The modular reactor head according to item 1, wherein the set of modular components includes at least two precursor gas modular components. (Item 3) The modular reactor head according to item 2, wherein the at least two precursor gas modular components are separated by at least one other modular component. (Item 4) At least one of the set of modular components is Reactor channels and A modular reactor head as described in item 1, comprising a reactor channel opening. (Item 5) The modular reactor head according to item 4, wherein the reactor channel opening delivers a gaseous or liquid material having a higher outlet velocity at one end of the reactor channel opening than at the opposite end of the reactor channel opening. (Item 6) <{ The modular reactor head according to item 1, wherein the set of modular components includes at least one of a precursor fluid component, an exhaust modular component, an inert gas modular component, a temperature control modular component, a chemical modular component, a cleaning modular component, and a plasma source modular component. (Item 7) <{ The aforementioned temperature control modular component is The modular reactor head according to item 6, comprising a metal plate for controlling the temperature of a modular component adjacent to the aforementioned temperature control modular component. (Item 8) The modular reactor head according to item 7, wherein the temperature control modular component comprises a reactor channel for receiving either a coolant for cooling the metal plate or a heating liquid for heating the metal plate. (Item 9) The modular reactor head according to item 1, wherein the set of modular components is mounted relative to each other at a predetermined height. (Item 10) A thin film deposition system, A substrate stage for supporting the substrate, A modular reactor head for depositing a thin film on the substrate, wherein the modular reactor head includes a set of modular components, and the set of modular components are adjacent to each other in a first direction within the reactor head. The set of modular components may be positioned relative to each other in a second direction. The second direction is substantially perpendicular to the first direction, The set of modular components includes a modular reactor head, which includes at least one precursor gas modular component for depositing at least two precursor gases onto a substrate, A thin film deposition system comprising: a modular reactor head positioning system for positioning the modular reactor head relative to the substrate on the substrate stage. (Item 11) The thin film deposition system according to item 10, wherein the modular reactor head positioning system comprises a linear displacement system. (Item 12) The linear displacement system, A set of displacement measuring devices, A thin film deposition system according to item 11, comprising a set of linear actuators. (Item 13) The aforementioned modular reactor head positioning system The thin film deposition system according to item 10, further comprising a leveling system for controlling the gap between the modular reactor head and the substrate stage. (Item 14) The aforementioned substrate stage, The thin film deposition system according to item 10, further comprising a vacuum system for holding the substrate relative to the substrate stage. (Item 15) The aforementioned substrate stage, An upper plate for supporting the aforementioned substrate, The thin film deposition system according to item 10, comprising a heating component for heating the upper plate. (Item 16) The thin film deposition system according to item 10, wherein the substrate stage comprises a linear motor system. (Item 17) The modular reactor head according to item 6, wherein the precursor fluid modular component comprises an actuator for controlling the deposition of the precursor fluid. [Brief explanation of the drawing]

[0012] To ensure a clear understanding of this disclosure, some embodiments of this disclosure are illustrated as examples and are not limited to those shown in the accompanying drawings.

[0013] [Figure 1] An embodiment of a thin-layer deposition system is shown. [Figure 2] This is an isometric view of an embodiment of a modular reactor head that includes multiple modular components. [Figure 3A] Figure 2 is a bottom view of the modular reactor head. [Figure 3B] Figure 2 is a bottom perspective view of the modular reactor head. [Figure 3C] This is a bottom view of a modular component having multiple slits. [Figure 4] Figure 2 is a side view of the modular reactor head. [Figure 5A] This is a side view of an embodiment of a modular reactor head having multiple modular components with adjustable, spaced elevations. [Figure 5B] Figure 5A is a front view of the modular reactor head. [Figure 5C] Figure 5A is an isometric view of the modular reactor head. [Figure 6] This is a perspective view of an embodiment of a cooling module component. [Figure 7] This is a perspective view of an embodiment of a modular reactor head. [Figure 8A] This is a front view of an embodiment of a thin-film deposition system including a reactor head positioning system. [Figure 8B] Figure 8A is a perspective view of the thin film deposition system. [Figure 9A] This is a perspective view of an embodiment of a substrate stage. [Figure 9B] Figure 9A is a cross-sectional view of the substrate stage. [Figure 10] Figure 9A is a perspective view of the four substrates held on the substrate stage. [Figure 11] This is a bottom perspective view of the upper plate embodiment. [Figure 12A] This shows different configurations of the heating stage. [Figure 12B] This shows different configurations of the heating stage. [Figure 13A] This is a schematic diagram of a reactor head having three reactor channels configured to deliver a uniform flow profile. [Figure 13B] This is a schematic diagram of a reactor head having a single reactor channel configured to deliver a non-uniform flow profile. [Figure 14A] This is a schematic diagram of the geometric shape of a reactor channel having a non-uniform flow profile for an embodiment of a modular component. [Figure 14B] Figure 14A is a graph showing the results of a computational fluid dynamics simulation, illustrating the flow velocity along the outlet of the precursor gas slit for the reactor channel geometry. [Figure 14C] This is a schematic diagram of a design for an embodiment of a reactor head having a non-uniform flow profile. [Figure 14D] Figure 14C is a photograph of the 3D printed reactor head. [Figure 15] This is a photograph of the zinc oxide (ZnO) film produced using the reactor head shown in Figure 14C. [Figure 16A] This graph shows the measured ZnO film thickness across the entire substrate for the thickness gradient film shown in Figure 15. [Figure 16B] Figure 16A shows a map of the film thickness on the substrate surface. [Figure 17A] This is a perspective view of an embodiment of a modular component comprising two symmetrical semi-parts. [Figure 17B] Figure 17A is an exploded perspective view of the modular components. [Figure 18] This is a perspective view of an embodiment of a substrate stage mounted on a linear motor system. [Figure 19] This diagram shows a flow chart of a method for depositing thin films using a modular reactor head. [Figure 20] This diagram shows a flow chart of the roll-to-roll method for depositing thin films using a modular reactor head. [Modes for carrying out the invention]

[0014] The terminology used herein is solely for the purpose of describing specific embodiments and is not intended to limit the system or disclosure. Where used herein, the terms “and / or” include any and all combinations of one or more of the enumerated items relating to the subject. Where used herein, the singular forms “a,” “an,” and “the” are intended to include the plural and singular forms unless the context otherwise expressly indicates. Where used herein, the terms “comprise(s)” and / or “comprising” specify the presence of the described features, steps, actions, elements, and / or components, but should be further understood not to exclude the presence or addition of one or more other features, steps, actions, elements, components, and / or groups thereof.

[0015] Figure 1 shows an embodiment of a thin film or thin layer deposition system 100, which includes a modular reactor head 102, a reactor head positioning system 104, and a substrate stage 108 for supporting a substrate 106. In one embodiment, the reactor head positioning system 104 controls the orientation of the reactor head 102 relative to the substrate 106, such as linear direction, rotation along an axis, and / or the distance between the reactor head and the substrate 106. The substrate stage 108 controls the position of the substrate 106 relative to the modular reactor head 102. During operation, the modular reactor head 102 deposits a thin film of precursor gas or material onto the substrate, as will be discussed in more detail below.

[0016] As used herein, the terms “thin layer” or “thin film” refer to layers of material deposited by spatial atomic layer deposition (SALD) and / or spatial chemical vapor deposition (SCVD). It has been shown that chemical vapor deposition can occur instead of atomic layer deposition by controlling processing conditions so that precursor gases can mix in a gas phase (not isolated from each other). This results in higher thin-film deposition rates, which are advantageous for several applications, while still producing conformal, pinhole-free films with precise control of film thickness on the nanometer scale. Thus, the terms “thin layer deposition” refer to spatial atomic layer deposition and / or spatial chemical vapor deposition.

[0017] In this embodiment, the modular reactor head 102, the reactor head positioning system 104, and the substrate stage 108 are positioned in the lower cabinet 110. Apparatus for delivering the precursor gas to the modular reactor head is located in the upper cabinet 112. This apparatus will be readily apparent to those skilled in the art. In one embodiment, the apparatus may include, but are not limited to, devices for generating the gas 180 of the precursor chemical, such as a bubbler and a bubbler heater;, but are not limited to, devices for controlling the flow rate 182 of the gas, such as a mass flow controller; and, but are not limited to, devices for dispersing the gas, such as valves, tubes, and manifolds 184. In one embodiment, the precursor gas may be directly introduced into the upper cabinet from an external source, or may be generated from liquid or solid chemicals by foaming or spraying a liquid chemical material, or by heating a solid chemical material. In another embodiment, instead of, or together with, the precursor gas, a liquid may be delivered from the upper cabinet to the modular reactor head.

[0018] Figure 2 is an isometric view of an embodiment of the modular reactor head 102. The modular reactor head 102 includes multiple or sets of modular components 114. In one embodiment, the modular reactor head 102 may include a set of modular components 114, so that each modular component performs a single function to enable thin-layer deposition. In some embodiments, multiple modular components may perform the same function as other modular components in other embodiments.

[0019] In one embodiment, the reactor head 102 may be oriented parallel to the substrate stage 108, with a set of modular components 114 adjacent to each other in a plane oriented along a first direction 128. The length of each of the set of modular components 114 may be considered to extend in a second direction 126 substantially perpendicular to the first direction 128. The reactor head 102 may be positioned at a certain distance from the substrate 106, and the distance may be measured along a direction 130 substantially perpendicular to the first and second directions. In some embodiments, the distance may be measured as an angle from the reactor head. Each of the set of modular components 114 may perform a different function, as will be discussed in more detail below.

[0020] In one embodiment, as shown by the dotted line in Figure 2, the modular component 114 includes a reactor channel 132 for receiving a gas or liquid, and a reactor channel opening 134 (which may be considered a slit) that allows the gas or liquid to enter or exit the reactor channel 132. The reactor channel opening typically has a length oriented parallel to the second direction 126, but in alternative embodiments, the reactor channel opening may be oriented at an angle to the second direction 126. In some embodiments, the modular component 114 may not include a reactor channel opening (as disclosed with respect to Figure 6), or the modular component may not include a reactor channel or reactor channel opening that may be a heating or cooling element powered by a power source. Non-exclusive examples of modular components include, but are not limited to, precursor gas components, exhaust components, inert gas components, heating components, cooling components, plasma sources, and other components according to various embodiments of the present disclosure.

[0021] When a precursor gas passing through the modular component 114 is supplied to the substrate from a precursor gas source, the modular component 114 may be considered a precursor gas component, and the reactor channel opening is called a precursor gas opening. Since thin-layer deposition typically requires at least two different precursor gases, at least two of the modular components of the reactor head provide the functionality of a precursor gas modular component. Alternatively, when an inert gas is supplied to the modular component 114, the modular component may be considered an inert gas modular component, and the reactor channel opening is called an inert gas opening. When a precursor fluid, such as a liquid and an actuator, is supplied to the modular component 114, the modular component may be considered a precursor fluid modular component and may be used to introduce different nanofabrication techniques, such as selective region deposition, slot die coating, inkjet printing, or spray deposition, but are not limited to these. If a modular component 114 is coupled to a vacuum source to draw gas into its reactor channel 132 through the reactor channel opening, the modular component 114 may be considered an exhaust modular component, and the reactor channel opening is called an exhaust opening. The modular component 114 may be considered a thermally controlled modular component, thereby allowing a thermal fluid to pass through the reactor channel. In a thermally controlled modular component, the reactor channel 132 does not include a reactor channel opening. If the thermally controlled modular component provides heat, the modular component may be called a modular heating component. If the thermally controlled modular component provides cooling, the thermal component may be called a modular cooling component. If plasma is introduced into the reactor channel, the modular component may be considered a plasma source or a plasma modular component.Alternatively, if the modular component 114 is supplied with a chemical substance such as a cleaning agent, or compressed air, the modular component may be considered a cleaning modular component and may be used to clear reactor channels for maintenance purposes or, if necessary, for cleaning the substrate. In an alternative embodiment, the chemical substance may be a reducing agent in which a material on the substrate (such as a metal) can catalyze other materials (such as a metal ion salt). In another embodiment, the chemical substance may be used to perform a surface modification or etching treatment on the substrate.

[0022] Figures 3A and 3B are bottom views of a modular reactor head 102 having reactor channel openings 134. In this embodiment, the set of modular components 114 includes a first precursor gas component 116, a second precursor gas component 118, three inert gas components 120, six exhaust components 122, and two cooling components 124, but it will be understood that this is just one arrangement of how the modular components can be configured. In some embodiments, the set of modular components includes at least two precursor gas components, while in other embodiments, one modular component may be used to deliver two or more precursor gases, such that the set of modular components includes only one modular component for delivering the precursor gases.

[0023] In this embodiment, the set of head modular components 114 is arranged to effectively separate the precursor gas for atomic layer deposition (ALD) by positioning at least one of the inert gas components 120 and at least one of the exhaust components 122 between the first precursor gas component 116 and the second precursor gas component 118. The arrangement of the modular components 114 is flexible so that, in an alternative embodiment, the arrangement of the modular components 114 may be configured to mix the precursor gas for chemical vapor deposition (CVD) (for example, the first and second precursor gas components 116 and 118 may be located directly adjacent to each other, not between the exhaust component 122 or the inert gas component 120).

[0024] Each modular reactor component 114 may be positioned along its long axis parallel to the second direction 126. A set of modular components 114 may be arranged such that each modular component 114 is positioned adjacent to at least one other modular component 114 extending in the first direction 128. In other words, the individual modular components 114 of the modular reactor head 102 are stacked horizontally to facilitate assembly. The arrangement of the modular components 114 depends on the configuration of the reactor head 102, and the arrangement can be changed by changing the position of one or more of the modular components 114 (i.e., changing the arrangement).

[0025] The modular reactor head of this disclosure may allow for easy scaling of the thin film deposition system by increasing the number of individual modular components or by increasing the length of the reactor channel openings. The number of ALD cycles that occur each time a substrate passes under the modular reactor head can be increased by increasing the number of precursor gas modular components or by increasing the number of reactor channel openings in the modular components. Figure 3C is a bottom view of a modular component having three slits, or reactor channel openings 134, but in alternative embodiments, the modular component may have two, four, or more slits 134. Each slit 134 may have its own reactor channel 132, or the slits 134 may be connected to a single reactor channel. Longer slits may allow for coating a large number of substrates or larger substrates with thin films.

[0026] The modular reactor head 102 may allow for functional flexibility, and different types of individual modular components may be easily added, such as a cooling channel, a heating channel, a plasma source, and a precursor gas modular component having reactor channel openings with unique characteristics (e.g., heterogeneous gas delivery for generating a film gradient, as considered below). Each modular component may be customized, installed, or swapped out for different functions and purposes.

[0027] Figure 4 is a side view of the modular reactor head 102. Each modular component 114 includes a plurality of slots 136. Each slot 136 is configured to accommodate a mounting rod (not shown) for supporting the modular component 114 within the modular reactor head 102. In this embodiment, each slot 136 is larger than the respective mounting rod in a direction parallel to the plane 130, allowing the position of each modular component 114 to vary relative to the position of the mounting rod, thereby allowing the position of each modular component 114 to vary along the plane 130. In other words, each modular component 114 is slidably mounted in the modular reactor head 102, allowing for adjustment of the position of each modular component 102 along the plane 130.

[0028] Figures 5A, 5B, and 5C show side, front, and isometric views of an embodiment of a modular reactor head 500 having multiple modular components 114 with adjustable spacing elevations and varying heights. The modular reactor head 500 may be substantially similar to the modular reactor head 102 and may be formed using the same multiple modular components 114 used to form the modular reactor head 102. In one embodiment, the reactor head 500 may include a first precursor gas component 116, a second precursor gas component 118, an inert gas component 120, an exhaust component 122, and a cooling component 124, although it will be understood that the modular components may vary such that at least two of the modular components are precursor gas components. The height of each modular component 114 relative to the substrate and other modular components (and thereby the height of each reactor channel opening) can be precisely mechanically adjusted relative to adjacent modular components 114 to achieve desired spacing elevations. For example, the height of each modular component 114 can be adjusted by sliding that modular component 114 (perpendicular to the rod axis) relative to an adjacent modular component 114. Spacing elevation adjustments can provide greater flexibility and control over the gas flow. In Figures 5A, 5B, and 5C, the exhaust component 120 moves slightly upward along the plane 130 to create a region into which the precursor gas flows naturally, improving exhaust efficiency and preventing or reducing the possibility of gas mixing.

[0029] Figure 6 is a perspective view of an embodiment of a modular component that may be used as a modular cooling (or heating) component 124. In some embodiments of the modular reactor head, thermal components (including heating and cooling components) may be positioned adjacent to precursor gas components. Thermal components allow for temperature control of at least a portion of the modular reactor head. For example, the temperature of a precursor gas component adjacent to a thermal component may be controlled relative to the temperature of a heated substrate stage to obtain desired thin film deposition conditions. In one embodiment, the reactor channel 132 of the modular cooling component 124 includes a cooling plate 138 for removing heat from an adjacent precursor gas modular component. In one embodiment, the cooling plate is made of a metal such as copper, but is not limited. In one embodiment, chilled water may circulate inside the reactor channel 132 of the modular cooling component to provide a temperature difference between the modular cooling component and an adjacent precursor gas modular component. In an alternative embodiment, chilled water may be replaced with hot water or a heating element for heating the precursor gas opening of the precursor gas modular component. More specifically, a modular cooling component, such as a cooling plate, is cooled as the chilled liquid passes through its reactor channels, drawing heat from adjacent modular components to ensure that the chemical reaction occurs on the substrate rather than on the adjacent modular component. Alternatively, for a modular heating element, the modular component cooling plate or heating element is heated to heat the reactor channels of an adjacent modular component for a precursor gas (e.g., an adjacent precursor gas modular component) that is prone to unwanted condensation on the cooling surface.

[0030] Figure 7 is a perspective view of an embodiment of the modular reactor head 700. The modular reactor head 700 may be substantially similar to the modular reactor head 102 and the modular reactor head 500. The modular reactor head 700 can be scaled within a thin film deposition system to increase the thin film deposition area and / or throughput. For example, the scale of the modular reactor head 700 can be increased in direction 126 by using modular components having reactor channel openings with increased length in direction 126. Increasing the scale of the modular reactor head 700 in direction 126 can increase the size of the film deposited on the substrate in direction 126, thereby increasing the film area or the number of substrates to which the film is deposited. The scale of the modular reactor head 700 can be increased in direction 128 by increasing the number of modular components forming the reactor head 700, for example, by adding additional modular components such as precursor gas components, but are not limited to. Increasing the scale of the modular reactor head 700 in direction 128 increases the thickness of the film deposited in one pass of the modular reactor head 700, which may increase the throughput of the modular reactor head 700.

[0031] Figures 8A and 8B show a front view and a perspective view of an embodiment of the thin film deposition system. The thin film deposition system 800 includes a reactor head positioning system 804. The thin film deposition system 800 may be substantially similar to the thin film deposition system 100. The reactor head positioning system 804 includes mounting elements (not shown) for receiving a reactor head 801, such as a modular reactor head 102, and is configured to maintain in a configurable orientation and position of the reactor head 801 relative to the substrate 806 on which the thin film is deposited. In particular, the reactor head positioning system 804 is configured to control the distance between the modular reactor head 800 and the substrate 806. In this embodiment, the reactor head positioning system 804 includes a linear displacement system including one or more laser displacement sensors 808 that function as displacement measuring devices and one or more linear actuators 810 that function as displacement control devices. In alternative embodiments, other displacement measuring devices and actuators may be used. In conjunction with the displacement measuring device and actuator, the distance between the reactor head 801 and the substrate 806 is dynamically monitored and adjusted using software, such as forms, modules, or instructions stored on a computer-readable medium. In one embodiment, a resolution of 1 micrometer is used. The ability to precisely control the reactor-substrate distance (i.e., plane 130) can control whether the precursor gas remains isolated (resulting in ALD) or mixes in the gas phase (resulting in CVD). An example of a conventional positioning system is a floating wafer system, but a floating wafer system is limited to substrates that can float. In other words, the positioning system of this embodiment can offer greater flexibility in terms of the size, number, or type of substrates that can be used for thin film deposition. In this embodiment, the reactor head positioning system 804 is configured to move the reactor head 801 along plane 130 to control the reactor-substrate distance between the substrate 806 and the reactor head 801, but in an alternative embodiment, the substrate 806 may move along plane 130 while the reactor head 801 remains stationary.

[0032] The deposition system may be equipped with loading and unloading mechanisms for the substrate, such as robotic arms, to fully automate the manufacturing process. The deposition system may also be compatible with roll-to-roll technologies, such as film deposition on plastics, textiles, or foils. In the case of a roll-to-roll system, the substrate stage may be configured to be compatible with a continuous web of plastic, textile, or foil, for example, the substrate stage may include rollers that hold a portion of the web close to the reactor head at least approximately a constant distance from the reactor head, and the system may achieve a desired thickness on the web by rolling / unrolling the web, controlling the position of the web and the number of deposits.

[0033] Figure 9A is a perspective view of an embodiment of the substrate stage 900. The substrate stage 900 may be substantially similar to the substrate stage 108. Figure 9B shows a cross-sectional view of an embodiment of the substrate stage 900. In this embodiment, the substrate stage 900 includes an upper plate 902 having a plurality of holes 904, heating components 905 (shown by dotted lines), such as heating elements embedded within the upper plate 902, and a vacuum reservoir 908 that is fluidly coupled to the plurality of holes 904 and provides suction to the plurality of holes 904. The upper plate 902 may be an upper metal plate.

[0034] The upper plate 902 is separated from the vacuum reservoir 908 by an insulating layer 906, which may be a gap, in order to thermally insulate the vacuum reservoir 908 from the upper plate 902, which is heated by the heating element 905. A substrate (not shown) may be placed on the upper plate 902, and when suction is provided, a plurality of holes 904 in the upper plate 902 can firmly hold the substrate in place on the upper plate 902. In other words, the vacuum reservoir 908 coupled to the plurality of holes 904 in the upper plate 902 forms a mechanism for holding the substrate on the substrate stage 900.

[0035] Figure 10 is a perspective view of four (4) substrates 912 held on a substrate stage 900. Substrates of varying size, geometry, thickness, and material (e.g., glass, silicon wafers) may be heated on or by the upper plate 902 (heated by a heating element) and held by a vacuum holding mechanism 908, provided the substrate is substantially flat within the dimensions of the substrate stage. Multiple holes 904 can be configured to accommodate substrates 912 of different sizes and geometric shapes. Caps (not shown) may be added to the multiple holes 904 as needed to prevent or reduce the possibility of suction at specific locations on the substrate stage 900.

[0036] In one embodiment, the upper plate 902 is offset by a predetermined distance, such as approximately 10 mm or more, from the vacuum reservoir 908 (which provides suction for holding the substrate 912 downwards), to provide an insulating gap 9. As discussed above, additional insulation can be added to isolate the vacuum reservoir 908 and the underlying system components from the heat generated by the heating element 905.

[0037] Figure 11 is a bottom perspective view of an embodiment of the upper plate 902, in which the upper plate 902 includes heating elements such as internally embedded heating elements 905. In alternative embodiments, two or more heating elements 905 may be embedded within the upper plate 902, as discussed below. Thermal grease may be used to increase the thermal conductivity between the heating elements 905 and the upper plate 902. The heating provided by the heating elements may alternatively be carried out via infrared heating elements or laser heating elements, thereby allowing these heating elements to perform other functions in addition to heating.

[0038] Figure 12A shows a top view of an embodiment of a heating element 1200 having a single heating unit 1202. Figure 12B shows a top view of an embodiment of a heating element 1204 having three heating units 1202 positioned in three heating zones 1206, 1208, and 1210, thereby allowing the heating element 1204 to be considered configured for zone-controlled heating. In alternative embodiments, the heating element 1204 may have two, four, or more heating units, and thus may have two, four, or more corresponding heating zones that can be controlled individually. The heating element may be configured for uniform or non-uniform heating depending on the selection and arrangement of the heating elements. This modular heating element design helps improve energy use for different substrate geometries, enables uniform and non-uniform zone heating of substrates, and allows for rapid prototyping by enabling deposition on a large number of substrates at different temperatures. Furthermore, non-uniform / zone heating can be used to determine the operating temperature ranges for ALD and CVD modes of different chemicals. In alternative embodiments, gradient heating may be used. Heating elements 1200 and 1204 may be substantially similar to heating element 905.

[0039] Figure 13A is a schematic diagram of a reactor head 1300 having a modular component 1301 having a reactor channel 1302, the reactor channel 1302 being configured to deliver a uniform flow profile as indicated by the arrow below the reactor channel. Conventional ALD techniques typically deposit films with uniform thickness and composition, which can be achieved by delivering a precursor gas having a uniform flow profile. The thin-layer deposition system of the present disclosure can deposit films with uniform as well as films with non-uniform thickness and composition. The geometry of the reactor channel in the modular component can be modified to control the flow profile of the precursor gas, or gas through the reactor channel, openings, thereby allowing different amounts of precursor gas to be delivered to different locations on the substrate.

[0040] Figure 13B is a schematic diagram of a reactor head 1304 having modular components, at least one of which has a reactor channel 1306 configured to deliver a non-uniform flow profile, as indicated by the arrows below the reactor channel 1306, where the fluid flows faster at one end where the arrows are closer together than at the other end where the arrows are further apart. The non-uniform flow profile allows more material to be deposited where more precursor gas is delivered. Depending on the flow profile of the fluid, gas, or liquid, linear, non-linear, or complex variations in thickness or composition can be generated across the entire film. In one embodiment, a specific flow profile of a precursor gas modular component can be obtained by designing the geometry of the reactor channel, or the precursor gas, slit, or opening, using computational fluid dynamics (CFD) simulations. Figures 13A and 13B illustrate how the precursor gas reactor channel opening can be customized to produce a film with a uniform flow of precursor gas, and therefore a film with a uniform thickness and composition (Figure 13A), or a film with a non-uniform flow of precursor gas, and therefore a film with a thickness and / or composition gradient (Figure 13B).

[0041] Figure 14A shows the schematic geometry or a portion of the reactor channel 1400 for delivering a non-uniform flow profile when used with modular components, for example, modular component 114. In this embodiment, the reactor channel 1400 includes a fluid inlet section 1410 which includes an inlet area 1412 for receiving fluid. As the fluid passes through the inlet area 1412, the fluid exits the inlet area (through the outlet point 1413) and flows downward toward the reactor channel opening 1414. As the fluid exits the inlet area 1412, the fluid flowing or moving toward the reactor channel opening 1414 closer to the outlet point 1413 (considered area 1414a) has a higher velocity than the fluid flowing or moving toward the reactor channel opening 1414 further from the outlet point (considered area 1414b).

[0042] Figure 14B shows a computational fluid dynamics (CFD) simulation of the flow through the reactor channel opening of a modular component having the reactor channel geometry shown in Figure 14A. In this embodiment, one end of the reactor channel opening delivers more precursor gas, resulting in a higher outlet velocity than the opposite end of the reactor channel opening. When reactor channel 1400 is used in a modular reactor head for CVD, this results in more mixing of the precursor gas at one end of the precursor gas slit or opening, which can result in a non-uniform deposition rate along the length of the precursor gas slit. Alternatively, when reactor channel 1400 is used in a modular reactor head for AP-SALD, at one end of the reactor channel opening, the substrate may be completely saturated with the precursor during each ALD cycle, while at the other end of the reactor channel opening, the substrate may not be completely saturated, again resulting in a non-uniform deposition rate along the length of the reactor channel opening. The geometry of the reactor channel opening may be varied for one or more reactor channel openings, which results in a non-uniform deposition rate for one or more components of the film. If all film components have the same non-uniform deposition rate, a film with non-uniform thickness in the first direction is produced. In other words, the film thickness can vary. If film components with uniform and non-uniform deposition rates (or different non-uniform deposition rates) are deposited simultaneously, the resulting film will have a non-uniform composition.

[0043] Figure 14C is a schematic diagram of reactor head 1402 having a heterogeneous flow profile. Figure 14D is a 3D print photograph of reactor head 1402. In this embodiment, all precursor gas reactor channel openings, inert gas reactor channel openings, and exhaust reactor channel openings (or precursor gas modular components, inert gas modular components, and exhaust modular components) are incorporated into a single reactor head component for small-scale testing. In alternative embodiments, the reactor head may include multiple modular components having heterogeneous flow profiles. For this embodiment, reactor head 1402 was used to deliver diethylzinc with a heterogeneous flow profile and water with a uniform flow profile to the surface of a substrate to which they react to form zinc oxide (ZnO). Using chemical vapor deposition (CVD) conditions, the delivery of more diethylzinc to one side of the substrate resulted in a higher deposition rate and a heterogeneous film thickness. Figure 15 is a photograph of an example of a zinc oxide film with a thickness gradient produced using reactor head 1402 and deposited using different precursor gas flow rates. The film thickness gradient is clearly visible from band 1404, which forms an interference pattern. Figure 16A shows the film thickness measurements across the substrate of the thickness gradient film from Figure 15. Figure 16B shows a map of the film thickness on the surface of the same substrate. Reactor head 1402 can be used to simultaneously deliver another film component having a uniform flow profile, resulting in a film with a composition gradient in the first direction. A non-exclusive example of another film component is trimethylaluminum, which can react with water to form aluminum oxide, in which case the amount of zinc in the resulting aluminum-zinc-oxide alloy film will vary across the film or substrate.

[0044] Figure 17A shows a schematic diagram of an embodiment of a modular component 1700 including two symmetrical semi-parts 1702 and 1704. Figure 17B shows an exploded perspective view of the modular component 1700. Each semi-part 1702 and 1704 has a relief portion 1706 with a uniform depth, and each relief portion 1706 of each semi-part 1702 and 1704 is positioned to form a reactor channel when the two semi-parts 1702 and 1704 are assembled. The use of two symmetrical semi-parts 1702 and 1704 can simplify the design for manufacturing the modular component by enabling low-cost manufacturing of the modular component with a non-uniform flow profile using additive manufacturing or machining. The two symmetrical semi-parts 1702 and 1704 can be assembled to form a modular component 1700 with a reactor channel of uniform width to deliver a uniform flow profile. Alternatively, the depth of each relief portion 1706 can be modified by additive manufacturing or machining to provide a non-uniform depth (or other contour) for each relief portion 1706, such that when the two half portions 1702 and 1704 are combined, a reactor channel with non-uniform flow is formed. By combining this fabrication technique with modular reactor head technology, each individual reactor head component can be easily customized, installed, or swapped out for different functions and purposes, for example, to enable rapid prototyping or the deposition of films with thickness or composition gradients for different functions.

[0045] Although not required in all embodiments, the thin-film or thin-layer deposition systems of the present disclosure may include a substrate positioning system that controls the position of a substrate held by a substrate stage relative to a modular reactor head. For example, the substrate positioning system may be a linear motor positioning system that vibrates the substrate held by the substrate stage, thereby enabling high-throughput and high-precision deposition. A linear motor-based substrate positioning system can maintain the top surface of the substrate at a uniform height during motion, thereby enabling precise control of the space between the modular reactor head and the substrate when combined with the reactor positioning system.

[0046] Figure 18 is a perspective view of an embodiment of a substrate stage 1800 mounted on a linear motor system 1801, which is mounted on a heavy mass such as a granite slab 1802, to vibrate the substrate stage 1800 and the substrate beneath the modular reactor head. The substrate stage 1800 and the substrate may be substantially similar to the substrate stages 108 and 106. In one particular embodiment, the substrate stage 1800, including the upper plate 1808 and the vacuum reservoir 1810, is mounted on a linear motor system 1801, which is mounted on a polished granite slab to absorb vibrations caused by the motion of the moving stage. In an alternative embodiment, the linear motor system 1801 may be mounted on a surface having a large mass and high flatness.

[0047] The linear motor positioning system 1801 can also enable non-uniform film deposition by vibrating the substrate stage 1800 and the substrate at a varying travel distance. The vibratory approach allows this technique to create thickness and composition gradients in the direction of substrate vibration (direction 128 in Figure 2). In other words, by varying the travel distance during vibration, at least one of the film thickness and composition can vary in this direction.

[0048] Overall, the thin-film deposition system of this disclosure can deposit films in which compositional or thickness gradients can be generated across the film width using precursor gas reactor channel openings having customized geometric shapes. Different thickness or compositional gradients can be generated across the film width by varying the progression pattern of the heated substrate stage.

[0049] Figure 19 shows a flow diagram of method 1900 for depositing thin films with a modular reactor head.

[0050] In 1902, the substrate is loaded onto a substrate stage. The substrate stage may be part of a thin-film deposition system. The substrate stage may include a vacuum reservoir and multiple holes. In 1904, the substrate is secured to the substrate stage by suction from the vacuum reservoir. Suction may be provided to the substrate through multiple holes.

[0051] In 1906, the gap between the modular reactor head and the substrate is adjusted using a reactor head positioning system. The reactor head positioning system may be part of the thin-film deposition system. Adjusting the gap involves controlling the distance between the modular reactor head and the substrate.

[0052] In 1908, numerous precursors, including precursor gases, are delivered simultaneously and continuously to a modular reactor head. The numerous precursor gases pass through the modular reactor head by passing through their respective reactor channels and exiting their respective reactor channel openings, which are oriented toward the substrate. The position where each precursor gas contacts the substrate is determined by the position of each individual precursor gas modular component within the modular reactor head.

[0053] In 1910, the substrate vibrates under a modular reactor head, and material is deposited on the substrate by modular components, thereby forming a film. The substrate may vibrate in a substrate positioning system. The substrate positioning system may be part of the thin film deposition system.

[0054] If, in step 1912, the deposited film thickness is insufficient, the process returns to step 1910. If the film thickness is sufficient, in step 1914, the substrate is removed from the substrate stage.

[0055] Figure 20 shows a flow diagram of the roll-to-roll method 2000 for depositing thin films with a modular reactor head.

[0056] In 2002, a continuous web of substrate wound around a first roll is loaded onto a first roller and coupled to a second roll mounted on a second roller.

[0057] In 2004, the tension of the substrate between the first roller and the second roller is automatically adjusted. In 2006, the temperature of the substrate is adjusted. Temperature adjustment may include heating the substrate.

[0058] In 2008, the gap between the modular reactor head and the substrate is adjusted using a reactor head positioning system. The reactor head positioning system may be part of the thin-film deposition system. Adjusting the gap involves controlling the distance between the modular reactor head and the substrate.

[0059] In 2010, numerous precursors, including precursor gases, are delivered simultaneously and continuously to the modular reactor head. The numerous precursor gases pass through the modular reactor head by passing through their respective reactor channels and exiting their respective reactor channel openings, which are oriented toward the substrate. The position where each precursor gas contacts the substrate is determined by the position of each individual precursor gas modular component within the modular reactor head.

[0060] In 2012, the substrate is wound under the modular reactor head, and the material (such as a precursor gas) is deposited on the substrate, thereby forming a film. If the substrate is wound around a first roll, the substrate can be wound under the modular reactor head by winding the substrate from the first roll to a second roll. If the substrate is wound around a second roll, the substrate can be wound under the modular reactor head by winding the substrate from the second roll to a first roll.

[0061] In step 2014, if the deposited film thickness is insufficient, the method reverts to step 2012. If the film thickness is sufficient, in step 2016, the substrate web is unloaded.

[0062] In some embodiments, the present disclosure may relate to a modular reactor head that can be equipped with different components (such as heating channels, cooling channels, and plasma sources), and which can be arranged and positioned in various configurations, including, but not limited to, modular components for each component that controls the gas flow and provides the ability to switch between ALD system configurations and CVD system configurations, as well as a reactor head having adjustable position and height, cooling / heating channels for controlling the temperature of adjacent precursor gas slits to obtain desired thin film deposition conditions, plasma sources, and / or expandable reactor slits that can increase deposition throughput.

[0063] In another embodiment, the disclosure may relate to a system for positioning a reactor head relative to a substrate. The reactor head may be modular or non-modular. The system may further control the distance between the reactor head and the substrate, thus enabling switching between ALD mode and CVD mode.

[0064] In another embodiment, the disclosure may relate to a heated substrate stage having suction and / or local temperature control. In one embodiment, the heated substrate stage may include a vacuum holding mechanism capable of maintaining the geometry and thickness of any substrate. In another embodiment, the heated substrate stage may include an insulating material for the heated substrate stage from other system components.

[0065] In another embodiment, the disclosure may relate to a customizable precursor gas slit design that can generate a uniform or non-uniform flow profile from the slit, enabling the deposition of a film having a non-uniform thickness and / or composition perpendicular to the direction of substrate motion.

[0066] In further embodiments, the disclosure may relate to a linear motor positioning system that vibrates a substrate relative to a modular reactor head, which a) suppresses vibrations and maintains the substrate at a uniform height during those vibrations, thereby enabling precise control of the distance between the substrate and the modular reactor head, and / or b) enables the deposition of a film having non-uniform thickness and / or composition in the direction of the substrate's motion. This can be combined with a customizable precursor gas slit design to produce films with different thickness and composition gradients in orthogonal directions.

[0067] In yet another embodiment, the disclosure may relate to a number of deposition systems that may include roll-to-roll technology and / or substrate loading and unloading mechanisms for high-throughput generation.

[0068] In another embodiment, the disclosure may relate to a modular reactor head, for example, depositing a thin layer of material on a fabric having copper oxide ALD onto a nonwoven fabric for an N95 mask. Conventional spray or wet coating of copper oxide onto fabric typically fills pores in the fabric, which can affect the performance of the mask, whereas copper oxide CVD and / or ALD may provide an antiviral coating to masks that have a reduced effect on mask performance compared to conventional coating techniques.

[0069] While this disclosure has been illustrated and described herein with reference to preferred embodiments and specific examples thereof, it will be readily apparent to those skilled in the art that other embodiments and examples may perform similar functions and / or achieve similar results. All such equivalent embodiments and examples are within the spirit and scope of this disclosure.

[0070] The foregoing description includes numerous details for explanatory purposes and to provide a thorough understanding of the embodiments. However, it will be apparent to those skilled in the art that these specific details may not be necessary. In other cases, well-known structures may be shown in block diagram form to avoid obscuring the understanding. For example, specific details are not provided regarding whether the elements of the embodiments described herein are implemented as software routines, hardware circuits, firmware, or a combination thereof.

Claims

1. A modular reactor head used in conjunction with a thin-film deposition system, The aforementioned modular reactor head comprises a set of modular components, The set of modular components is adjacent to each other in a first direction within the reactor head, The set of modular components can be positioned relative to each other in a second direction, the second direction being substantially perpendicular to the first direction. The set of modular components includes at least two precursor gas modular components for depositing at least two precursor gases onto a substrate, The aforementioned at least two precursor gas modular components are separated by at least one other modular component. The at least one other modular component includes a temperature control modular component. The temperature control modular component comprises a modular reactor head, which includes a metal plate for controlling the temperature of a modular component adjacent to the temperature control modular component.

2. At least one of the modular components in the set of modular components is Reactor channels and Reactor channel opening and A modular reactor head according to claim 1, comprising:

3. The modular reactor head according to claim 2, wherein the shape of the reactor channel opening causes gaseous or liquid material to be delivered at one end of the reactor channel opening having a higher outlet velocity than at the opposite end of the reactor channel opening.

4. The modular reactor head according to claim 1, wherein the temperature control modular component comprises a reactor channel for receiving either a cooling liquid for cooling the metal plate or a heating liquid for heating the metal plate.

5. The modular reactor head according to claim 1, wherein multiple modular components from the set of modular components are mounted at a predetermined height relative to each other.

6. A thin film deposition system, wherein the thin film deposition system is A substrate stage for supporting the substrate, A modular reactor head for depositing a thin film on the substrate and Equipped with, The modular reactor head includes a set of modular components, The set of modular components is adjacent to each other in a first direction within the reactor head, The set of modular components can be positioned relative to each other in a second direction, the second direction being substantially perpendicular to the first direction. The set of modular components includes at least two precursor gas modular components for depositing at least two precursor gases onto a substrate, The aforementioned at least two precursor gas modular components are separated by at least one other modular component. The at least one other modular component includes at least one of the following: a precursor fluid component, an exhaust modular component, an inert gas modular component, a temperature control modular component, a chemical modular component, a cleaning modular component, and a plasma source modular component. The thin film deposition system further comprises a modular reactor head positioning system for positioning the modular reactor head relative to the substrate on the substrate stage, The substrate stage is a thin film deposition system equipped with a linear motor system.

7. The thin film deposition system according to claim 6, wherein the modular reactor head positioning system comprises a linear displacement system.

8. The linear displacement system is, A set of displacement measuring devices, A set of linear actuators and The thin film deposition system according to claim 7, comprising:

9. The thin film deposition system according to claim 6, wherein the modular reactor head positioning system is configured to control the gap between the modular reactor head and the substrate stage.

10. The thin film deposition system is The thin film deposition system according to claim 6, further comprising a vacuum system for holding the substrate relative to the substrate stage.

11. The aforementioned substrate stage is An upper plate for supporting the aforementioned substrate, Heating components for heating the upper plate and The thin film deposition system according to claim 6, comprising:

12. A modular reactor head used in conjunction with a thin film deposition system, The aforementioned modular reactor head comprises a set of modular components, The set of modular components is adjacent to each other in a first direction within the reactor head, The set of modular components can be positioned relative to each other in a second direction, the second direction being substantially perpendicular to the first direction. The set of modular components includes at least two precursor gas modular components for depositing at least two precursor gases onto a substrate, The aforementioned at least two precursor gas modular components are separated by at least one other modular component. The at least one other modular component includes a precursor fluid component, The precursor fluid component is a modular reactor head equipped with an actuator for controlling the deposition of the precursor fluid.

Images