Methods and systems for depositing a layer and methods for forming a layer on a substrate

Abstract

The described invention pertains to systems and related methods for depositing materials. The system allows a precursor to be condensed or deposited onto a substrate, followed by curing of the condensed or deposited precursor to form a layer.

Description

Technical Field

[0001] This disclosure generally relates to systems and methods applicable to depositing layers on substrates. Prior Technology

[0002] Vapor deposition processes are widely used in semiconductor device manufacturing. Various deposition processes require the deposition of materials. This is true, for example, in processes used to fill recesses, trenches, or gaps in a substrate. Other processes involving the deposition of dielectric materials include those for dielectric materials. However, depositing various materials remains challenging, especially when trade-offs need to be struck between repeatability, layer quality, and process speed. Therefore, there is a continued need for improved methods and apparatus for material deposition.

[0003] Any discussion presented in this section, including discussions of problems and solutions, is included in this disclosure solely for the purpose of providing background context. Such discussion should not be construed as an admission that any or all of the information was known at the time of completion of this invention or otherwise constituted prior art. Summary of the Invention

[0004] The present invention can be presented in a simplified form to describe a series of concepts that are further described in detail below. The present invention is not intended to necessarily identify the key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0005] This document describes a system comprising a reaction chamber, a precursor source, a gas injection system, and a curing unit. The reaction chamber includes a substrate support, which in turn includes a substrate cooling unit. The precursor source is configured to introduce a precursor into the reaction chamber via the gas injection system, which is fluidly connected to the reaction chamber. The precursor source includes a precursor source heater. The gas injection system heater is configured to heat the gas injection system.

[0006] In some embodiments, the gas injection system includes a spray head injector. In such embodiments, the spray head injector includes a spray head injector heater.

[0007] In some embodiments, the curing unit includes a lower electrode and an upper electrode. The lower electrode is contained in a substrate support. The upper electrode is contained in a spray head injector. In such embodiments, the system further includes a radio frequency (RF) power source configured to generate an RF power waveform. The RF power source is electrically connected to one of the lower and upper electrodes.

[0008] In some embodiments, the curing unit includes an infrared source.

[0009] In some embodiments, the curing unit includes a UV source.

[0010] In some embodiments, the curing unit includes a microwave source.

[0011] In some embodiments, the curing unit includes a remote plasma source.

[0012] In some embodiments, one or more grid plates are positioned between the distal plasma source and the substrate support.

[0013] In some embodiments, the system further includes a controller. The controller includes a gas flow control unit, a precursor source temperature control unit, a gas injection system temperature control unit, a substrate support temperature control unit, and a curing unit control unit. The gas flow control unit is configured to control the gas flow into the gas injection system. The precursor source temperature control unit is configured to maintain the precursor source at a predetermined precursor source temperature. The gas injection system temperature control unit is configured to maintain the gas injection system at a predetermined gas injection system temperature. The gas injection system temperature is higher than the precursor source temperature. The substrate support temperature control unit is configured to maintain the substrate support at a predetermined substrate support temperature. The substrate support temperature is lower than the precursor source temperature. The curing unit control unit is configured to control the operation of the curing unit, i.e., its functional operation.

[0014] In some embodiments, the system further includes a substrate heating unit. In some embodiments, the substrate heating unit is included in a substrate support.

[0015] This document further describes a method for forming a layer on a substrate. The method includes a step of providing a system comprising a precursor source. The system further comprises a gas injection system, a reaction chamber, and a curing unit. The precursor source comprises a precursor. The reaction chamber comprises a substrate support. The method further comprises maintaining the precursor source at a precursor source temperature and maintaining the gas injection system at a gas injection system temperature. The gas injection system temperature is higher than the precursor source temperature. The method further comprises maintaining the substrate support at a substrate support temperature. The substrate support temperature is lower than the precursor source temperature. The method further comprises positioning a substrate on the substrate support. Then, the method comprises providing a precursor to the reaction chamber. It should be understood that the precursor is provided from the precursor source and via the gas injection system to the reaction chamber. Therefore, the precursor is condensed or deposited on the substrate to form a condensed or deposited precursor. Then, the method comprises curing the condensed or deposited precursor by means of the curing unit.

[0016] In some embodiments, the gas injection system includes a spray head injector. The spray head injector includes a spray head injector heater. In such embodiments, the method further includes maintaining the spray head injector at a spray head injector temperature by means of the spray head injector heater. It should be understood that the spray head injector temperature is higher than or equal to the gas injection system temperature.

[0017] In some embodiments, the curing unit includes a lower electrode and an upper electrode. The lower electrode is contained in a substrate support. The upper electrode is contained in a spray head injector. In such embodiments, the curing unit further includes a radio frequency (RF) power source configured to generate an RF power waveform. The RF power source is electrically connected to one of the lower and upper electrodes. Furthermore, in such embodiments, the curing process involves condensing or depositing a precursor to form a plasma between the upper and lower electrodes.

[0018] In some embodiments, the curing unit includes an infrared source. In such embodiments, curing a condensed or deposited precursor involves exposing the precursor to infrared radiation.

[0019] In some embodiments, the curing unit includes an ultraviolet radiation source. In such embodiments, curing a condensed or deposited precursor involves exposing the precursor to ultraviolet radiation.

[0020] In some embodiments, the curing unit includes a remote plasma source. In such embodiments, curing a condensed or deposited precursor involves exposing the condensed or deposited precursor to one or more activated species.

[0021] In some embodiments, the curing unit includes a distal plasma source, one or more grid plates positioned between the distal plasma source and a substrate support, and curing the condensed or deposited precursor includes exposing the precursor to free radicals.

[0022] In some embodiments, the precursor comprises a boron precursor, and curing the condensed or deposited precursor comprises exposing the precursor to a reactant.

[0023] In some embodiments, the method includes performing a plurality of deposition cycles. A deposition cycle includes a precursor pulse and a curing pulse. The precursor pulse includes providing a precursor to a reaction chamber. The curing pulse includes curing the condensed or deposited precursor.

[0024] In some embodiments, the cured precursor further includes providing a reactant to the reaction chamber.

[0025] This document further describes a method for forming a layer on a substrate. The method includes the step of providing a system comprising a first precursor source containing a first precursor, a second precursor source containing a second precursor, a gas injection system, a reaction chamber containing a substrate support, and a curing unit. The method further includes maintaining the first precursor source at a first precursor source temperature. The method further includes maintaining the second precursor source at a second precursor source temperature. The method further includes maintaining the gas injection system at a gas injection system temperature. The gas injection system temperature is higher than the first precursor source temperature. The gas injection system temperature is higher than the second precursor source temperature. The method further includes maintaining the substrate support at a substrate support temperature. The substrate support temperature is lower than the first precursor source temperature. The substrate support temperature is lower than the second precursor source temperature. The method further includes positioning a substrate on the substrate support. The method further includes performing one or more first cycles. A first cycle includes providing the first precursor from the first precursor source to the reaction chamber via the gas injection system. Therefore, the first precursor is condensed or deposited on a substrate to form a condensed or deposited first precursor. A first cycle further includes curing the condensed or deposited first precursor by a curing unit. The method further includes performing one or more second cycles. A second cycle includes supplying a second precursor from a second precursor source to a reaction chamber via a gas injection system. Therefore, the second precursor is condensed or deposited on a substrate to form a condensed or deposited second precursor. Then, the condensed or deposited second precursor is cured by a curing unit.

[0026] In some embodiments, the method includes two or more superloops. A superloop includes executing one or more first loops and executing one or more second loops.

[0027] In some embodiments, the methods employed herein are implemented in systems as described herein.

[0028] Those skilled in the art will readily understand these and other embodiments from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any of the specific embodiments disclosed. Simple Explanation of the Diagram

[0029] A more complete understanding of the embodiments disclosed herein can be obtained by considering the following illustrative drawings, with reference to the implementation methods and the claims. Figure 1 shows an embodiment of the system (100) as disclosed herein. Figure 2 shows another embodiment of the system (200) as disclosed herein. Figure 3 shows another embodiment of the system (300) as disclosed herein. Figure 4 illustrates an embodiment of a method for forming a layer on a substrate as described herein. Figure 5 illustrates another embodiment of a method for forming a layer on a substrate as described herein. Figure 6 shows an embodiment of the controller (600) used in the system as described herein. It will be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, some elements in the drawings may be enlarged relative to other elements to help improve understanding of the embodiments illustrated in this disclosure. Implementation

[0030] The illustrative descriptions of the methods, structures, apparatuses, and systems provided below are merely illustrative and intended for purposes of explanation only; the following descriptions are not intended to limit the scope of this disclosure or the claims. Furthermore, the listing of multiple embodiments having the stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. For example, various embodiments are presented as illustrative examples and may be enumerated in the appendix. Unless otherwise noted, the illustrative embodiments or their components may be combined or used separately.

[0031] The methods and related systems described herein are for example, for depositing materials in a repeatable manner.

[0032] In some embodiments, "gas" may include materials that are gaseous at ambient temperature and atmospheric pressure (NTP), vaporized solids, and / or vaporized liquids, and may consist of a single gas or a mixture of gases depending on the context. Gases other than process gases (i.e., gases introduced without passing through gas distribution equipment, other gas distribution devices, or the like) may be used, for example, to seal the reaction space, and may include a sealing gas (such as a rare gas). In some cases, the term "precursor" may refer to a compound that participates in a chemical reaction to produce another compound, and particularly to a compound that constitutes one of the main components of the membrane matrix or membrane; the term "reactant" may be used interchangeably with the term "precursor." Alternatively, "reactant" may refer to a compound that reacts with the substrate surface to form a volatile reaction product. Thus, "reactant" can be used in deposition processes or etching processes, or both.

[0033] In some embodiments, "substrate" can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films can be formed. The substrate may include a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (such as germanium), or other semiconductor materials (such as group II-VI or III-V semiconductor materials), and may include one or more layers overlying or underlying the bulk material. Further, the substrate may include various features, such as recesses, protrusions, and the like formed within or on at least a portion of a layer of the substrate. As an example, the substrate may include a bulk semiconductor material and an insulating or dielectric material layer overlying at least a portion of the bulk semiconductor material. Exemplary substrates include wafers (such as silicon wafers), such as 200 mm, 300 mm, or 450 mm wafers.

[0034] In some embodiments, "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers, partial or complete atomic layers, atomic and / or molecular clusters, or layers composed of separate atoms and / or molecules. Films or layers may contain materials or layers with pinholes, which may be continuous or discontinuous.

[0035] In some embodiments, a “cyclic deposition process” or “cyclical deposition process” may refer to the sequential introduction of multiple precursors (and / or reactants) into a reaction chamber to deposit a layer over a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and a hybrid cyclic deposition process including an ALD component and a cyclic CVD component.

[0036] In some embodiments, "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle is performed in a process chamber, and generally refers to a plurality of consecutive deposition cycles. When performed with alternating pulses of precursor / reactive gases and flushing (e.g., inert carrier) gases, the term "atomic layer deposition" as used herein also means to include processes specified by related terms, such as: chemical vapor deposition, atomic layer epitaxy, molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy.

[0037] As used herein, "dew point" refers to the temperature at which the precursor condenses, that is, the temperature at which the precursor changes from a gaseous phase to a liquid phase. Those skilled in the art will understand that the dew point of a precursor depends on pressure. Therefore, it should be understood that when the term "dew point" is used herein, it refers to the dew point of the precursor at the pressure in the reaction chamber.

[0038] Furthermore, in this disclosure, any two numbers of a variable may constitute the working range of the variable, and any indicated range may include or exclude endpoints. Additionally, any numerical value of the indicated variable (whether or not it is indicated by "about") may refer to an exact value or an approximate value and include equivalent values, and may refer to an average, median, representative value, multi-value, or similar. Furthermore, in this disclosure, the term "comprising" indicates that the referred embodiment includes those features, but does not exclude the presence of other features, provided that they do not render the corresponding embodiment inoperable. On the other hand, "consisting of" indicates that the embodiment of interest does not have any further features other than those following the wording, except for optional further features that do not substantially affect the essential characteristics of the corresponding embodiment. It should be understood that the term "comprising" includes the meaning of "consisting of".

[0039] This document describes a system for depositing a single layer. The system includes a reaction chamber with a substrate support, a substrate cooling unit, a precursor source, a precursor source heater, a gas injection system, a gas injection system heater, and a curing unit.

[0040] The reaction chamber includes a substrate support. The substrate support suitably provides mechanical support to the substrate during the deposition process. Suitable substrates include semiconductor wafers, such as silicon wafers, including p-type silicon wafers. The substrate can have any size. An exemplary substrate is circular and has a diameter of 200 mm, 300 mm, or 450 mm.

[0041] The substrate support includes a substrate cooling unit. During normal operation, the substrate can be heated to the desired process temperature by means of heated process gases and / or heat from the gas injection system and / or precursor sources. Therefore, a substrate heater is not strictly necessary. However, in some embodiments, the substrate support further includes a substrate heater. Accordingly, the substrate can be rapidly heated to the desired process temperature. Once the substrate is at that process temperature, a substrate cooler can be used to ensure that the substrate temperature does not exceed the desired process temperature.

[0042] Suitable substrate coolers include various heat exchangers known in the art. For example, a substrate cooler may include a meandering conduit containing cooling fluid, the conduit being housed within a substrate support. Alternatively or additionally, a substrate cooler may include a network of interconnecting cooling conduits, the network being housed within the substrate support. Alternatively or additionally, a substrate cooler may include a Peltier cooling element.

[0043] In some embodiments, the system is configured to maintain the substrate at a temperature of at least -75°C to at most 600°C, or at least 0°C to at most 400°C, or at least 25°C to at most 200°C, or at least 50°C to at most 100°C.

[0044] The precursor source is configured to provide a precursor and, optionally, a carrier gas. A gas injection system is fluidly connected to both the precursor source and the reaction chamber. The gas injection system is configured to provide the precursor from the precursor source and, optionally, the carrier gas to the reaction chamber. The precursor source includes a precursor source heater, which can be suitably configured during normal use to maintain the precursor source at a predetermined temperature, i.e., a predetermined precursor source temperature.

[0045] As previously described, the gas injection system is configured to provide a precursor from a precursor source and optionally a carrier gas to the reaction chamber. The gas injection system includes a gas injection system heater. The gas injection system heater is configured to heat the gas injection system.

[0046] In some embodiments, a suitable gas injection system includes one or more pipes and / or gas manifolds. The gas injection system may include, for example, an insulating heating jacket surrounding one or more pipes and / or gas manifolds. The heating jacket may include, for example, a resistance heater and / or pipes containing a heating fluid.

[0047] In some embodiments, the gas injection system includes one or more heated gas lines. In some embodiments, the heated gas lines are heated to a temperature below the temperature of the spray head injectors included in the system and above the temperature of the substrate support. In some embodiments, the heated gas lines are heated to a temperature higher than the temperature of the precursor source included in the system. In some embodiments, the heated gas lines are heated to a temperature ranging from at least 50°C to at most 1000°C, or to a temperature ranging from at least 100°C to at most 600°C, or to a temperature ranging from at least 150°C to at most 400°C, for example, to a temperature of 200°C. Heating of the heated gas lines may be achieved, for example, by means of a heating mantle, such as a resistance heating mantle.

[0048] In some embodiments, the gas injection system includes a spray head injector. The spray head injector may be suitably configured parallel to a substrate support. The spray head injector includes a spray head injector heater. In some embodiments, the spray head injector heater includes a plurality of tubes containing heated fluid. Additionally or alternatively, the spray head injector heater may include a resistance heater in some embodiments.

[0049] The system further includes a curing unit. The curing unit can be advantageously used for solidifying and / or densifying condensed or deposited precursors on substrates. Various types of curing units can be employed.

[0050] In some embodiments, the curing unit includes a lower electrode, an upper electrode, and an RF power source. The lower electrode may be suitably included in a substrate support. The upper electrode may be suitably located in a spray head injector as described herein. Alternatively, the spray head injector or a portion thereof may function as the upper electrode. The RF power source is configured to generate an RF power waveform and is electrically connected to one of the lower and upper electrodes. It should be understood that electrodes not electrically connected to the RF power source are electrically grounded via a ground. Therefore, in some embodiments, the lower electrode is grounded, while the RF power source is electrically connected to the upper electrode. Alternatively, the lower electrode may be electrically connected to the RF power source, while the upper electrode may be grounded.

[0051] In some embodiments, the curing unit includes an infrared source. The infrared source may, for example, include an infrared lamp disposed outside the reaction chamber, the infrared lamp being directly opposite the substrate in a straight line of sight through a window in the reaction chamber wall. It should be understood that the window is at least partially transparent to infrared light. Suitably, the window may be heated, for example, by resistance heating. Alternatively, the window may be heated by the infrared source. Heating the window advantageously prevents precursor condensation on the window.

[0052] In some embodiments, the curing unit includes a UV source, i.e., an ultraviolet source. An infrared source may, for example, include an ultraviolet lamp disposed outside the reaction chamber, the ultraviolet lamp being directly opposite the substrate in a straight line of sight through a window in the reaction chamber wall. It should be understood that the window is at least partially transparent to ultraviolet light. Suitably, the window may be heated, for example, by resistance heating. Alternatively, the window may be heated by a UV source. Heating the window advantageously prevents precursor condensation on the window.

[0053] In some embodiments, the curing unit includes a distal plasma source. The distal plasma source may, for example, include any of a microwave plasma source, a capacitively coupled plasma source, and an inductively coupled plasma source. Suitably, the distal plasma source may be located outside the reaction chamber. Alternatively, the distal plasma source may be located inside the reaction chamber. Optionally, one or more mesh plates are positioned between the distal plasma source and the substrate support.

[0054] In some embodiments, the curing unit includes a microwave source. Therefore, in some embodiments, the method described herein may include curing a condensed or deposited precursor using a microwave source. The microwave source may be located, for example, inside or outside the reaction chamber. It should be understood that when the microwave source is located outside the reaction chamber, the microwave source is suitably operatively connected to the reaction chamber via a microwave waveguide.

[0055] In some embodiments, the system further includes an exhaust manifold for removing unused reactants and / or reaction products from the reaction chamber. The exhaust manifold may suitably be fluidly connected to a gas venting component (such as a pump, e.g., a turbopump, and / or a condensate trap). The system described herein may or may not include a gas venting component.

[0056] In some embodiments, the system further includes a wall heater. Therefore, the walls of the reaction chamber can be heated, and the viscosity coefficient of the gas on the reactor walls can be controlled, preventing or reducing precursor deposition or condensation on the reaction chamber walls. Any chamber wall heater can be used, including but not limited to wall heaters comprising one or more resistance heating elements, or wall heaters comprising one or more pipes containing heating fluid. In some embodiments, the walls of the reaction chamber can be heated to temperatures ranging from at least 50°C to at most 1000°C, or to temperatures ranging from at least 100°C to at most 800°C, or to temperatures ranging from at least 400°C to at most 700°C, such as to 600°C, such as to 500°C. Therefore, the temperature of the reaction chamber walls can be effectively controlled, and necessarily the viscosity coefficient of the gases used in the reaction chamber (such as precursors or reactants) can also be controlled.

[0057] In some embodiments, the reaction chamber is insulated, for example, by double-wall insulation. Reaction chamber insulation can advantageously improve temperature control within the reaction chamber. Additionally or alternatively, reaction chamber insulation can reduce heat loss to the environment. In some embodiments, the outer surface of the reaction chamber can be cooled by a cooling jacket (e.g., a water-containing cooling jacket).

[0058] In some embodiments, the system described herein may further include a loading lock and / or a wafer handling system. Accordingly, when a wafer (e.g., a semiconductor wafer, such as a silicon wafer) is used as a substrate, the substrate can be efficiently and optionally automatically moved from the loading station (i.e., the loading lock) to the reaction chamber.

[0059] In some embodiments, the system further includes an outer shell surrounding the reaction chamber. The outer shell may contain, for example, a heat-resistant material, such as steel.

[0060] In some embodiments, the system further includes a controller comprising a gas flow control unit, a precursor source temperature control unit, a gas injection system temperature control unit, a substrate support temperature control unit, and a curing unit control unit. The curing unit control unit is configured to control the operation of the curing unit. The gas flow control unit is configured to control the gas flow into the gas injection system. The precursor source temperature control unit is configured to maintain the precursor source at a predetermined precursor source temperature. The gas injection temperature control unit is configured to maintain the gas injection system at a predetermined injection system temperature. The gas injection system temperature is higher than the precursor source temperature. The substrate support temperature control unit is configured to maintain the substrate support at a predetermined substrate support temperature. The substrate support temperature is lower than the precursor source temperature. The curing unit control unit may suitably control a switching mechanism for shutting down the curing unit during the step of depositing or condensing the precursor on the substrate, and for opening the curing unit during the curing step.

[0061] In some embodiments, the substrate support temperature is below the dew point of the precursor at the reaction chamber pressure. Therefore, a liquid precursor phase can be formed on the substrate support. Forming a liquid phase can be particularly advantageous for filling narrow gaps or recesses.

[0062] In some embodiments, the substrate support is above the dew point of the precursor at the reaction chamber pressure, or the reaction chamber is at a pressure where no liquid precursor phase forms, such as at a very low pressure. In such embodiments, the precursor may form a solid phase on a substrate positioned on a cooled substrate support. That solid phase may then be cured as described elsewhere herein.

[0063] A controller may include modules, such as software or hardware components, like FPGAs or ASICs, that perform certain tasks. It should be understood that where a controller includes a software component performing a particular task, the controller is programmed to perform that specific task. Modules can advantageously be configured to reside on addressable storage media (i.e., memory) of the controller and can be configured to control, for example, any specific function of the system.

[0064] This document further describes a method for depositing a layer on a substrate. The method includes providing a system, such as the system described herein. The system includes a precursor source. The precursor source includes a precursor. The system further includes a gas injection system, a reaction chamber, and a curing unit. The reaction chamber includes a substrate support. The method further includes maintaining the precursor source at a predetermined precursor source temperature, maintaining the gas injection system at a predetermined gas injection system temperature, and maintaining the substrate support at a predetermined substrate support temperature. The gas injection system temperature is higher than the predetermined source temperature, and the substrate support temperature is lower than the predetermined precursor source temperature. The method further includes positioning a substrate on the substrate support. The method further includes providing the precursor from the precursor source to the reaction chamber via the gas injection system. Optionally, the precursor is introduced into the reaction chamber by a carrier gas. Depending on the precursor involved and depending on the pressure in the reaction chamber, the precursor is condensed or deposited onto the substrate. The condensed or deposited precursor is then cured. Advantageously, the method described herein allows for the deposition of very thin layers. Furthermore, these methods allow for precise thickness control of the layers.

[0065] In some embodiments, the step of condensing or depositing the precursor onto the substrate includes closing the inlet valve included in the gas injection system and the outlet valve included in the exhaust of the reaction chamber. Therefore, for the introduction of the precursor into the reaction chamber, a time period (e.g., from at least 0.1 seconds to at most 20 seconds) can be given for condensation or deposition onto the substrate without allowing the precursor to flow into and out of the reaction chamber, thereby minimizing precursor consumption.

[0066] In some embodiments, the method includes maintaining the reaction chamber at a predetermined reaction chamber pressure.

[0067] In some embodiments, the reaction chamber pressure is sufficiently high and the substrate support temperature is sufficiently low to allow the precursor to form a condensed liquid phase on the substrate. Those skilled in the art will understand that the precise temperature and pressure at which these conditions occur depend on the precursor used and are readily determined in practice. Therefore, in some embodiments, the precursor has a dew point at the reaction chamber pressure that is lower than the precursor source temperature and higher than the substrate support temperature. Accordingly, the precursor condenses on the substrate to form a condensed precursor. The condensed precursor is a liquid.

[0068] In some embodiments, the reaction chamber pressure is sufficiently low and the substrate support temperature is sufficiently high to allow the precursor to transition directly from a gaseous phase to a solid phase. In such embodiments, the precursor is deposited on the substrate to form a deposited precursor. The deposited precursor is a solid. Those skilled in the art will understand that the precise temperature and pressure at which these conditions occur depend on the precursor used and are readily determined in practice.

[0069] In some embodiments, the substrate support temperature is from at least -20°C to at most 40°C, the precursor source temperature is from at least 10°C to at most 100°C, and the gas injection system temperature is between at least 30°C and at most 150°C, provided that the substrate support temperature is lower than the precursor source temperature and the precursor source temperature is lower than the gas injection system temperature.

[0070] In some embodiments, the substrate support temperature is at least 1°C lower than the precursor source temperature. In some embodiments, the substrate support temperature is at least 2°C lower than the precursor source temperature. In some embodiments, the substrate support temperature is at least 5°C lower than the precursor source temperature. In some embodiments, the substrate support temperature is at least 10°C lower than the precursor source temperature. In some embodiments, the substrate support temperature is at least 20°C lower than the precursor source temperature. In some embodiments, the substrate support temperature is at least 50°C lower than the precursor source temperature.

[0071] In some embodiments, the precursor source temperature is at least 1°C lower than the gas injection system temperature. In some embodiments, the precursor source temperature is at least 2°C lower than the gas injection system temperature. In some embodiments, the precursor source temperature is at least 5°C lower than the gas injection system temperature. In some embodiments, the precursor source temperature is at least 10°C lower than the gas injection system temperature. In some embodiments, the precursor source temperature is at least 20°C lower than the gas injection system temperature. In some embodiments, the precursor source temperature is at least 50°C lower than the gas injection system temperature.

[0072] In some embodiments, the temperature of the gas injection system increases continuously from the precursor source to the reaction chamber. In other words, there may be a temperature gradient in the gas injection system. It should be understood that in such embodiments, the term "gas injection system temperature" refers to a temperature range spanning from the lowest temperature of the gas injection system to the highest temperature of the gas injection system.

[0073] In some embodiments, the method employs a system in which a gas injection system includes a spray head injector. In some embodiments, the spray head injector may be configured to be substantially parallel to a substrate support. The spray head injector includes a spray head injector heater. In such embodiments, the method further includes maintaining the spray head injector at a spray head injector temperature by means of the spray head injector heater. The spray head injector heater can maintain the spray head injector at a spray head injector temperature, where the spray head injection gas temperature may be higher than or equal to the gas injection system temperature. In some embodiments, the gas injection system temperature gradually increases from a precursor source temperature near the precursor source to a spray head injector temperature near the spray head injector.

[0074] In some embodiments, the curing unit includes a lower electrode and an upper electrode. The lower electrode is contained in a substrate support. The upper electrode is contained in a spray head injector. In such embodiments, the curing unit further includes a radio frequency (RF) power source configured to generate an RF power waveform. The RF power source is electrically connected to one of the lower and upper electrodes. It should be understood that the electrode not electrically connected to the RF power source is electrically grounded. In such embodiments, curing the condensed or deposited precursor involves generating a plasma, i.e., a capacitively coupled plasma, between the upper and lower electrodes.

[0075] In some embodiments, plasma is continuously generated in the reaction chamber. Alternatively, the plasma may be a pulsed plasma, comprising a sequence of pulses for plasma on and off. In other words, the plasma may be an intermittent plasma.

[0076] It should be understood that plasma generation in the reaction chamber involves supplying plasma gas to the reaction chamber. Suitable plasma gases include nitrogen, hydrogen, rare gases such as He, Ne, and Ar; and mixtures thereof.

[0077] In some embodiments, the curing unit includes an infrared source. In such embodiments, curing a condensed or deposited precursor involves exposing the precursor to infrared radiation.

[0078] In some embodiments, the curing unit includes an ultraviolet (UV) radiation source. In such embodiments, curing a condensed or deposited precursor involves exposing the precursor to ultraviolet radiation.

[0079] In some embodiments, the substrate is exposed to a curing atmosphere, in other words, a curing gas, during exposure to infrared or ultraviolet radiation. Suitable curing atmospheres include nitrogen, hydrogen, rare gases such as He, Ne, and Ar; and mixtures thereof.

[0080] In some embodiments, the curing unit includes a remote plasma source. In such embodiments, curing a condensed or deposited precursor involves exposing the precursor to one or more excited species. Examples of excited species include electromagnetic radiation, ions, and free radicals.

[0081] In some embodiments, the curing unit includes a distal plasma source, and one or more grid plates are positioned between the distal plasma source and a substrate support. In such embodiments, electromagnetic radiation and ions can advantageously be at least partially blocked by the one or more grid plates, while free radicals can pass through relatively unimpeded. Therefore, in such embodiments, curing the condensed or deposited precursor involves exposing the precursor to free radicals.

[0082] Remote plasma can be generated using any suitable plasma gas. Suitable plasma gases include nitrogen, hydrogen, rare gases such as He, Ne, and Ar; and mixtures thereof.

[0083] In some embodiments, the curing unit includes a microwave source. In such embodiments, curing a condensed or deposited precursor involves exposing the condensed or deposited precursor to microwave energy.

[0084] In some embodiments, the precursor comprises a boron precursor. Therefore, a boron-containing layer can be formed on the substrate.

[0085] In some embodiments, the boron precursor comprises boron and nitrogen. In some embodiments, the boron precursor comprises boron, nitrogen, and hydrogen.

[0086] In some embodiments, the precursor may be represented by a chemical formula according to formula (i).

[0087] (i)

[0088] R1, R2, R3, R4, R5, and R6 are each independently selected from H, NH2, alkyl groups, and halogens.

[0089] In some embodiments, at least one of R1, R2, R3, R4, R5, and R6 is F or Cl.

[0090] In some embodiments, the precursor is borazine.

[0091] In some embodiments, the precursor comprises a boron precursor, and curing the precursor comprises exposing the condensed or deposited precursor to the reactants. In some embodiments, the reactants contain nitrogen. Additionally or alternatively, the reactants may contain rare gases. Exposing the condensed or deposited precursor to the reactants can advantageously be done simultaneously with exposing the substrate to direct plasma, simultaneously with exposing the substrate to reactive species, simultaneously with exposing the substrate to free radicals, simultaneously with exposing the substrate to ultraviolet (UV) radiation, and / or simultaneously with exposing the substrate to infrared (IR) radiation.

[0092] In some embodiments, the boron precursor comprises a boron halide. For example, the boron precursor may be selected from boron chloride, boron bromide, and boron iodide.

[0093] In some embodiments, the boron precursor comprises a borohydride. Suitable borohydrides include diborane and decaborane.

[0094] In some embodiments, the boron precursor comprises an organoboron, i.e., a compound comprising boron, carbon, and hydrogen. Suitable organoboron compounds include triethylborane.

[0095] In some embodiments, the boron precursor comprises an alkylaminoborane. Suitable alkylaminoboranes include tris(methylamino)borane.

[0096] In some embodiments, the boron precursor comprises boraneammonium (NH3·BH3).

[0097] In some embodiments, the precursor comprises a boron precursor and a silicon precursor. Therefore, in some embodiments, both the boron precursor and the silicon precursor are condensed or deposited on the substrate. In some embodiments, the silicon precursor comprises a silicon halide. In some embodiments, the silicon halide comprises silicon, hydrogen, and fluorine. In some embodiments, the silicon halide comprises silicon, hydrogen, and chlorine. In some embodiments, the silicon halide comprises silicon, hydrogen, and bromine. In some embodiments, the silicon halide comprises silicon, hydrogen, and iodine. In some embodiments, the silicon halide is selected from tetrachlorosilane, diiodosilane, and tetraiodosilane. Therefore, a layer comprising silicon and boron can be formed on the substrate. In some embodiments,

[0098] In some embodiments, the precursor comprises a boron precursor and a silicon precursor, wherein the boron precursor comprises boron and nitrogen. For example, the precursor may comprise boronazynylene or an alkyl-substituted derivative thereof. In such embodiments, a silicon-doped boron nitride layer may be formed on the substrate by first depositing or condensing the silicon and boron precursors on the substrate, and then curing the silicon and boron precursors.

[0099] In some embodiments, the precursors comprise a boron precursor and a silicon precursor, the boron precursor comprising boron and a halide, and the silicon precursor comprising silicon and a halide, and the curing step comprises generating a nitrogen-containing plasma in a reaction chamber. Thus, a silicon-doped boron nitride layer can be formed on a substrate. In one exemplary embodiment, the boron precursor comprises BBr3, the silicon precursor comprises SiI2H2, and generating the direct nitrogen-containing plasma in the reaction chamber comprises providing N2 and optionally H2 to the reaction chamber.

[0100] In some embodiments, curing a condensed or deposited precursor by a curing unit includes providing a reactant to a reaction chamber. In some embodiments, the reactant contains silicon. In some embodiments, the reactant contains a silicon halide, such as at least one of a silicon- and fluorine-containing compound, a silicon- and chlorine-containing compound, and a silicon- and bromine-containing compound. In some embodiments, the silicon halide is selected from tetrachlorosilane and tetraiodosilane. In some embodiments, the silicon halide contains a compound selected from SiH3Cl, SiH2Cl2, SiH3Cl, and SiCl4. In some embodiments, the silicon halide contains a compound selected from SiBr4, SiHBr3, SiH2Br2, SiH3Br, and SiBr4. In some embodiments, the silicon halide contains a compound selected from SiH3I, SiH2I2, SiH3I, and SiI4. Therefore, a silicon-containing layer, such as a silicon-doped boron nitride layer, can be formed on a substrate.

[0101] In some embodiments, the methods described herein include a plurality of deposition cycles. A deposition cycle includes a precursor pulse and a curing pulse. The precursor pulse includes providing a precursor to a reaction chamber as described herein. The curing pulse includes curing the condensed or deposited precursor as described herein. Optionally, the precursor pulse and the curing pulse are separated by an intra-cycle rinse. Additionally or alternatively, in some embodiments, subsequent cycles may be separated by an inter-cycle rinse.

[0102] In some embodiments, the method includes heating the walls of the reaction chamber using a reaction chamber wall heater. This allows control of the gas adhesion coefficient on the reactor walls and avoids or reduces precursor deposition or condensation on the reaction chamber walls. Any wall heater can be used, including, but not limited to, wall heaters comprising one or more resistance heating elements, or wall heaters comprising one or more pipes containing heating fluid.

[0103] In some embodiments, the reaction chamber is maintained at a pressure of at least 1.10-11 mbar to at most 1 bar, or at least 1.10-10 mbar to at most 1.10-1 bar, or at least 1.10-9 mbar to at most 1 mbar, or at least 1.10-8 mbar to at most 1.10-2 mbar, or at least 1.10-7 mbar to at most 1.10-4 mbar.

[0104] Figure 1 shows an embodiment of the system (100) as disclosed herein. The system (100) can be used in certain embodiments of the methods described herein. The system (100) includes a reaction chamber (120). The reaction chamber (120) includes a lower conductive plate electrode (122) and an upper conductive plate electrode (121). The lower plate electrode (121) suitably serves as a substrate support. The upper conductive plate electrode (121) can suitably serve as a gas injector, i.e., as a spray head injector, for supplying one or more reaction gases (e.g., precursors and / or reactants) to the reaction chamber (120). One or more reaction gases can be supplied to the upper conductive plate electrode (121) from one or more precursor sources (e.g., a first precursor source (112)) via one or more gas lines (e.g., via a first gas line (111)). Unused reaction gases, carrier gases, reaction products, and the like can be removed from the reaction chamber (120) via an exhaust (124). Optionally, the system (110) includes one or more additional gas inlets (126) for providing further gas to the reaction chamber (120).

[0105] The lower conductive plate electrode (122), which serves as a substrate support, includes a cooling element and a heating element. The upper conductive plate electrode (121), which serves as a spray head injector, includes a spray head heating element. The precursor source (112) includes a first gas source heating element, and the first gas line (111) includes a first gas line heating element. For clarity, the various heating elements are not shown in FIG1. ​​Therefore, a temperature profile can be maintained in the system (100). Specifically, the upper conductive plate electrode (121) can be maintained at a temperature higher than that of the first gas line (111), the first gas line (111) can be maintained at a temperature higher than that of the first precursor source (112), and the lower conductive plate electrode (122) can be maintained at a temperature lower than that of the first precursor source (112). Therefore, the precursor can be efficiently deposited or condensed on the substrate located on the lower conductive plate electrode (122), while avoiding or at least minimizing the condensation or deposition of the precursor in the first gas line (111) and on the upper conductive plate electrode (121).

[0106] A reaction zone (123) is disposed within a reaction chamber (120), and specifically, is substantially located between the lower plate electrode (121) and the upper conductive plate electrode (121). Reactive species can be formed by plasma within the reaction zone (123). Plasma can be generated by operably connecting an RF power source (131) (i.e., an electrical power source that generates electrical power in the form of alternating current at frequencies in the radio frequency (RF) range) to the upper plate electrode (122), and by grounding the lower plate electrode (121) via an electrical ground (133).

[0107] Alternatively (not shown in the embodiment), the RF power source and the lower plate electrode can be connected by an operating ground, and the upper plate electrode can be grounded by an electrical ground, where plasma has been generated in the reaction zone.

[0108] The system (100) further includes a controller (not shown), which may include electronic circuitry and software to selectively operate RF power sources, valves, manifolds, heaters, pumps, and other components included in the system (100). Such circuitry and components are operated to introduce them from separate sources of precursors, reactants, and / or purge gases. In some embodiments, the controller may control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide appropriate operation of the system (100). The controller may include modules, such as software or hardware components, like FPGAs or ASICs, that perform certain tasks. Modules may advantageously be configured to reside on addressable storage media of the controller and may be configured to perform one or more processes. Various configurations of the system are possible, including various numbers and types of precursor sources, plasma gas sources, and purge gas sources.

[0109] Figure 2 shows another embodiment of the system (200) as disclosed herein. The system (200) can be used in certain embodiments of the methods described herein. The system (200) includes a reaction chamber (220). The reaction chamber (220) includes a substrate support (222) and a gas injector (221) for supplying one or more reaction gases (e.g., precursors and / or reactants) to the reaction chamber (220). Suitable injectors include spray head injectors, nozzles, injection guns, and the like. One or more reaction gases can be supplied to the injector (222) from one or more precursor sources (e.g., a first precursor source (212)) via one or more gas lines (e.g., via a first gas line (211)). Unused reaction gases, carrier gases, reaction products, and the like can be removed from the reaction chamber (220) via an exhaust (224). Optionally, the system (200) includes one or more additional gas inlets (226) for providing further gas to the reaction chamber (220).

[0110] The substrate support (222) includes a cooling element and a heating element. The precursor source (212) includes a first gas source heating element, and the first gas line (211) includes a first gas line heating element. For clarity, the various heating elements are not shown in FIG1. ​​Therefore, a temperature profile can be maintained in the system (200). Specifically, the injector (221) can be maintained at a temperature higher than that of the first gas line (211), the first gas line (211) can be maintained at a temperature higher than that of the first precursor source (212), and the substrate support (222) can be maintained at a temperature lower than that of the first precursor source (212). Therefore, the precursor can be efficiently deposited or condensed on the substrate located on the substrate support (222), while avoiding or at least minimizing the condensation or deposition of the precursor in the first gas line (211) and on the injector (221).

[0111] The system (200) further includes a radiation source (240) operatively coupled to the reaction chamber (220). Suitable radiation sources (240) include ultraviolet lamps and infrared lamps, as known in the art. The radiation source (240) may be separated from the reaction chamber (220) by a transparent window (241). It should be understood that the window (241) only needs to be at least partially transparent to the radiation generated by the radiation source (240), and not to other types of radiation. Optionally, the window (241) is heated. Providing a heated window (241) can suitably prevent or reduce precursor deposition or condensation on the window (241), thereby avoiding, for example, particulate problems or the need for frequent preventative maintenance.

[0112] The system (200) further includes a controller (not shown), which may include electronic circuitry and software to selectively operate the radiation source (240), valves, manifolds, heaters, pumps, and other components included in the system (200). Such circuitry and components are operated to introduce them from separate sources of precursors, reactants, and / or flushing gases. In some embodiments, the controller may control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide appropriate operation of the system (200). The controller may include modules, such as software or hardware components, like FPGAs or ASICs, that perform certain tasks. Modules may advantageously be configured to reside on addressable storage media of the controller and may be configured to perform one or more processes. Various configurations of the system are possible, including various numbers and types of precursor sources, plasma gas sources, and flushing gas sources.

[0113] Figure 3 shows another embodiment of the system (300) as disclosed herein. The system (300) can be used in certain embodiments of the methods described herein. The system (300) is similar to the system (200) of Figure 2; and the system (300) of Figure 3 includes a reaction chamber (320) comprising a substrate support (322) and a gas injector (321), a first precursor source (312), a first gas line (311), an exhaust (324), a controller, and optionally one or more additional gas inlets (326). The system (300) of Figure 3 includes a distal plasma source (340) operatively coupled to the reaction chamber (320), rather than a radiation source. Such suitable distal plasma sources (340) are known in the art and include inductively coupled plasma sources, microwave plasma sources, and capacitive plasma sources. The distal plasma source can be positioned adjacent to the reaction chamber, or it can be positioned at a distance from the reaction chamber, for example, at a distance of at least 1.0 meter to at most 10.0 meters. When the distal plasma source (340) is positioned at a distance from the reaction chamber (320), the distal plasma source (340) can be operatively connected to the reaction chamber (320) via an active species conduit (341). The active species conduit may comprise a tube. Optionally, the tube may contain one or more mesh plates. The mesh plates may at least partially block some reactive species, such as ions and electromagnetic radiation, while allowing other reactive species (e.g., free radicals) to pass through.

[0114] It should be understood that the system according to any of Figures 1 to 3 may include additional precursor and reactant sources. Some or all of these additional precursor and reactant sources may be maintained at a temperature higher than the substrate support temperature and lower than the gas injection system temperature, for example, lower than the temperature of the gas line and / or injector.

[0115] Figure 4 illustrates an embodiment of a method for forming a layer on a substrate as described herein. The method employs a system as described herein and includes positioning the substrate on a substrate support (411). The method then includes cyclically performing one or more cycles (415), for example, multiple cycles, such as 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 5000 or more cycles. A cycle includes, in the following order: a step of condensing or depositing a precursor on the substrate (412), and a step of curing the precursor (413). Optionally, the step of condensing or depositing the precursor on the substrate (412) and the step of curing the precursor may be separated by an intra-cycle rinse (416). Additionally or alternatively, in some embodiments, subsequent cycles may be separated by an inter-cycle rinse (417). This cyclic deposition process results in the deposition of material (i.e., a layer) on the substrate. The amount of material deposited on the substrate depends on the amount of cycle (415) performed. The method ends (414) after an appropriate amount of material has been deposited. The substrate is maintained at a temperature below the temperature of the precursor source, as described elsewhere herein, at least during the step of depositing or condensing the precursor on the substrate.

[0116] In some embodiments, step (413) of curing the precursor includes exposing the substrate to electromagnetic radiation. Suitable examples of electromagnetic radiation include ultraviolet light, visible light, and infrared light. Alternatively, and in some embodiments, step (413) of curing the precursor includes exposing the substrate to a distal plasma. Alternatively, and in some embodiments, step (413) of curing the precursor may include generating a direct plasma in a reaction chamber. In some embodiments, the direct plasma is continuously turned on throughout step (413) of curing the precursor. In some embodiments, the direct plasma is pulsed, i.e., the direct plasma is intermittently turned on and off multiple times.

[0117] In an exemplary embodiment of the method according to Figure 4, boronazine is used as a precursor to form a boron nitride-containing layer. In this exemplary embodiment, the substrate can be maintained at a temperature of 21°C, the precursor source can be maintained at a temperature of 40°C, the injector can be maintained at a temperature of 60°C, and the gas line carrying the precursor from the precursor source to the injector has a gradually increasing temperature from the precursor source to the injector. Therefore, boronazine can be condensed on the substrate. The condensed boronazine can then be cured by the techniques described herein.

[0118] Figure 5 illustrates another embodiment of a method for forming a layer on a substrate as described herein. The method employs a system as described herein and includes positioning the substrate on a substrate support (511). The method then includes cyclically performing one or more first cycles (518), for example, a plurality of first cycles, such as 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 5000 or more first cycles. A first cycle includes a step (512) of condensing or depositing a first precursor on the substrate, and a step (516) of curing the first precursor. Optionally, the step (512) of condensing or depositing the first precursor on the substrate and the step (516) of curing the first precursor can be separated by rinsing. After the first cycle (518) has been completed, the method includes cyclically performing one or more second cycles (519), such as a plurality of second cycles, for example 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 5000 or more second cycles. Optionally, the first cycle (518) and the second cycle (519) are separated by a rinse. A second cycle includes a step (513) of condensing or depositing a second precursor onto a substrate, and a step (517) of curing the second precursor. Optionally, the step (513) of condensing or depositing the second precursor onto a substrate and the step (517) of curing the second precursor may be separated by a rinse. Optionally, the first cycle (518) and the second cycle (519) may be repeated one or more times in a supercycle (515). Optionally, subsequent supercycles (515) are separated by a rinse. At least during the steps of depositing or condensing the first precursor on the substrate and depositing or condensing the second precursor on the substrate, the substrate temperature is maintained below the temperature of the first precursor source and below the temperature of the second precursor source, as described elsewhere herein.

[0119] This cyclic deposition process results in the formation of a layer on a substrate. The layer comprises one or more first sublayers and one or more second sublayers. The first sublayer contains an element contained in a first precursor, and the second sublayer contains an element contained in a second precursor. It should be understood that the first and second precursors are different. Therefore, the method described herein can lead to the formation of a superlattice comprising alternating first and second sublayers. Alternatively, intermixing between the first and second sublayers may occur during the method described herein or during subsequent process steps (such as annealing).

[0120] In some embodiments, the first precursor comprises a boron precursor as described herein. In some embodiments, the second precursor comprises a silicon precursor as described herein. When the first precursor comprises a boron precursor and the second precursor comprises a silicon precursor, a boron- and silicon-containing layer may be suitably formed. When the first precursor comprises boron and nitrogen and the second precursor comprises silicon, a silicon-doped boron nitride layer may be suitably formed.

[0121] In some embodiments, at least one of the steps (512) of curing the first precursor and (517) of curing the second precursor includes exposing the substrate to electromagnetic radiation. Suitable examples of electromagnetic radiation include ultraviolet light, visible light, and infrared light. Alternatively, and in some embodiments, at least one of the steps (512) of curing the first precursor and (517) of curing the second precursor includes exposing the substrate to a distal plasma. Alternatively, and in some embodiments, at least one of the steps (512) of curing the first precursor and (517) of curing the second precursor may include generating a direct plasma in a reaction chamber. In some embodiments, the direct plasma is continuously turned on throughout the entire period of at least one of the steps (512) of curing the first precursor and (517) of curing the second precursor. In some embodiments, the direct plasma is pulsed, i.e., the direct plasma is intermittently turned on and off multiple times.

[0122] Figure 6 shows an embodiment of a controller (600) used in a system as described herein. The controller includes a gas flow control unit (610), a precursor source temperature control unit (620), a gas injection system temperature control unit (630), a substrate support temperature control unit (640), and a curing unit control unit (650). The operation of a suitable controller (600) is described elsewhere herein.

[0123] The exemplary embodiments described herein do not limit the scope of the invention, as these embodiments are merely examples of examples of the invention, which is defined by the claims and their legal equivalents described below. Any equivalent embodiments are intended to fall within the scope of the invention. In fact, in addition to what is shown and described herein, various modifications to this disclosure will be apparent to those skilled in the art from this specification, such as substitutions of the described elements and combinations thereof. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

[0124] In this disclosure, where conditions and / or structures are not specified, those skilled in the art can readily propose such conditions and / or structures that pertain to routine experimental matters, in view of this disclosure.

[0125] 100, 200, 300: System 111, 211, 311: First gas pipeline 112, 212, 312: First precursor source 120, 220, 320: Reaction chamber 121: Upper conductive plate electrode 122: Lower conductive plate electrode 123,223,323: Reaction Zone 124, 224, 324: Exhaust components 126, 226, 326: Gas inlet 131: RF Power Source 221, 321: Gas Injector 222, 322: Substrate support 240: Radiation source 241: Transparent Window 340: Remote plasma source 341: Active Species Pipeline 411,412,413,416,417,511,512,513,516,517: Steps 414,514: Method ends 415: Loop 511, 512, 513, 516, 517: Steps 515: Hypercycle 518: First Cycle 519: Second Cycle 600: Controller 610: Gas Flow Control Unit 620: Precursor Material Source Temperature Control Unit 630: Gas injection system temperature control unit 640: Temperature control unit for substrate support 650: Curing Unit Control Unit

Claims

1. A system for depositing a layer, comprising: - a reaction chamber including a substrate support including a substrate cooling unit; - a precursor source for introducing a precursor into the reaction chamber via a gas injection system fluidly coupled to the reaction chamber, the precursor source including a precursor source heater; - a gas injection system heater configured to heat the gas injection system and maintain the gas injection system at a gas injection system temperature; and - a curing unit, wherein the gas injection system includes a spray head injector including a spray head injector heater, the spray head injector heater maintaining the spray head injector at a spray head injector temperature higher than or equal to the gas injection system temperature.

2. The system as claimed in claim 1, wherein the curing unit comprises: - a lower electrode and an upper electrode, the lower electrode being contained in the substrate support and the upper electrode being contained in the spray head injector; - a radio frequency power source configured to generate a radio frequency power waveform, the radio frequency power source being electrically connected to one of the lower electrode and the upper electrode.

3. The system as claimed in claim 1, wherein the curing unit comprises one or more of an infrared source, a UV source, a microwave source, and a remote plasma source.

4. The system as claimed in claim 1, wherein the curing unit includes a distal plasma source, and wherein one or more grid plates are positioned between the distal plasma source and the substrate support.

5. The system as described in any one of claims 1 to 4, further comprising a controller including: - a gas flow control unit configured to control the gas flow into the gas injection system; - a precursor source temperature control unit configured to maintain the precursor source at a predetermined precursor source temperature; - a gas injection system temperature control unit configured to maintain the gas injection system at a gas injection system temperature higher than the precursor source temperature; - a substrate support temperature control unit configured to maintain the substrate support at a predetermined substrate support temperature lower than the precursor source temperature; and - a curing unit control unit configured to control the operation of the curing unit.

6. The system as described in any one of claims 1 to 4, wherein the reaction chamber further includes a substrate heating unit contained within the substrate support.

7. A method for forming a layer on a substrate, the method comprising the steps of: - providing a system comprising a precursor source including a precursor, a gas injection system, a reaction chamber including a substrate support, and a curing unit, the gas injection system including a spray nozzle injector, the spray nozzle injector including a spray nozzle injector heater; - maintaining the precursor source at a precursor source temperature; - maintaining the gas injection system at a gas injection system temperature higher than the precursor source temperature; - maintaining the substrate support at a substrate support temperature lower than the precursor source temperature; - positioning a substrate on the substrate support; - supplying a precursor from the precursor source to the reaction chamber via the gas injection system, thereby condensing or depositing the precursor on the substrate to form a condensed or deposited precursor; - curing the condensed or deposited precursor by the curing unit; and - The spray head injector is maintained at a temperature higher than or equal to the gas injection system temperature by the spray head injector heater.

8. The method as described in claim 7, wherein: - The curing unit includes: a lower electrode and an upper electrode, the lower electrode being contained in the substrate support and the upper electrode being contained in the spray head injector; and a radio frequency power source configured to generate a radio frequency power waveform, the radio frequency power source being electrically connected to one of the lower electrode and the upper electrode; and wherein curing the condensed or deposited precursor involves generating a plasma between the upper electrode and the lower electrode.

9. The method as described in claim 7 or 8, wherein the curing unit includes an infrared source, and wherein curing the condensed or deposited precursor includes exposing the precursor to infrared radiation.

10. The method as claimed in claim 7 or 8, wherein the curing unit includes an ultraviolet radiation source, and wherein curing the condensed or deposited precursor includes exposing the precursor to ultraviolet radiation.

11. The method as claimed in claim 7 or 8, wherein the curing unit includes a remote plasma source, and wherein curing the condensed or deposited precursor includes exposing the condensed or deposited precursor to one or more activated species.

12. The method as described in claim 7 or 8, wherein the curing unit includes a distal plasma source, wherein one or more grid plates are positioned between the distal plasma source and the substrate support, and wherein curing the condensed or deposited precursor includes exposing the precursor to free radicals.

13. The method as described in claim 7 or 8, wherein the precursor comprises a boron precursor, and wherein curing the condensed or deposited precursor comprises exposing the precursor to a reactant.

14. The method as described in claim 7 or 8, comprising performing a plurality of deposition cycles, each deposition cycle comprising a precursor pulse and a curing pulse, the precursor pulse comprising providing the precursor to the reaction chamber, and the curing pulse comprising curing the condensed or deposited precursor.

15. The method as described in claim 7 or 8, wherein curing the precursor further comprises providing a reactant to the reaction chamber.

16. A method for forming a layer on a substrate, the method comprising the steps of: - providing a system comprising a first precursor source including a first precursor, a second precursor source including a second precursor, a gas injection system, a reaction chamber including a substrate support, and a curing unit, the gas injection system including a spray head injector, the spray head injector including a spray head injector heater; - maintaining the first precursor source at a first precursor source temperature; - maintaining the second precursor source at a second precursor source temperature; - maintaining the gas injection system at a gas injection system temperature higher than the first precursor source temperature and higher than the second precursor source temperature; - maintaining the substrate support at a substrate support temperature lower than the first precursor source temperature and lower than the second precursor source temperature; The process includes: - maintaining a spray head injector at a temperature higher than or equal to the gas injection system temperature by means of a spray head injector heater; - positioning a substrate on a substrate support; - performing one or more first cycles, each first cycle comprising: - supplying the first precursor from the first precursor source to the reaction chamber via the gas injection system, thereby condensing or depositing the first precursor onto the substrate to form a condensed or deposited first precursor; - curing the condensed or deposited first precursor by means of a curing unit; - performing one or more second cycles, each second cycle comprising: - supplying the second precursor from the second precursor source to the reaction chamber via the gas injection system, thereby condensing or depositing the second precursor onto the substrate to form a condensed or deposited second precursor; - curing the condensed or deposited second precursor by means of a curing unit.

17. The method as described in claim 16, comprising two or more superloops, each superloop comprising executing one or more first loops and executing one or more second loops.

18. The method as described in claim 7, wherein the system is one of the systems described in claim 1.

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