Device for providing gas mixture into reaction chamber, and method for using the same

Abstract

To provide a deposition process, and a device for supplying a gas mixture to a reaction chamber.SOLUTION: A deposition process comprises: preparing a device including a gas injection port 110, a mixing device 112 positioned upstream of the gas injection port and fluid-communicating with the gas injection port, a first vessel and a first gas supply source 114 for storing a reactant in the first vessel, and a second vessel and a second gas supply source 116 for storing a first precursor in the second vessel, wherein the mixing device has a first inlet and a second inlet, and the first inlet is positioned upstream of the second inlet; supplying the reactant to the mixing device through the first inlet; and supplying the first precursor to the mixing device through the second inlet.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application is a continuation - in - part application claiming priority based on U.S. Patent Application No. 17 / 842,057, filed on June 16, 2022, entitled "Apparatus for Providing a Gas Mixture to a Reaction Chamber and Method of Using the Same", which is a regular application based on U.S. Provisional Patent Application No. 63 / 213,089, filed on June 21, 2021, entitled "Apparatus for Providing a Gas Mixture to a Reaction Chamber and Method of Using the Same", and claims the priority and benefit thereof. The content of each application is incorporated herein by reference.

[0002] The present disclosure generally relates to a gas - phase reactor system and a method of using the same. More specifically, the present disclosure relates to an apparatus for providing a gas mixture to a reaction chamber of a reactor system.

Background Art

[0003] Gas - phase reactors such as chemical vapor deposition (CVD), plasma - enhanced CVD (PECVD), atomic layer deposition (ALD), and the like can be used for various applications such as deposition and etching of materials on a substrate surface. For example, a gas - phase reactor can be used to deposit and / or etch a layer on a substrate to form semiconductor devices, flat - panel display devices, photovoltaic devices, micro - electro - mechanical systems (MEMS), and the like.

[0004] A typical gas-phase reactor system includes one or more reactors, each reactor including one or more reaction chambers, one or more precursor gas sources and / or reactant gas sources fluidly connected to the one or more reaction chambers, one or more carrier gas sources and / or purge gas sources fluidly connected to the one or more reaction chambers, one or more gas distribution systems for delivering gas (e.g., one or more precursor gases / reactant gases and / or one or more carrier gases or one or more purge gases) to the surface of a substrate within any of the reaction chambers, and at least one exhaust source fluidly connected to the one or more reaction chambers.

[0005] In some of the processes carried out within the reaction chamber, it may be desirable to provide two or more types of gas to the reaction chamber simultaneously or with a temporal overlap. For example, two, three, four, or more types of gas may be provided to the reaction chamber separately, either simultaneously or with a temporal overlap. Such an apparatus may be suitable for some applications, but providing gas to the reaction chamber separately may introduce undesirable variations in the process. As a result, an improved apparatus for providing a gas mixture to the reaction chamber is desired.

[0006] The discussion of the problems and solutions related to the related art included in this disclosure is for the purpose of providing context for this disclosure only, and should not be construed as an admission that any or all of those discussions were known at the time the present invention was made.

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEM

[0007] Various embodiments of the present disclosure relate to an apparatus for providing a gas mixture to a reactor or reaction chamber, a system including the apparatus, and a method of using the apparatus and system. The apparatus, system, and method can be used in connection with various applications such as, for example, the manufacture of electronic devices. How various embodiments of the present disclosure address the drawbacks of conventional methods and systems will be considered in more detail below, but generally, various embodiments of the present disclosure provide improved apparatus, systems, and methods suitable for providing a mixture of two or more gases to a reaction chamber. Exemplary apparatus can, for example, reduce the time scale for diffusion of the gases, thereby improving the mixing of the gases and / or reducing the length of time for mixing the gases before entering the reaction chamber. Further examples of the present disclosure provide improved apparatus and methods for providing pulses of the mixed gas.

[0008] According to at least one embodiment of the present disclosure, an apparatus for providing a gas mixture to a reaction chamber includes a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas source containing a first precursor therein, a second container and a second gas source containing a second precursor therein, a first gas pulse valve fluidly connected to the first container and the mixing device, a second gas pulse valve fluidly connected to the second container and the mixing device, and a first pressure flow control valve fluidly connected between the first container and a carrier gas source. In some cases, the gas injection port can be considered to form part of the reactor rather than part of the apparatus. According to a further example of the present disclosure, the apparatus further includes a purge valve fluidly connected to the first gas pulse valve and the second gas pulse valve. According to a further example of the present disclosure, the apparatus includes three, four, or more gas sources connected to the mixing device.

[0009] According to a further embodiment of the present disclosure, an apparatus for providing a gas mixture to a reaction chamber includes a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas source containing a first precursor therein, a second container and a second gas source containing a second precursor therein, a first gas valve fluidly connected to the first container and the mixing device, a second gas valve fluidly connected to the second container and the mixing device, a first pressure flow control valve fluidly connected between the first container and a carrier gas source, and a pulse valve between the mixing device and the gas injection port. Similarly, the gas injection port may form part of the reactor. According to an exemplary aspect of these embodiments, the apparatus further includes a bypass valve downstream of the mixing device. According to a further aspect, the apparatus further includes a purge gas source and a purge gas valve in fluid communication with the pulse valve. According to a further embodiment of the present disclosure, the apparatus includes three, four, or more gas sources connected to the mixing device.

[0010] According to one or more embodiments of the present disclosure, the mixing device includes a plurality of sections to facilitate rapid and / or desired mixing of two or more gases. For example, the mixing device can include a first section having a first inlet, a first outlet, and a first space 403 therebetween, and a second section having a second inlet, a second outlet, and a second space 419 therebetween. The first inlet can be upstream of the second inlet, the first outlet can be downstream of the second inlet, and / or the first outlet can be upstream of the second outlet. According to a further embodiment, the mixing device can further include a third section. The third inlet can be downstream of the second inlet and upstream of the second outlet, the second outlet can be within the third space, and / or the first outlet can be within the second space.

[0011] According to an additional embodiment of the present disclosure, a method of controlling the gas flow to a reaction chamber using an apparatus as described in the present disclosure is disclosed.

[0012] According to still further embodiments of the present disclosure, a system including an apparatus as described in the present disclosure is disclosed.

[0013] According to further embodiments of the present disclosure, a deposition process is provided. According to examples of these embodiments, the deposition process includes providing an apparatus including a gas injection port and a mixing device, providing reactants to the mixing device through a first inlet, and providing a first precursor to the mixing device through a second inlet. The apparatus may further include a first container and a first gas supply source for containing reactants in the first container, a second container and a second gas supply source for containing the first precursor in the second container, a first gas pulse valve fluidly connected to the first container and the mixing device, and a second gas pulse valve fluidly connected to the second container and the mixing device. As described above, the mixing device can be upstream of the gas injection port and can be in fluid communication with the gas inlet port. The mixing device may have a first inlet and a second inlet, and the first inlet may be upstream of the second inlet. The gas injection port and the mixing device may be similar to the gas injection port and the gas mixing device described above and elsewhere in the present disclosure. According to examples of these embodiments, the step of providing reactants to the mixing device includes pulsing the reactants to the mixing device. According to further examples, the step of providing the first precursor to the mixing device includes pulsing the first precursor to the mixing device. According to further examples, the process includes maintaining a steady-state pressure in the first container and providing a controlled flow of reactants to the mixing device. In some cases, the process includes providing a second precursor to the mixing device and mixing the second precursor with the first precursor within the mixing device. According to further examples, the process includes, for example, forming a plasma within a reaction chamber.

[0014] According to further additional embodiments of the present disclosure, the deposition process comprises providing an apparatus comprising a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas source containing a first precursor therein, and a second container and a second gas source containing a second precursor mixture therein; and pulsing a mixture of the first precursor and the second precursor from the mixing device to the gas injection port. According to an example of these embodiments, the mixing device has a first inlet and a second inlet, and the first inlet is upstream of the second inlet. The method may further comprise providing reactants to the mixing device. In such a case, the reactants may be provided to the first inlet and / or upstream of the first precursor and the second precursor. According to various examples of these embodiments, the process comprises pulsing reactants to the gas injection port, and the step of pulsing the reactants and the step of pulsing the mixture are performed in a temporally separated manner, i.e., not overlapping in time. According to still further examples, a combination of reactants and the mixture is pulsed to the gas injection port.

[0015] According to yet other exemplary embodiments of the present disclosure, an apparatus for providing a gas mixture to a reaction chamber includes a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas source containing a reactant in the first container, a second container and a second gas source containing a first precursor in the second container, a third container and a third gas source containing a second precursor in the third container, a first gas valve fluidly coupled to the first container and the mixing device, and a second gas valve fluidly coupled to the second container and the mixing device. According to an example of these embodiments, the mixing device has a first inlet, a second inlet, and a third inlet, the first inlet being upstream of the second inlet, the second inlet being upstream of the third inlet, the reactant being provided to the first inlet, the first precursor being provided to the second inlet, and the second precursor being provided to the third inlet. According to some examples of these embodiments, the apparatus includes a controller configured to provide the reactant to the first inlet. In some cases, the controller is configured to provide the reactant to the first inlet to the reaction chamber after a predetermined number of deposition cycles or pulses (e.g., only) of the first precursor, the second precursor, and / or the gas mixture. In some cases, the first precursor and the second precursor are mixed within the mixing device to form a gas mixture. According to yet further examples of the present disclosure, the apparatus further includes a pulse valve between the mixing device and the gas injection port.

[0016] These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of any embodiments taken in reference to the accompanying drawings, but the invention is not limited to any one or more of the disclosed specific embodiments.

[0017] A more complete understanding of exemplary embodiments of the present disclosure can be obtained by referring to the following detailed description of embodiments for carrying out the invention and the claims in view of the following exemplary drawings.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

[0019] It will be understood that the elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, some dimensions of elements in the figures may be exaggerated relative to other elements to assist in improving the understanding of the illustrated embodiments of the present disclosure.

[0020] While certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the scope of the present invention extends beyond the specifically disclosed embodiments and / or uses, and their obvious modifications and equivalents. Accordingly, it is intended that the scope of the disclosed invention not be limited by the specific disclosed embodiments described below.

[0021] This disclosure generally relates to vapor phase apparatuses, reactor systems, and methods (also referred to herein as processes). Apparatuses, systems, and methods as described in this disclosure can be used to process substrates, such as semiconductor wafers, for example, to form electronic devices. By way of example, the systems and methods described in this disclosure can be used to form or grow multi-component layers, such as layers of crystalline or amorphous indium gallium zinc oxide, or crystalline or amorphous mixtures containing at least two of indium, gallium, or zinc, and oxygen, or crystalline or amorphous mixtures containing at least one of indium, gallium, or zinc, and at least a second metal or metalloid, and oxygen.

[0022] In this disclosure, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), vaporized solids, and / or vaporized liquids, and can in some situations consist of a single gas or a mixture of gases. Gases other than process gases, i.e., gases introduced without passing through a gas dispersion assembly, another gas dispersion device, or the like, can be used, for example, to seal a reaction space and can include seal gases such as noble gases.

[0023] The term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound. The term "reactant" can be used interchangeably with the term "precursor". The term "inert gas" can refer to a gas that does not participate in a chemical reaction and / or does not become part of a layer to a significant extent. Exemplary inert gases include helium and argon and any combination thereof. In some cases, molecular nitrogen and / or hydrogen can be inert gases. A carrier gas can be an inert gas or can include an inert gas.

[0024] As used herein, the term "substrate" may refer to any one or more underlying materials that can be used to form a device, circuit, or film, or any one or more underlying materials on which a device, circuit, or film may be formed. The substrate can include a bulk material such as silicon (e.g., single crystal silicon), another Group IV material such as germanium, or a compound semiconductor material such as GaAs, and can also include one or more layers on or under the bulk material. Further, the substrate may include various topologies (such as recesses, lines, and the like) formed within or on at least a portion of the layers of the substrate.

[0025] The term "cyclic deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber for depositing a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD components and cyclic CVD components. The process may include a purge step during the introduction of the precursors. In some cases, one or more reactants and / or precursors can be continuously provided to the reaction chamber, and one or more other reactants and / or precursors can be pulsed into the reaction chamber. In some instances, plasma power can be pulsed, e.g., each cycle of the cyclic deposition process can include one or more pulses of plasma power.

[0026] The term "atomic layer deposition" can refer to a deposition process in which deposition cycles (typically a plurality of consecutive deposition cycles) are performed in a process chamber. As used herein, the term "atomic layer deposition" also means including processes indicated by related terms (such as chemical vapor deposition atomic layer deposition) when performed with alternating pulses of precursor / reactant gas(es) and purge (e.g., inert carrier) gas(es).

[0027] As used in this disclosure, the term "plasma enhanced atomic layer deposition" (PEALD) may refer to an ALD process in which one or more precursors, reactants, and / or other gases are exposed to a plasma to form excited species.

[0028] Furthermore, in this disclosure, any two numbers of a variable can constitute the executable range of that variable, and any range shown may include or exclude endpoints. Additionally, any value of a variable shown (regardless of whether they are shown with "about") refers to an exact value or an approximate value, may include equivalent values, and may also refer to an average value, median value, representative value, or the majority or the like. Further, in this disclosure, the terms "comprising", "consisting of", and "having" can independently refer to "typically or broadly comprising", "comprising", "essentially consisting of", or "consisting of" in some embodiments. In this disclosure, any defined meaning does not necessarily exclude the ordinary meaning and customary meaning in some embodiments.

[0029] Turning now to the drawings, FIG. 1 illustrates a reactor system 100 according to at least one embodiment of the present disclosure. The reactor system 100 includes a reaction chamber 102, an apparatus 104 for providing a gas mixture to the reaction chamber 102, a vacuum source 106, and a controller 108.

[0030] The reaction chamber 102 can be or include a reaction chamber suitable for gas-phase reactions. The reaction chamber 102 can be formed from a suitable material such as quartz, metal, or the like, and may be configured to hold one or more substrates for processing. The reactor system 100 can include any suitable number of reaction chambers 102 and, optionally, may be configured to include one or more substrate handling systems.

[0031] The reaction chamber 102 can be configured as a CVD reactor, a cyclic deposition process reactor (e.g., a cyclic CVD reactor), an ALD reactor, a PEALD reactor, or the like, any of which may include a plasma device such as a direct plasma device and / or a remote plasma device.

[0032] FIG. 2 illustrates an exemplary apparatus 200 suitable for use as a PEALD reactor. The apparatus 200 includes a reaction chamber 3 suitable for use as and / or in connection with (i.e., as a part of) the reaction chamber 102 of the system 100.

[0033] As shown in FIG. 2, a pair of conductive flat plate electrodes 2, 4 may be provided parallel to and facing each other within the interior 11 (reaction zone) of the reaction chamber 3, and RF power is applied from a power source 25 to one side (e.g., at 13.56 MHz and / or 27 MHz), and the other side 12 is electrically grounded, whereby plasma can be generated between the electrodes 2, 4. A temperature regulator may be provided on the lower stage 2, i.e., the lower electrode. The substrate 1 is disposed on the stage / lower electrode 2, and the temperature of the stage 2 and / or the substrate may be maintained at a desired temperature. The upper electrode 4 may also function as a gas distribution device such as a shower plate, and various gases such as a plasma gas, a reactant gas, and / or a dilution gas, and, if present, a gas mixture can be introduced into the reaction chamber 3 through the gas line 21 and the gas line 22 and through this shower plate 4. For example, a gas mixture (e.g., a gas mixture containing two or more precursors) from an apparatus 104 for providing the gas mixture to the reaction chamber may be provided to the gas injection port 26 via the line 22, or a reactant from a reactant source 27 may be provided to the gas injection port 26 via the line 21. As shown, the line 21 may desirably be upstream of the line 22.

[0034] Inside the reaction chamber 3, a circular duct 13 having an exhaust line 7 is provided, and through this, the gas inside the interior 11 of the reaction chamber 3 is exhausted. In addition, the transfer chamber 5 is arranged below the reaction chamber 3, and the transfer chamber 5 is provided with a gas seal line 24 for introducing a seal gas into the interior 11 of the reaction chamber 3 through the interior 16 of the transfer chamber 5, and a separation plate 14 for separating the reaction zone and the transfer zone is provided. A gate valve through which the substrate can be transferred into or out of the transfer chamber 5 is omitted from this figure. The transfer chamber is also provided with an exhaust line 6.

[0035] Returning to FIG. 1, the apparatus 104 for providing a gas mixture to the reaction chamber includes a gas injection port 110, a mixing device 112, a first gas supply source 114, a second gas supply source 116, a third gas supply source 118, a first gas pulse valve 120, a second gas pulse valve 122, a third gas pulse valve 124, a first pressure flow control valve 126, a second pressure flow control valve 128, a third pressure flow control valve 130, one or more carrier gas supply sources 132, a purge valve 134, and a purge gas supply source 136. By providing pulses of two or more types of gas to the mixing device 112 downstream of the one or more pulse valves, the apparatus 104 can be used to mix the gases from the two or more gas supply sources 114 - 118. The apparatus 104 provides flexibility in timing (for example, the start of one type of gas can be before or after the other gases flow into the mixing device 112). Further, the apparatus 104 can be easily shifted to a single gas injection system without delay.

[0036] The gas injection port 110 may be configured to include a pipe or the like for providing the gas mixture to the reaction zone of the reaction chamber. The gas injection port 110 may be integrated with the reaction chamber 102 or may be separate. An exemplary gas injection port 26 suitable for use as the injection port 110 is illustrated in FIG. 2.

[0037] The mixing device 112 is configured to inject two or more types of gases from two or more of, for example, the first gas supply source 114, the second gas supply source 116, and the third gas supply source 118 before entering the reaction chamber 102. As shown in the figure, the mixing device 112 may be upstream of the gas injection port 110 or may be configured to be in fluid communication with the gas injection port 110. The mixing device 112 may be configured to include a space larger than the space of the gas injection port 110 / 26. As an example, the volume of the space of the mixing device 112 can range from about 5 to about 50 cc. The configuration of the mixing device 112 may be different according to the application. The mixing device 112 may be configured to include a tortuous path or may be configured as a static mixer. In some cases, the mixing device 112 may be configured to include a housing 138, and the housing 138 may be, for example, a substantially hollow cylinder having caps on each end. Another embodiment of a suitable mixing device will be described in more detail below with reference to FIG. 4.

[0038] The first gas supply source 114, the second gas supply source 116, and the third gas supply source 118 may each have a configuration including a container and a precursor accommodated in each container. As an example, the first gas supply source 114 may have a configuration including a container and an indium precursor, the second gas supply source 116 may have a configuration including a container and a gallium precursor, and the third gas supply source 118 may have a configuration including a container and a zinc precursor. Exemplary indium precursors include TEI, TMI, 3-(dimethylamino)propyl]dimethyl-indium (DADI), DMZ, DEZ, In(acac)3, In(dmamp)2(OiPr), In(dmamp)3, In(dpguan)3, In(EtCp), InCp, In(iPrAMD)3, In(iPrFMD)3, In(N(SiMe3)2)Et2, In(PrNMe2)Me2, In(thd)3, InCl3, InMe2(edpa), InMe3(MeO(CH2)2NHtBu), InMe3, InEt3, [EtZn(damp)]2. Exemplary gallium precursors include TDMAG, TMGa, TEGa, GaCl3, GaEt2Cl, (GaMe2NH2)3, Ga(acac)3, Ga(CpMe5), Ga(thd), Ga2(NMe2)6, GaMe2(OiPr), GaMe2NH2, GaMe3(CH3OCH2CH2NHtBu). Exemplary zinc precursors include Zn(DMP)2, Zn(eeki)2, Zn(OAc)2, ZnCl2, ZnEt2, ZnMe2, ZnMe(OiPr). Although three gas supply sources 114 to 118 are shown, an exemplary apparatus may have a configuration including any suitable number of two or more gas supply sources (for example, four or more) connected to the mixing device 112. Further, the reactor system 100 or the apparatus 104 for providing a gas mixture to the reaction chamber may have a configuration including a reactant supply source 142 that can be connected to the gas injection port 110 and / or the mixing device 112. The reactant supply source 142 may have a configuration including one or more reactant containers and one or more reactant supply sources. The reactant supply source may have a configuration including one or more of an oxygen reactant, a nitrogen reactant, and / or a carbon reactant.As discussed in more detail below, according to embodiments of the present disclosure, at least one reactant source 142 includes an oxygen reactant. Exemplary oxygen reactants are described below. In some cases, the reactant source 142 is configured to include a plurality of reactants such as a plurality of oxygen reactants (e.g., H2O and O3), or to provide such a plurality of reactants to the mixing device simultaneously or substantially simultaneously (e.g., as defined herein). Also, as shown, the reactor system 100 may include an excitation source 146 such as a remote plasma unit or an ozone generator, configured to form excited species from the reactants from the reactant source 142, and the excited species can be flowed to the mixing device 112 and / or the gas injection port 110.

[0039] Two or more of the first gas supply source 114, the second gas supply source 116, and the third gas supply source 118, or each of them, may be configured to be connected to the mixing device 112 using pulse valves. Additional gas supply sources may be similarly configured to be connected to the mixing device 112. For example, as shown, the first gas supply source 114 (e.g., its container) can be connected to the mixing device 112 via the first gas pulse valve 120, the second gas supply source 116 (e.g., its container) can be connected to the mixing device 112 via the second gas pulse valve 122, and the third gas supply source 118 (e.g., its container) can be connected to the mixing device 112 via the third gas pulse valve 124. The apparatus 104 and / or the reactor system 100 may additionally include a pulse valve 144 between the reactant source 142 and the gas injection port 110 and / or the mixing device 112. The pulse valves 120-124, 144 can be used to provide a desired amount (pulse) of gas to the mixing device 112 (or the gas injection port 110). As an example, one or more of the gas pulse valves 120-124, 144 or other pulse valves described in the present disclosure may be configured with an air valve or an electric solenoid valve.

[0040] As further illustrated, a carrier gas (which may include one or more carrier gas sources) from the carrier gas source 132 may be used to supply one or more of the first, second, and / or third precursors and / or an additional gas (e.g., a fourth gas) to the reaction chamber 102 as described in the present disclosure. In the illustrated example, the carrier gas source 132 is connected to the first pressure flow control valve 126 to supply the first precursor at a desired concentration to the first gas pulse valve 120, the carrier gas source 132 is connected to the second pressure flow control valve 128 to supply the second precursor at a desired concentration to the second gas pulse valve 122, and the carrier gas source 132 is connected to the third pressure flow control valve 130 to supply the third precursor at a desired concentration to the third gas pulse valve 124. The pressure control valves 126, 128, 130 can be used to maintain a constant / desired pressure in each of the first container, the second container, and the third container to provide a controlled flow rate of each of the first precursor, the second precursor, and the third precursor. By way of example, the pressure control valve may be configured as, or may include, a pressure flow controller or a mass flow controller.

[0041] The vacuum source 106 may be configured to include, for example, one or more vacuum sources. Exemplary vacuum sources include one or more dry vacuum pumps and / or one or more turbomolecular pumps.

[0042] The controller 108 may be configured to perform various functions and / or processes as described in the present disclosure. The controller 108 may be configured to include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although the controller 108 is illustrated as a single unit, alternatively, it may be configured to include a plurality of devices. By way of example, the controller 108 may be used to control the gas flow to the mixing device 112 and the gas mixture from the mixing device 112 to the vacuum source 106 and / or the reaction chamber 102. In some cases, the controller 108 may be used to pulse two or more precursors (e.g., from the sources 114-118) and / or reactants from the reactant source 142 to the mixing device 112 and / or the gas injection port 110. As a further example, the controller 108 may independently control each pressure flow control valve 126-130 and each gas pulse valve 120-124 to independently provide the relative concentrations and relative amounts or ratios (e.g., mass ratio) of two or more precursors to the mixing device 112. In the embodiment illustrated in FIG. 1, the controller 108 may be configured to open each pulse valve 120-124 substantially simultaneously (e.g., within about 0.001 or about 0.005 seconds). The pulse duration described in the present disclosure may be from about 0.01 seconds to about 600 seconds or from about 0.02 seconds to about 10 seconds.

[0043] Also, the system 100 may be configured to include a purge valve 134 fluidly connected to the purge gas source 136 and to one or more of the first gas pulse valve 120, the second gas pulse valve 122, and / or the third gas pulse valve 124. The purge valve 134 may be connected to and used by the controller 108 to purge the pulse valves 120-124 and the mixing device 112. The purge gas source 136 may be configured to include a purge gas such as a container and one or more of nitrogen, argon, helium, or the like contained in the container. The purge valve 134 may be, for example, an air valve or an electric solenoid type valve.

[0044] Turning now to FIG. 3, another apparatus 300 for providing a gas mixture to the reaction chamber is illustrated. Apparatus 300 is configured to mix the gases upstream of the pulse valve. This configuration allows for a larger mixing space and can facilitate more complete mixing of one or more of the gases within the mixing device. Apparatus 300 can be used in place of apparatus 104 within a reactor system such as reactor system 100.

[0045] Apparatus 300 includes a gas injection port 302, a mixing device 304, a first gas source 306, a second gas source 308, a third gas source 310, a first gas valve 312, a second gas valve 314, a third gas valve 316, a first pressure flow control valve 318, a second pressure flow control valve 320, a third pressure flow control valve 322, one or more carrier gas sources (not separately illustrated in FIG. 3), a pulse valve 324, and a purge gas source 326. Apparatus 300 includes a pulse valve 324 between the mixing device 304 and the gas injection port 302 such that mixing of the gases within the mixing device 304 occurs upstream of the pulse valve 324. Also, apparatus (or system) 300 may be configured to include a reactant gas source 142 and a pulse valve 144 as described above with reference to FIG. 1.

[0046] The gas injection port 302, the mixing device 304, the first gas supply source 306, the second gas supply source 308, the third gas supply source 310, the first pressure flow control valve 318, the second pressure flow control valve 320, the third pressure flow control valve 322, one or more carrier gas supply sources, and the purge gas supply source 326 can be the same as or similar to the gas injection port 110, the mixing device 112, the first gas supply source 114, the second gas supply source 116, the third gas supply source 118, the first pressure flow control valve 126, the second pressure flow control valve 128, the third pressure flow control valve 130, one or more carrier gas supply sources 132, and the purge gas supply source 136 described above in connection with FIG. 1. Further, the apparatus 300 may also include a bypass valve 328 which can be an air valve or an electric solenoid type valve, and a purge valve 330 which can be the same as or similar to the purge valve 134.

[0047] As described above, by using the first pressure flow control valve 126, the second pressure flow control valve 128, and / or the third pressure flow control valve 130 to control the (e.g., constant) pressure in the corresponding container, and thereby controlling the flow of the precursor from the gas supply source to the mixing device 304 and / or the desired or predetermined concentration, the amount of the carrier gas flowing to each of the first gas supply source 306, the second gas supply source 308, and the third gas supply source 310 can be controlled. For example, the amount of gas from each gas from the supply sources 306 - 310 can be set by the supply source vapor pressure / carrier gas pressure ratio using the carrier gas pressure controlled by each of the first pressure flow control valve 126, the second pressure flow control valve 128, and the third pressure flow control valve 130. The carrier gas / precursor flow may be configured to be controlled by, for example, a fixed orifice, a needle valve, a mass flow controller, or a volume flow controller.

[0048] The first gas valve 312, the second gas valve 314, and the third gas valve 316 may be configured to include an air valve or an electric solenoid type valve, and / or may be configured to form part of a flow meter and / or a mass flow controller. In the illustrated embodiment, the first gas valve 312, the second gas valve 314, and the third gas valve 316 provide a metered amount of the first gas, the second gas, and the third gas from the first gas supply source 306, the second gas supply source 308, and the third gas supply source 310 to the mixing device 304.

[0049] As an example, one or more of the first gas valve 312, the second gas valve 314, and the third gas valve 316 (e.g., each of such valves) form part of a mass flow controller. In these cases, the set point for the mass flow controller can determine the composition of the gas mixture within the mixing device 304 provided to the injection port 302. An exemplary sequence for providing the gas mixture to the injection port 302 may be configured to include filling the mixing device 304 by opening and (e.g., controllably) flowing the gas into the mixing device 304 using the first gas valve 312, the second gas valve 314, and the third gas valve 316. Substantially simultaneously, it may be configured to open the first gas valve 312, the second gas valve 314, the third gas valve 316, and the pulse valve 324 to supply the gas mixture to the injection port 302. The valves may be controlled using one or more controllers such as the controller 108.

[0050] To pulse the gas mixture from the mixing device 304 and / or to pulse the purge gas from the purge gas source 326 and / or the reactants from the mixing device 304 or the reactant source 142 to the gas injection port 302, the pulse valve 324 can be used. According to an embodiment of the present disclosure, the first gas valve 312, the second gas valve 314, the third gas valve 316, and / or the reactant gas pulse valve 144 and the pulse valve 324 open and close substantially simultaneously, for example, within about 0.001 seconds or about 0.005 seconds, to pulse the gas (e.g., the mixture) into a reaction chamber such as the reaction chamber 102.

[0051] According to a further embodiment of the present disclosure, the apparatus 300 includes a pressure monitor 332 for measuring the pressure of the mixing device 304. In these cases, the controller (e.g., the controller 108) may be further configured to fill the mixing device 304 to a desired (e.g., set) pressure. When the pressure is reached, the first gas valve 312, the second gas valve 314, and the third gas valve 316 are shut off. Alternatively, the first gas valve 312, the second gas valve 314, and the third gas valve 316 may be configured to be opened at a set flow rate for a period of time to fill the mixing device 304. In these cases, there is no significant additional space downstream of the pulse valve 324 and between the mixing device 304 and the gas injection port 302.

[0052] To purge the pulse valve 324 and the injection port 302, the purge valve 330 can be opened and the pulse valve 324 can pulse the purge gas from the purge gas source 326 into the injection port 302 and / or into the reaction chamber.

[0053] The controller 108 or one or more similar controllers can be used to control the valves 144, 312 - �16, 320, 324, 330, and 328, the pressure monitor 332 can be used to set and monitor the pressure, and other functions described herein in connection with FIGS. 1 - 3 can be performed.

[0054] Figure 4 illustrates a mixing device 400 suitable for use as the mixing device 112 or 304. The mixing device 400 includes a first section 402, a second section 404, and a third section 406. As illustrated, the first section 402, the second section 404, and the third section 406 can be cascaded such that the outlet of the first section 402 is within the second section 404 and the outlet of the second section 404 is within the third section 406. Additionally or alternatively, the first section 402, the second section 404, and the third section 406 can be coaxial, for example, about an axis 408. Although the illustrated cascaded mixing device has three sections, it can suitably include two or more sections as described in the present disclosure.

[0055] The first section 402 includes a first inlet 410 having a diameter D4, a first outlet 412 having a diameter D3, and a space 403 therebetween. In the illustrated embodiment, D3 is larger than D4.

[0056] The second section 404 may be configured to include one or more second inlets 414, 415, 416, 417, a second outlet 418, and a second space therebetween. The diameter D2 of the outlet 418 can be larger than each or the sum of the diameters of the one or more inlets 414, 416. Further, the diameter D2 can be larger than D3 and / or D4.

[0057] As illustrated, the first inlet 410 may be upstream of the second inlets 414, 416. Further, the first outlet 412 may be downstream (e.g., with respect to one or more gases) of the second inlets 414, 416. And the first outlet 412 may be upstream of the second outlet 418.

[0058] The third section 406 may be configured to include a third inlet 420, 421, a third outlet 422, and a space 423 therebetween. The third outlet 422 may be configured to be connected to a reaction chamber, a gas injection port, and / or one or more valves (e.g., a pulse valve) as described in the present disclosure. The space 423 may be configured to have a diameter of D1 or a similar cross-section, and D1 can be made larger than D2, D3, and / or D4. Further, as shown, the third inlet 420 is downstream of the second inlets 414, 416 and upstream of the second outlet 418.

[0059] According to an embodiment of the present disclosure, one or more reactants are provided to a mixing device upstream of one or more precursors. For example, the reactants can be provided to the first inlet 410, the first precursor can be provided to the second inlet 414 or another inlet downstream of the first inlet 410, and the second precursor can be provided to the third inlet 420 or another inlet downstream of the first inlet 410.

[0060] Referring to FIGS. 1 and 4, a controller, such as controller 108, may be configured to provide (e.g., selectively) a reactant to the first inlet, e.g., via a pulse valve 144 or a gas injection port 110. For example, the controller 108 may be configured to provide the reactant to the first inlet 410 during each deposition cycle and / or after a predetermined number of deposition cycles and / or after a predetermined number of substrates have been processed.

[0061] According to some embodiments of the present disclosure, a deposition process is provided. An exemplary deposition process may be configured to use the reactor system 100, the apparatus 300, and / or the mixing device 400 as described above. For example, an exemplary deposition process may be configured to include preparing a reactor system or apparatus described in the present disclosure, supplying reactants, and supplying at least one precursor. More specifically, an exemplary deposition process includes a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas supply source for containing reactants therein, a second container and a second gas supply source for containing a first precursor therein, a first gas pulse valve fluidly connected to the first container and the mixing device, and a second gas pulse valve fluidly connected to the second container and the mixing device, and the mixing device has a first inlet and a second inlet, and the first inlet is upstream of the second inlet, and preparing an apparatus including: supplying the reactants to the mixing device through the first inlet; and supplying a first precursor to the mixing device through the second inlet. Supplying reactants to the mixing device upstream of one or more precursors can reduce particle formation and / or peeling of the grown film that might otherwise occur and / or extend the life of the mixing device. Reactants can be introduced during a deposition cycle that includes pulsing a mixture of precursors and pulsing the reactants separately. Additionally or alternatively, to extend the life of the mixing device, i.e., to extend the period during which the mixing device can be used without cleaning or repair, the deposition process may be configured to include periodically pulsing reactants to the mixing device after several deposition cycles and / or after treating several substrates. The surface of the mixing device can be refreshed using reactants such as oxygen reactants (e.g., O2, H2O2, O3, H2O, oxygen radicals, atomic oxygen, or its excited species (e.g., formed from plasma or other excitation sources)). Such periodic pulsing can be performed, for example, before or after the substrate is treated.For example, the reactants may be supplied to the mixing device while the substrate is not in the reaction chamber. The reactants used to condition the mixing device and the reactants used in the deposition reaction may be the same or different and may include a plurality of reactants (e.g., H2O and O3, or any other combination of reactants described in this disclosure). When a plurality of reactants are supplied to the mixing device, it is desirable that at least one or each, or the reactants, can be provided upstream of any of the precursor supplies. For example, refer to FIG. 4.

[0062] In some embodiments, the material grown up to and / or within the mixing device upstream of the gas injection port has a density of about 50% to about 120%, about 70% to about 110%, about 80% to about 100%, about 85% to about 99% relative to the bulk density of the grown material. In some embodiments, the material grown up to and / or within the mixing device upstream of the gas injection port contains impurities such as halides (e.g., Cl) or carbon in ranges such as <30 at%, <20 at%, <10 at%, <7 at%, <5 at%, <3 at%, <2 at%, or <1 at%. In some embodiments, the material grown up to and / or within the mixing device upstream of the gas injection port contains impurities such as halides (e.g., Cl) or carbon in ranges such as 50% to about 500%, 90% to about 300%, 100% to about 250%, 105% to about 200%, 105% to about 200%, 105% to about 200% compared to the material grown on the substrate.

[0063] According to examples of these embodiments, the deposition process may be configured to include pulsing one or more types of reactants into the apparatus. For example, a pulse valve 144 can be used to pulse reactants (e.g., oxidants) into the mixing device.

[0064] The deposition process may be configured to further include supplying a second precursor and / or a third precursor to a mixing device. The first precursor, the second precursor, and / or the third precursor can be pulsed into the mixing chamber as described above. Two or more of the first precursor, the second precursor, and the third precursor can be mixed within the mixing device.

[0065] According to an embodiment of the present disclosure, the steady-state pressures in the first container used to supply the first precursor, the second container used to supply the second precursor, the third container used to supply the third precursor, and / or the reactant container used to supply the reactants are maintained at a steady-state pressure (e.g., within about + / - 10% or + / - 5% or + / - 2% of a target pressure) to provide a controlled flow of reactants to the mixing device.

[0066] An exemplary deposition process may be configured to further include supplying a purge gas to one or more gas pulse valves, such as the gas pulse valve described above, to purge the gas pulse valve.

[0067] According to another embodiment, the deposition process may be configured to include a step of forming a plasma. For example, a remote excitation source (e.g., a remote plasma unit) 146 can be used to form excited species from one or more reactants before introducing them into the mixing device and / or the gas injection port.

[0068] According to a further embodiment of the present disclosure, the deposition process comprises an apparatus having a gas injection port, a mixing device upstream of the gas injection port and in fluid communication with the gas injection port, a first container and a first gas source containing a first precursor therein, and a second container and a second gas source containing a second mixed precursor therein, wherein the mixing device has a first inlet and a second inlet, and the first inlet is upstream of the second inlet, and pulsing a mixture of the first precursor and the second precursor from the mixing device to the gas injection port. The method may further comprise, for example, providing reactants to the mixing device as described above. For example, the reactants may be supplied upstream of the inlets used to provide one or more precursors to the mixing device. An exemplary method may further comprise pulsing the reactants to the gas injection port. In such a case, the step of pulsing the reactants and the step of pulsing the mixture may be performed separately in time. In some cases, a combination of reactants and mixture is pulsed to the gas injection port. In some cases, the reactants, the first precursor, and the second precursor are mixed within the mixing device to form a gas mixture. Such a mixture may be pulsed to the gas injection port and / or the reaction chamber.

[0069] According to a further embodiment, the deposition process may comprise purging one or more of the pulse valves using a purge gas. According to yet a further embodiment, the deposition process may comprise controlling the flow of an inert gas to one or more of the first gas source, the second gas source, and / or the third gas source.

[0070] The above exemplary embodiments are merely examples of embodiments of the present invention, and these exemplary embodiments of the present disclosure do not limit the scope of the present invention. For example, although an example having three gas supply sources is illustrated, it is also possible to configure an embodiment having two, four, or more gas supply sources, which may have the same configuration as the illustrated embodiment. Any equivalent embodiments are intended to be within the scope of the present invention. Also, various modifications of the present disclosure will be apparent to those skilled in the art from this description, in addition to those illustrated and described in the present disclosure, such as alternative useful combinations of the described elements. Such modifications and embodiments are also intended to be included within the scope of the appended claims.

Claims

1. A deposition process comprising: a gas injection port; a mixing device upstream of the gas injection port and in fluid communication with the gas injection port; a first container and a first gas supply source for containing a reactant in the first container; a second container and a second gas supply source for containing a first precursor in the second container; a first gas pulse valve fluidly connected to the first container and the mixing device; a second gas pulse valve fluidly connected to the second container and the mixing device; an apparatus comprising: the mixing device having a first inlet and a second inlet; the first inlet being upstream of the second inlet; preparing the apparatus; supplying the reactant to the mixing device through the first inlet; supplying the first precursor to the mixing device through the second inlet, the deposition process.

2. The deposition process according to claim 1, wherein supplying the reactant to the mixing device comprises pulsing the reactant to the mixing device.

3. The deposition process according to claim 1, wherein supplying the first precursor to the mixing device comprises pulsing the first precursor to the mixing device.

4. The deposition process according to claim 1, further comprising maintaining a steady state pressure in the first container and providing a controlled flow of the reactant to the mixing device.

5. The deposition process according to claim 1, further comprising supplying a second precursor to the mixing device and mixing the second precursor with the first precursor in the mixing device.

6. The deposition process according to claim 1, further comprising supplying a purge gas to the first gas pulse valve to purge the first gas pulse valve.

7. The deposition process according to claim 1, further comprising forming a plasma.

8. A deposition process comprising: a gas injection port; a mixing device upstream of the gas injection port and in fluid communication with the gas injection port; a first container and a first gas supply source for containing a first precursor in the first container; a second container and a second gas supply source for containing a second precursor in the second container; an apparatus comprising: the mixing device having a first inlet and a second inlet; wherein the first inlet is upstream of the second inlet, providing the apparatus, a deposition process comprising pulsing a mixture of the first precursor and the second precursor from the mixing device to the gas injection port. **Claim 9** The deposition process according to claim 8, further comprising supplying a reactant to the mixing device. **Claim 10** The deposition process according to claim 9, wherein the reactant is supplied to the first inlet and upstream of the first precursor and the second precursor. **Claim 11** The deposition process according to claim 9, further comprising pulsing the reactant to the gas injection port, wherein the step of pulsing the reactant and the step of pulsing the mixture are performed in a temporally separated manner. **Claim 12** The deposition process according to claim 9, wherein a combination of the reactant and the mixture is pulsed to the gas injection port. **Claim 13** The deposition process according to claim 8, further comprising a step of purging a pulse valve using a purge gas. **Claim 14** The deposition process according to claim 8, further comprising controlling a flow of an inert gas to the first gas supply source. **Claim 15** The deposition process according to claim 14, further comprising controlling the flow of the inert gas to the second gas supply source. **Claim 16** An apparatus for supplying a gas mixture to a reaction chamber, comprising: a gas injection port; a mixing device upstream of the gas injection port and in fluid communication with the gas injection port; a first container and a first gas supply source for containing a reactant therein; a second container and a second gas supply source for containing a first precursor therein; a third container and a third gas supply source for containing a second precursor therein; a first gas valve fluidly connected to the first container and the mixing device; a second gas valve fluidly connected to the second container and the mixing device; wherein the mixing device has a first inlet, a second inlet, and a third inlet, the first inlet is upstream of the second inlet, the second inlet is upstream of the third inlet, the reactant is supplied to the first inlet, the first precursor is supplied to the second inlet, and the second precursor is supplied to the third inlet. **Claim 17** The apparatus according to claim 16, further comprising a controller configured to supply the reactant to the first inlet.

18. The apparatus according to claim 17, wherein the controller is configured to supply the reactant to the first inlet after a predetermined number of deposition cycles.

19. The apparatus according to claim 17, wherein the reactant, the first precursor, and the second precursor are mixed in the mixing device to form the gas mixture.

20. The apparatus according to claim 16, further comprising a pulse valve between the mixing device and the gas injection port.

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