Apparatus for providing gas mixture to reaction chamber and method of using same

Abstract

Apparatus for mixing two or more gases prior to entering a reaction chamber, reactor systems including the apparatus, and methods of using the apparatus and systems are disclosed. Systems and methods as described herein can be used, for example, to pulse a mixture of two or more precursors to a reaction chamber.

Description

[0001] Cross - Reference to Related Applications

[0002] This application is a partial continuation application that claims the priority of Application No. 17 / 842,057, titled "APPARATUS FOR PROVIDING A GAS MIXTURE TO A REACTION CHAMBER AND METHOD OF USING SAME", filed on June 16, 2022. This application is a non - provisional application of U.S. Provisional Patent Application No. 63 / 213,089, titled "APPARATUS FOR PROVIDING A GAS MIXTURE TO A REACTION CHAMBER AND METHOD OF USING SAME", filed on June 21, 2021, and claims its priority and benefits. Their respective contents are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to gas - phase reactor systems and methods 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

[0004] Gas - phase reactors (such as chemical vapor deposition (CVD), plasma - enhanced CVD (PECVD), atomic layer deposition (ALD), etc.) can be used for various applications, including depositing and etching materials on a substrate surface. For example, a gas - phase reactor can be used to deposit and / or etch layers on a substrate to form semiconductor devices, flat - panel display devices, photovoltaic devices, micro - electro - mechanical systems (MEMS), etc.

[0005] A typical gas - phase reactor system includes one or more reactors, each reactor including one or more reaction chambers; one or more precursor and / or reactant gas sources fluidly coupled to the reaction chambers; one or more carrier gas sources and / or purge gas sources fluidly coupled to the reaction chambers; one or more gas distribution systems for delivering gases (e.g., (multiple) precursor / reactant gases and / or (multiple) carrier or purge gases) to the substrate surface within the reaction chamber; and at least one exhaust source fluidly coupled to the reaction chamber.

[0006] In some processes carried out in the reaction chamber, it may be desirable to provide two or more gases to the reaction chamber simultaneously or with temporal overlap. For example, two, three, four, or more gases can be provided to the reaction chamber separately, either simultaneously or with temporal overlap. While such an apparatus may be suitable for some applications, providing gases to the reaction chamber separately may result in undesirable variability in the process. Therefore, there is a need for an improved apparatus for providing a gas mixture to the reaction chamber.

[0007] Any discussion of the problems and solutions involved in the related art has been included in this disclosure solely to provide the background of this disclosure and should not be construed as an admission that any or all of the discussion was known at the time the present invention was made. Summary of the Invention

[0008] Various embodiments of the present disclosure relate to apparatuses for providing a gas mixture to a reactor or reaction chamber, systems including such apparatuses, and methods of using such apparatuses and systems. The apparatuses, systems, and methods can be used in conjunction with various applications, including, for example, the manufacture of electronic devices. Although the manner in which various embodiments of the present disclosure address the shortcomings of existing methods and systems is discussed in more detail below, generally speaking, the various embodiments of the present disclosure provide improved apparatuses, systems, and methods suitable for providing a mixture of two or more gases to a reaction chamber. Exemplary apparatuses can, for example, reduce the time scale of gas diffusion, thereby improving gas mixing and / or reducing the amount of time the gas mixture is mixed before entering the reaction chamber. Further examples of the present disclosure provide improved apparatuses and methods for providing pulses of the mixed gas.

[0009] 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 and in fluid communication with the gas injection port, a first gas source including a first container and a first precursor therein, a second gas source including a second container and a second precursor therein, a first gas pulse valve fluidly coupled to the first container and the mixing device, a second gas pulse valve fluidly coupled to the second container and the mixing device, and a first pressure flow control valve fluidly coupled 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 coupled 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 coupled to the mixing device.

[0010] According to a further example 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 and in fluid communication with the gas injection port, a first gas source including a first container and a first precursor therein, a second gas source including a second container and a second precursor therein, a first gas valve fluidly coupled to the first container and the mixing device, a second gas valve fluidly coupled to the second container and the mixing device, a first pressure flow control valve fluidly coupled between the first container and a carrier gas source, and a pulse valve between the mixing device and the gas injection port. Similar to the above, the gas injection port may form part of a 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 valve in fluid communication with a purge gas source and the pulse valve. According to a further example of the present disclosure, the apparatus includes three, four, or more gas sources coupled to the mixing device.

[0011] 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 may include: a first section including a first inlet, a first outlet, and a first volume 403 therebetween; and a second section including a second inlet, a second outlet, and a second volume 419 therebetween. The first inlet may be upstream of the second inlet, the first outlet may be downstream of the second inlet, and / or the first outlet may be upstream of the second outlet. According to a further example, the mixing device may further include a third section. The third inlet may be downstream of the second inlet and upstream of the second outlet, the second outlet may be within the third volume, and / or the first outlet may be within the second volume.

[0012] According to a further embodiment of the present disclosure, a method of controlling the gas flow to a reaction chamber using the apparatus as described herein is disclosed.

[0013] According to a further example of the present disclosure, a system including the apparatus as described herein is disclosed.

[0014] According to further embodiments of the present disclosure, a deposition process is provided. By way of example 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 gas source, a second gas source, a first gas pulse valve, and a second gas pulse valve, where the first gas source includes a first container and the reactants therein, the second gas source includes a second container and the first precursor therein, the first gas pulse valve is fluidly coupled to the first container and the mixing device, and the second gas pulse valve is fluidly coupled to the second container and the mixing device. As described above, the mixing device may be suitably located upstream of the gas inlet port and in fluid communication with the gas inlet port. The mixing device may include a first inlet and a second inlet, where the first inlet is 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 herein. By way of example of these embodiments, the step of providing reactants to the mixing device includes pulsing the reactants into the mixing device. By a further example, the step of providing the first precursor to the mixing device includes pulsing the first precursor into the mixing device. By a further example, the method includes maintaining a steady state pressure within the first container to provide a controlled flow of reactants to the mixing device. In some instances, the process includes providing a second precursor to the mixing device and mixing the second precursor with the first precursor within the mixing device. By a further example, the process includes forming a plasma—for example, within a reaction chamber.

[0015] According to further embodiments of the present disclosure, a deposition process includes providing an apparatus including a gas injection port, a mixing device upstream of and in fluid communication with the gas injection port, a first gas source including a first container and a first precursor therein, and a second gas source including a second container and a second mixture precursor therein; and pulsing a mixture of the first precursor and the second precursor from the mixing device to the gas injection port. By way of example of these embodiments, the mixing device includes a first inlet and a second inlet, where the first inlet is upstream of the second inlet. The method may further include 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 embodiments of these embodiments, the method includes pulsing the reactants to the gas injection port, where the step of pulsing the reactants and the step of pulsing the mixture are temporally separated—i.e., not overlapping in time. By a further example, a combination of the reactants and the mixture is pulsed to the gas injection port.

[0016] According to another exemplary 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 and in fluid communication with the gas injection port, a first gas source including a first container and a reactant therein, a second gas source including a second container and a first precursor therein, a third gas source including a third container and a second precursor therein, 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 includes a first inlet, a second inlet, and a third inlet, where the first inlet is upstream of the second inlet, where the second inlet is upstream of the third inlet, where the reactant is provided to the first inlet, where the first precursor is provided to the second inlet, and where the second precursor is provided to the third inlet. According to an example 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 (e.g., only) after a predetermined number of deposition cycles or pulses of the first precursor, the second precursor, and / or the gas mixture to the reaction chamber. In some cases, the first precursor and the second precursor are mixed within the mixing device to form a gas mixture. According to another example of the present disclosure, the apparatus further includes a pulse valve between the mixing device and the gas injection port.

[0017] These and other embodiments will become apparent to those skilled in the art from a detailed description of certain embodiments with reference to the accompanying drawings; the invention is not limited to any particular embodiment disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by reference to the detailed description and the claims when considered in conjunction with the following illustrative drawings.

[0019] Figure 1 A reactor system including an apparatus according to at least one embodiment of the present disclosure is shown.

[0020] Figure 2 A reactor according to an example of the present disclosure is shown.

[0021] Figure 3 Another apparatus according to the present disclosure is shown.

[0022] Figure 4 A gas mixing device according to an example of the present disclosure is shown.

[0023] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0024] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Accordingly, it is intended that the scope of the invention as disclosed should not be limited by the specific disclosed embodiments described below.

[0025] This disclosure generally relates to gas-phase apparatuses, reactor systems, and methods (also referred to herein as processes). The apparatuses, systems, and methods described herein can be used to process substrates, such as semiconductor wafers, to form, for example, electronic devices. By way of example, the systems and methods described herein can be used to form or grow multiple sets of layers, such as a crystalline or amorphous indium gallium zinc oxide or a crystalline or amorphous mixture comprising at least two of indium, gallium, or zinc and oxygen or a crystalline or amorphous mixture comprising at least one of indium, gallium, or zinc and at least a second metal or metalloid and oxygen.

[0026] In this disclosure, "gas" can include materials that are gases at normal temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and can consist of a single gas or a gas mixture, depending on the context. Gases other than the process gas (i.e., gases introduced without passing through a gas distribution assembly, other gas distribution devices, etc.) can be used, for example, to seal the reaction space and can include seal gases, such as noble gases.

[0027] 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 or include an inert gas.

[0028] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which a device, circuit, or film can be formed. The substrate can comprise a bulk material, such as silicon (e.g., single-crystalline silicon), other Group IV materials (e.g., germanium), or compound semiconductor materials (e.g., GaAs), and can comprise one or more layers overlying or underlying the bulk material. Additionally, the substrate can include various topologies, such as recesses, lines, etc., formed within or on at least a portion of the layers of the substrate.

[0029] The term "cyclic deposition process" or "cyclic deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit 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 an ALD component and a cyclic CVD component. The method can include a purge step between the introduction of precursors. In some cases, one or more reactants and / or precursors can be continuously supplied to the reaction chamber, and one or more other reactants and / or precursors can be pulsed into the reaction chamber. In some cases, the plasma power can be pulsed - for example, each cycle of the cyclic deposition process can include one or more plasma power pulses.

[0030] The term "atomic layer deposition" can refer to a vapor deposition process in which deposition cycles are performed in a processing chamber, typically a plurality of consecutive deposition cycles. As used herein, the term "atomic layer deposition" is also intended to include processes designated by related terms, such as chemical vapor atomic layer deposition when performed with alternating pulses of a precursor / reactant gas and a purge gas (e.g., an inert carrier gas).

[0031] As used herein, the term "plasma-enhanced atomic layer deposition" (PEALD) can 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.

[0032] In addition, in the present disclosure, any two numbers of a variable can constitute a workable range of the variable, and any indicated range can include or exclude endpoints. Additionally, any value of the indicated variable (whether or not they are indicated with "about") can refer to an exact value or an approximate value and include equivalents, and can refer to an average value, a median value, a representative value, a majority value, etc. Further, in the present disclosure, the terms "comprising," "consisting of," and "having" can independently refer to "generally or broadly encompassing," "including," "substantially consisting of," or "consisting of" in some embodiments. In the present disclosure, the meaning of any defined term does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0033] Turning now to the drawings, Figure 1 A reactor system 100 is shown in accordance with at least one embodiment of the present disclosure. The reactor system 100 includes a reaction chamber 102, an apparatus 104 for supplying a gas mixture to the reaction chamber 102, a vacuum source 106, and a controller 108.

[0034] The reaction chamber 102 can be or include a reaction chamber suitable for gas-phase reactions. The reaction chamber 102 can be formed of a suitable material, such as quartz, metal, etc., and can be configured to hold one or more substrates for processing. The reactor system 100 can include any suitable number of reaction chambers 102, and can optionally include one or more substrate handling systems.

[0035] The reaction chamber 102 can be configured as a CVD reactor, a cyclic deposition process reactor (such as a cyclic CVD reactor), an ALD reactor, a PEALD reactor, etc., any of which can include plasma devices, such as direct and / or remote plasma devices.

[0036] Figure 2 An exemplary apparatus 200 suitable for use as a PEALD reactor is shown. The apparatus 200 includes a reaction chamber 3, which is suitable for use as the reaction chamber 102 and / or is connected to the system 100 (i.e., as part of the system 100).

[0037] As Figure 2 shown, by providing a pair of conductive plate electrodes 2, 4 that can be arranged in parallel and facing each other in the interior 11 (reaction zone) of the reaction chamber 3, applying RF power (such as 13.56 MHz and / or 27 MHz) from a power source 25 to one side, and grounding the other side 12, a plasma can be generated between the electrodes 2, 4. A temperature regulator can be provided in the lower platform 2 (i.e., the lower electrode). The substrate 1 is placed on the platform / lower electrode 2, and the temperature of the platform 2 and / or the substrate can be maintained at a desired temperature. The upper electrode 4 can be used as a gas distribution device, such as a shower plate, etc., and various gases (such as plasma gases, reactant gases, and / or dilution gases (if any)) and gas mixtures can be introduced into the reaction chamber 3 through the gas line 21 and the gas line 22 and through the shower plate 4. For example, a gas mixture (such as containing two or more precursors) from the device 104 for supplying the gas mixture to the reaction chamber can be provided to the gas injection port 26 via the line 22, and the reactant from the reactant source 27 can be provided to the gas injection port 26 via the line 21. As shown in the figure, the line 21 can ideally be upstream of the line 22.

[0038] In the reaction chamber 3, a circular conduit 13 having an exhaust pipe line 7 is provided, and the gas in the interior 11 of the reaction chamber 3 is discharged through this conduit. Additionally, a transfer chamber 5 is provided below the reaction chamber 3, and a gas seal line 24 is provided to introduce a sealing gas into the interior 11 of the reaction chamber 3 via the interior 16 of the transfer chamber 5, where a separation plate 14 for separating the reaction zone and the transfer zone is provided. Gate valves are omitted from this figure, through which the substrate can be transferred into the transfer chamber 5 or from the transfer chamber 5. The transfer chamber is also provided with an exhaust pipe line 6.

[0039] Return to Figure 1 The apparatus 104 for supplying a gas mixture to the reaction chamber includes a gas injection port 110, a mixing device 112, a first gas source 114, a second gas source 116, a third gas 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 sources 132, a purge valve 134, and a purge gas source 136. The apparatus 104 can be used to mix gases from two or more gas sources 114 - 118 by supplying pulses of two or more gases to the mixing device 112, which is located downstream of the pulse valves. The apparatus 104 allows flexibility in timing (e.g., one gas can start before or after the other gases flow to the mixing device 112). Additionally, the apparatus 104 can be easily switched to a single gas injection system without delay.

[0040] The gas injection port 110 can include a pipe or the like to supply the gas mixture to the reaction zone of the reaction chamber. The gas injection port 110 can be integrated into the reaction chamber 102 or can be separate. Figure 2 An exemplary gas syringe port 26 suitable for use as the injection port 110 is shown in

[0041] The mixing device 112 is configured to receive two or more gases from, for example, two or more of the first gas source 114, the second gas source 116, and the third gas source 118 before entering the reaction chamber 102. As shown, the mixing device 112 can be upstream of the gas injection port 110 and in fluid communication with the gas injection port 110. The mixing device 112 can include a volume greater than the volume of the gas injection port 110 / 26. For example, the volume of the mixing device 112 can range from about 5 cc to about 50 cc. The configuration of the mixing device 112 can vary depending on the application. The mixing device 112 can include a tortuous path or can be configured as a static mixer. In some cases, the mixing device 112 can include a housing 138, which can be, for example, a substantially hollow cylinder with caps on each end. Another example of a suitable mixing device is discussed in more detail below in connection with Figure 4 Another example of a suitable mixing device is discussed in more detail below.

[0042] The first gas source 114, the second gas source 116, and the third gas source 118 may each include a container and a precursor stored in the respective container. For example, the first gas source 114 may include a container and an indium precursor; the second gas source 116 may include a container and a gallium precursor; and the third gas source 118 may include 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 shown as having three gas sources 114-118, the exemplary device may include any suitable number (e.g., four or more) of two or more gas sources coupled to the mixing device 112. Additionally, the reactor system 100 or the device 104 for providing a gas mixture to the reaction chamber may include a reactant source 142, which may be coupled to the gas injection port 110 and / or the mixing device 112. The reactant source 142 may include one or more reactant containers and one or more reactant sources. The reactant source may include one or more of an oxygen reactant, a nitrogen reactant, and / or a carbon reactant. As discussed in more detail below, according to an example 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 includes or is configured to provide multiple reactants, such as multiple oxygen reactants (e.g., H2O and O3), to the mixing device simultaneously or substantially simultaneously (e.g., as defined herein). As shown, the reactor system 100 may also include an excitation source 146, such as a remote plasma unit or an ozone generator, to form an excited species from the reactants from the reactant source 142, which may flow to the mixing device 112 and / or the gas injection port 110.

[0043] Two or more or each of the first gas source 114, the second gas source 116, and the third gas source 118 may be connected to the mixing device 112 using pulse valves. Additional gas sources may be similarly connected to the mixing device 112. For example, as shown, the first gas source 114 (e.g., its container) may be connected to the mixing device 112 via the first gas pulse valve 120; the second gas source 116 (e.g., its container) may be connected to the mixing device 112 via the second gas pulse valve 122; and the third gas source 118 (e.g., its container) may be connected to the mixing device 112 via the third gas pulse valve 124. The apparatus 104 and / or the reactor system 100 may further 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 may be used to provide a desired amount (pulse) of gas to the mixing device 112 (or the gas injection port 110). By way of example, one or more of the gas pulse valves 120 - 124, 144 or other pulse valves described herein may include pneumatic or electric solenoid valves.

[0044] As further shown, carrier gas from the carrier gas source 132 (which may include one or more carrier gas sources) may be used to supply one or more of the first precursor, the second precursor, and / or the third precursor to the reaction chamber 102 and / or additional gas (e.g., a fourth gas) as described herein. In the example shown, the carrier gas source 132 is connected to the first pressure flow control valve 126 to supply a desired concentration of the first precursor to the first gas pulse valve 120; the carrier gas source 132 is connected to the second pressure flow control valve 128 to supply a desired concentration of the second precursor 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 a desired concentration of the third precursor to the third gas pulse valve 124. The pressure control valves 126, 128, 130 may be used to maintain a stable / desired pressure within the respective first, second, and third containers to provide a controlled flow of the respective first, second, and third precursors. By way of example, the pressure control valve may be or include a pressure flow controller or a mass flow controller.

[0045] The vacuum source 106 may include, for example, one or more vacuum sources. Exemplary vacuum sources include one or more dry vacuum pumps and / or one or more turbo molecular pumps.

[0046] The controller 108 can be configured to perform various functions and / or steps as described herein. The controller 108 can include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although shown as a single unit, the controller 108 can alternatively include multiple devices. For example, the controller 108 can 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 to the reaction chamber 102. In some cases, the controller 108 can be used to pulse two or more precursors (e.g., from sources 114 - 118) and / or reactants from the reactant source 142 to the mixing device 112 and / or the gas injection port 110. As another example, the controller 108 can 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., by mass) of two or more precursors to the mixing device 112. In Figure 1 the example shown, the controller 108 can be configured to open each pulse valve 120 - 124 substantially simultaneously (e.g., within about 0.001 or about 0.005 seconds). The duration of the pulse as described herein can be from about 0.01 to about 600 seconds or from about 0.02 to about 10 seconds.

[0047] The system 100 can also include a purge valve 134 that is fluidly coupled to a purge gas source 136 and fluidly coupled 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 can be coupled to the controller 108 and is used to purge the pulse valves 120 - 124 and the mixing device 112. The purge gas source 136 can include a container and a purge gas therein, such as one or more of nitrogen, argon, helium, etc. The purge valve 134 can be, for example, a pneumatic or electromagnetic type valve.

[0048] Now turning to Figure 3 , another device 300 for providing a gas mixture to a reaction chamber is shown. The device 300 is configured to mix gases upstream of the pulse valve. This configuration allows for a larger mixing volume and can facilitate more complete mixing of one or more gases within the mixing device. The device 300 can be used in place of the device 104 in a reactor system (e.g., reactor system 100).

[0049] The device 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 ( Figure 3(not shown separately), a pulse valve 324, and a purge gas source 326. The apparatus 300 includes a pulse valve 324 between the mixing device 304 and the gas injection port 302 such that gas mixing in the mixing device 304 occurs upstream of the pulse valve 324. The apparatus (or system) 300 may also include a reactant gas source 142 and a pulse valve 144 as described above in connection with Figure 1 as described.

[0050] The gas injection port 302, the mixing device 304, the first gas source 306, the second gas source 308, the third gas 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 sources, and the purge gas source 326 may be the same as or similar to the gas injection port 110, the mixing device 112, the first gas source 114, the second gas source 116, the third gas 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 sources 132, and the purge gas source 136 described above in connection with Figure 1 The apparatus 300 may also include a bypass valve 328 and a purge valve 330. The bypass valve 328 may be a pneumatic or electromagnetic type valve, and the purge valve 330 may be the same as or similar to the purge valve 134.

[0051] As described above, the first pressure flow control valve 126, the second pressure flow control valve 128, and / or the third pressure flow control valve 130 may be used to control the amount of carrier gas flowing to the respective first gas source 306, second gas source 308, and third gas source 310 by controlling the (e.g., steady) pressure within the respective container, thereby controlling the flow rate and / or the desired or predetermined concentration of the precursor from the gas source to the mixing device 304. For example, the gas amount of each gas from sources 306 - 310 may be set by the source vapor pressure / carrier gas pressure ratio, where the carrier gas pressure is controlled by the respective first pressure flow control valve 126, second pressure flow control valve 128, and third pressure flow control valve 130. The carrier gas / precursor flow may be controlled by, for example, a fixed orifice, a needle valve, a mass flow controller, or a volume flow controller.

[0052] The first gas valve 312, the second gas valve 314, and the third gas valve 316 may include pneumatic or electromagnetic type valves and / or may form part of a flow meter and / or a mass flow controller. In the illustrated example, the first gas valve 312, the second gas valve 314, and the third gas valve 316 supply metered amounts of the first gas, the second gas, and the third gas from the first gas source 306, the second gas source 308, and the third gas source 310 to the mixing device 304.

[0053] 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 valve or such valves) form part of a mass flow controller. In these cases, a setpoint for the mass flow controller can determine the composition of the gas mixture within the mixing device 304, which is provided to the injection port 302. An exemplary sequence for providing the gas mixture to the injection port 302 can include filling the mixing device 304 by opening the gas using the first gas valve 312, the second gas valve 314, and the third gas valve 316 and (e.g., controllably) flowing the gas to the mixing device 304. Substantially simultaneously, the first gas valve 312, the second gas valve 314, the third gas valve 316, and the pulse valve 324 can be opened to supply the gas mixture to the injection port 302. One or more controllers (such as controller 108) can be used to control the valves.

[0054] The pulse valve 324 can be used to pulse the gas mixture from the mixing device 304 and / or the purge gas from the purge gas source 326 and / or the reactant from the mixing device 304 or the reactant source 142 to the gas injection port 302. According to an example 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 at approximately the same time (e.g., within about 0.001 or about 0.005 seconds) to pulse the gas (e.g., mixture) into the reaction chamber, such as the reaction chamber 102.

[0055] According to a further example of the present disclosure, the device 300 includes a pressure monitor 332 to measure the pressure of the mixing device 304. In these cases, the controller (e.g., controller 108) can be further configured to fill the mixing device 304 to a desired (e.g., set) pressure. Once the pressure is reached, the first gas valve 312, the second gas valve 314, and the third gas valve 316 are closed. Alternatively, the first gas valve 312, the second gas valve 314, and the third gas valve 316 can be opened to a set flow rate for a period of time to fill the mixing device 304. In these cases, there is no significant additional volume downstream of the pulse valve 324 and between the mixing device 304 and the gas injection port 302.

[0056] 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 the reaction chamber.

[0057] The controller 108 or one or more similar controllers can be used to control the valves 144, 312 - 320, 324, 330, and 328, set and monitor the pressure using the pressure monitor 332, and perform the operations described herein in connection with Figure 1-3Other functions described.

[0058] Figure 4 A mixing device 400 suitable for use as mixing device 112 or 304 is shown. The mixing device 400 includes a first part 402, a second part 404, and a third part 406. As shown, the first part 402, the second part 404, and the third part 406 may be cascaded such that the outlet of the first part 402 is within the second part 404, and the outlet of the second part 404 is within the third part 406. Additionally or alternatively, the first part 402, the second part 404, and the third part 406 may be coaxial—e.g., about an axis 408. Although shown with three parts, a cascaded mixing device may suitably include two or more parts as described herein.

[0059] The first part 402 includes a first inlet 410 having a diameter D4, a first outlet 412 having a diameter D3, and a volume 403 therebetween. In the illustrated example, D3 is greater than D4.

[0060] The second part 404 may include one or more second inlets 414, 415, 416, 417, a second outlet 418, and a second volume therebetween. The diameter D2 of the outlet 418 may be greater than the diameter of one or more (individually or in total) of the inlets 414, 416. Additionally, the diameter of D2 may be greater than D3 and / or D4.

[0061] As shown, the first inlet 410 may be upstream of the second inlets 414, 416. Additionally, the first outlet 412 may be downstream of the second inlets 414, 416 (e.g., for one or more gases). And, the first outlet 412 may be upstream of the second outlet 418.

[0062] The third part 406 may include one or more third inlets 420, 421, a third outlet 422, and a volume 423 therebetween. The third outlet 422 may be coupled to a reaction chamber, a gas injection port, and / or one or more (e.g., pulse) valves as described herein. The volume 423 may have a diameter of D1 or a similar cross-section, where D1 may be greater than D2, D3, and / or D4. Additionally, as shown, the third inlet 420 is downstream of the second inlets 414, 416 and upstream of the second outlet 418.

[0063] According to an example of the present disclosure, one or more reactants are provided to a mixing device upstream of one or more precursors. For example, a reactant may be provided to the first inlet 410, a first precursor may be provided to the second inlet 414 or another inlet downstream of the first inlet 410, and a second precursor may be provided to the third inlet 420 or another inlet downstream of the first inlet 410.

[0064] ReferenceFigure 1 and Figure 4 ,a controller (e.g., controller 108) can be configured (e.g., selectively) to provide reactants to the first inlet—e.g., via pulse valve 144 or gas injection port 110. For example, controller 108 can be configured to provide reactants 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.

[0065] In accordance with various examples of the present disclosure, a deposition process is provided. An exemplary deposition process can use the reactor system 100, the apparatus 300, and / or the mixing device 400 described above. For example, an exemplary deposition process can include providing a reactor system or apparatus as described herein, providing reactants, and providing at least one precursor. More specifically, an exemplary deposition process can include providing an apparatus that includes a gas injection port, a mixing device upstream of and in fluid communication with the gas injection port, a first gas source that includes a first container and reactants therein, a second gas source that includes a second container and a first precursor therein, a first gas pulse valve fluidly coupled to the first container and the mixing device, and a second gas pulse valve fluidly coupled to the second container and the mixing device, where the mixing device includes a first inlet and a second inlet, and where the first inlet is upstream of the second inlet; providing reactants to the mixing device through the first inlet; and providing the first precursor to the mixing device through the second inlet. Providing reactants to the mixing device upstream of the precursor can reduce particle formation and / or spalling of the grown film (which might otherwise occur) and / or increase the life of the mixing device. Reactants can be introduced during a deposition cycle that includes pulsing a mixture of precursors and separately pulsing reactants. Additionally or alternatively, the deposition process can include periodically pulsing reactants to the mixing device after processing a plurality of deposition cycles and / or a plurality of substrates to extend the life of the mixing device—i.e., the period of time during which the mixing device can be used without cleaning or refurbishment. 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 excited species thereof (e.g., formed by plasma or other excitation sources), etc.). Such periodic pulsing can occur, for example, before or after processing a substrate. For example, reactants can be supplied to the mixing device when there is no substrate in the reaction chamber. The reactants used to condition the mixing device and the reactants for the deposition reaction can be the same or different and can include multiple reactants (e.g., H2O and O3, or any other combination of reactants described herein). When multiple reactants are provided to the mixing device, at least one or each reactant can desirably be provided upstream of any precursor. For example, referring to Figure 4 .

[0066] In some embodiments, the material grown upstream of the gas injection port and / or in the mixing device has a density that is from about 50% to about 120%, from about 70% to about 110%, from about 80% to about 100%, from about 85% to about 99% of the bulk density of the growth material. In some embodiments, the material grown upstream of the gas injection port and / or in the mixing device has impurities of <30 atomic %, <20 atomic %, <10 atomic %, <7 atomic %, <5 atomic %, <3 atomic %, <2 atomic % or <1 atomic %, such as halides e.g. Cl or carbon. In some embodiments, when compared to the material grown on the substrate, the material grown upstream of the gas injection port and / or in the mixing device has impurities of 50% to about 500%, 90% to about 300%, 100% to about 250%, 105% to about 200%, 105% to about 200%, 105% to about 200%, such as halides e.g. Cl or carbon.

[0067] According to examples of these embodiments, the deposition process can include pulsing reactants into the device. For example, a pulse valve 144 can be used to pulse a reactant (e.g., an oxidizer) into the mixing device.

[0068] The deposition process can also include providing a second precursor and / or a third precursor to the mixing device. As described above, the first precursor, the second precursor, and / or the third precursor can be pulsed into the mixing chamber. Two or more of the first precursor, the second precursor, and the third precursor can be mixed within the mixing device.

[0069] According to examples of the present disclosure, the steady-state pressure within the first container for supplying the first precursor, the second container for supplying the second precursor, the third container for supplying the third precursor, and / or the reactant container for supplying the reactant is maintained at a steady-state pressure (e.g., within about + / -10% or + / -5% or + / -2% of the target pressure) to provide a controlled reaction stream to the mixing device.

[0070] An exemplary deposition process can also include providing a purge gas to one or more gas pulse valves (such as the gas pulse valve described above) to purge the gas pulse valves.

[0071] According to additional examples, the deposition process can include the step of forming a plasma. For example, a remote excitation source such as a remote excitation source (e.g., a remote plasma unit) 146 can be used to form an excited species from one or more reactants before introduction into the mixing device and / or the gas injection port.

[0072] According to a further example of the present disclosure, a deposition process includes providing an apparatus that includes a gas injection port, a mixing device upstream of and in fluid communication with the gas injection port, a first gas source including a first container and a first precursor therein, and a second gas source including a second container and a second precursor mixture therein, where the mixing device includes a first inlet and a second inlet, where 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 include providing reactants to the mixing device—such as as described above. For example, reactants may be provided upstream of an inlet for providing one or more precursors to the mixing device. Exemplary methods may further include pulsing the reactants to the gas injection port. In such a case, the steps of pulsing the reactants and pulsing the mixture may be separated in time. In some cases, a combined pulse of the reactants and the 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 a reaction chamber.

[0073] According to a further example, the deposition process may include the step of purging one or more of the pulse valves with a purge gas. According to a further example, the deposition process may include controlling an inert gas flow to one or more of the first gas source, the second gas source, and / or the third gas source.

[0074] The example embodiments of the present disclosure described above do not limit the scope of the invention because these embodiments are merely examples of embodiments of the invention. For example, although three gas sources are shown, the examples may include two, four, or more gas sources that may be configured in a manner similar to the shown examples. Any equivalent embodiments are intended to fall within the scope of the invention. Indeed, various modifications of the present disclosure, such as alternative useful combinations of the described elements, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A deposition process, comprising: Providing an apparatus, the apparatus comprising: A gas injection port; A mixing device, which is upstream of the gas injection port and in fluid communication with the gas injection port; A first gas source, which includes a first container and a reactant therein; A second gas source, which includes a second container and a first precursor therein; A first gas pulse valve, which is fluidly coupled to the first container and the mixing device; and A second gas pulse valve, which is fluidly coupled to the second container and the mixing device, wherein the mixing device includes a first inlet and a second inlet, and wherein the first inlet is upstream of the second inlet, Providing the reactant to the mixing device through the first inlet; and Providing the first precursor to the mixing device through the second inlet.

2. The deposition process according to claim 1, wherein The step of providing the reactant to the mixing device includes pulsing the reactant into the mixing device.

3. The deposition process according to claim 1, wherein, The step of providing the first precursor to the mixing device includes pulsing the first precursor into the mixing device.

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

5. The deposition process according to claim 1, further comprising providing 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 providing 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 the step of forming a plasma.

8. A deposition process, comprising: Providing an apparatus, the apparatus comprising: A gas injection port; A mixing device, which is upstream of the gas injection port and in fluid communication with the gas injection port; A first gas source, which includes a first container and a first precursor therein; and A second gas source, which includes a second container and a second mixture precursor therein, wherein the mixing device includes a first inlet and a second inlet, and wherein 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.

9. The deposition process according to claim 8, further comprising providing a reactant to the mixing device.

10. The deposition process according to claim 9, wherein, The reactant is provided to the first inlet and is provided upstream of the first precursor and the second precursor.

11. The deposition process according to claim 9, further comprising pulsing the reactant to the gas injection port, wherein the steps of pulsing the reactant and pulsing the mixture are temporally separated.

12. The deposition process according to claim 9, wherein, The combination of the reactant and the mixture is pulsed to the gas injection port.

13. The deposition process according to claim 8, further comprising the step of purging the pulse valve with a purge gas.

14. The deposition process according to claim 8, further comprising controlling the flow rate of an inert gas to the first gas source.

15. The deposition process according to claim 14, further comprising controlling the flow rate of the inert gas to the second gas source.

16. An apparatus for providing a gas mixture to a reaction chamber, the apparatus comprising: A gas injection port; A mixing device, which is upstream of the gas injection port and in fluid communication with the gas injection port; A first gas source, which includes a first container and reactants therein; A second gas source, which includes a second container and a first precursor therein; A third gas source, which includes a third container and a second precursor therein; A first gas valve, which is fluidly coupled to the first container and the mixing device; And A second gas valve, which is fluidly coupled to the second container and the mixing device, wherein the mixing device includes a first inlet, a second inlet, and a third inlet, wherein the first inlet is upstream of the second inlet, wherein the second inlet is upstream of the third inlet, wherein the reactants are provided to the first inlet, wherein the first precursor is provided to the second inlet, and wherein the second precursor is provided to the third inlet.

17. The apparatus according to claim 16, further comprising a controller configured to provide the reactants to the first inlet.

18. The device according to claim 17, wherein, The controller is configured to provide the reactants to the first inlet after a predetermined number of deposition cycles.

19. The device according to claim 17, wherein, The reactants, the first precursor, and the second precursor are mixed within 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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