Semiconductor cleaning to remove fluorine-containing byproducts

Abstract

Exemplary cleaning methods may include etching an aluminum-containing material on a substrate. The etching may introduce an aluminum-containing byproduct to a coating disposed on one or more components of a semiconductor processing chamber. The methods may include contacting the coating with plasma effluents of a first cleaning precursor to remove an exposed portion of the aluminum-containing byproduct. The methods may include contacting the coating with the plasma effluents of a second cleaning precursor. The contacting may remove a portion of the coating to expose an embedded portion of the aluminum-containing byproduct. The methods may include contacting the coating with the plasma effluents of the first cleaning precursor to remove the embedded portion of the aluminum-containing byproduct.

Description

SEMICONDUCTOR CLEANING TO REMOVE FLUORINE- CONTAINING BYPRODUCTSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit and priority of U. S. Patent Application No. 63 / 568.597, filed March 22. 2024. entitled “SEMICONDUCTOR CLEANING TO REMOVE FLUORINE-CONTAINING BYPRODUCTS”, which is hereby incorporated by reference in its entirety.TECHNICAL FIELD

[0002] The present technology relates to semiconductor cleaning operations. More specifically, the present technology relates to methods of cleaning semiconductor surfaces or components.BACKGROUND

[0003] Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods of formation and removal of exposed material. After deposition and / or etching processes have been performed within a chamber, chamber components may include residual materials from the deposition and / or etching process. Chamber cleaning operations may remove residues from the chamber, however the process may erode chamber components over time.

[0004] Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.SUMMARY

[0005] Exemplary cleaning methods may include providing one or more etchant precursors to a processing region of a semiconductor processing chamber. A substrate may be disposed on a substrate support within a processing region of the semiconductor processing chamber. The methods may include etching an aluminum-containing material on the substrate. The etching may introduce an aluminum-containing byproduct to a coating disposed on one ormore components of the semiconductor processing chamber. The methods may include providing a first cleaning precursor to the processing region. The methods may include forming plasma effluents of the first cleaning precursor. The methods may include contacting the coating with the plasma effluents of the first cleaning precursor. The contacting may remove an exposed portion of the aluminum-containing byproduct. The methods may include providing a second cleaning precursor to the processing region. The methods may include forming plasma effluents of the second cleaning precursor. The methods may include contacting the coating with the plasma effluents of the second cleaning precursor. The contacting may remove a portion of the coating to expose an embedded portion of the aluminum-containing byproduct. The methods may include providing the first cleaning precursor to the processing region. The methods may include forming plasma effluents of the first cleaning precursor. The methods may include contacting the coating with the plasma effluents of the first cleaning precursor. The contacting may remove the embedded portion of the aluminum-containing byproduct.

[0006] In some embodiments, the one or more etchant precursors may be or include a fluorine-containing precursor. The substrate support may be or include an aluminum- containing material. The substrate may further include a carbon-containing material. The aluminum-containing byproduct may be or include an aluminum-and-fluorine-containing byproduct. The coating may be or include a silicon-and-oxygen-containing material. The first cleaning precursor may include one or more chlorine-containing precursors. The first cleaning precursor may include boron trichloride (BCh) and diatomic chlorine (Ch). The methods may include halting a flow of the first cleaning precursor prior to providing the second cleaning precursor. The second cleaning precursor may be or include one or more fluorine-containing precursors.

[0007] Some embodiments of the present technology may encompass cleaning methods. The methods may include i) purging a processing region of a semiconductor processing chamber to bring an aluminum-and-fluorine-containing byproduct to the processing region. The methods may include ii) providing a hydrogen-containing precursor to the processing region. The methods may include iii) forming plasma effluents of the hydrogen-containing precursor. The methods may include iv) contacting the aluminum-and-fluorine-containing byproduct with the plasma effluents of the hydrogen-containing precursor. The contacting may reduce the aluminum-and-fluorine-containing byproduct to an aluminum-containing material. The methods may include v) providing an oxygen-containing precursor to theprocessing region. The methods may include vi) forming plasma effluents of the oxygencontaining precursor. The methods may include vii) contacting the aluminum-containing material with the plasma effluents of the oxygen-containing precursor. The contacting may oxidize the aluminum-containing material to form an aluminum-and-oxygen-containing material. The methods may include viii) providing an etchant precursor to the processing region. The methods may include ix) forming plasma effluents of the etchant precursor. The methods may include x) contacting the aluminum-and-oxygen-containing material with the plasma effluents of the etchant precursor. The contacting may form volatile material comprising an aluminum-and-chlorine-containing material.

[0008] In some embodiments, the methods may include xi) pumping the aluminum-and- chlorine-containing material from the processing region. The methods may include cyclically repeating operations i) through xi) a plurality of cycles. The hydrogen-containing precursor may be or include diatomic hydrogen (H2). The oxygen-containing precursor may be or include diatomic oxygen (O2). The etchant precursor may be or include boron trichloride (BCI3) and diatomic chlorine (Ch).

[0009] Some embodiments of the present technology may encompass cleaning methods. The methods may include i) performing a first chamber cleaning operation to remove aluminum-containing byproduct within a coating disposed on one or more components of a semiconductor processing chamber. The methods may include ii) performing a second chamber cleaning operation to remove aluminum-and-fluorine-containing particles from the semiconductor processing chamber. The methods may include iii) performing a third chamber cleaning operation to remove aluminum-containing byproduct within the coating disposed on one or more components of a semiconductor processing chamber.

[0010] In some embodiments, the first chamber cleaning operation and the third chamber cleaning operation may include providing a first cleaning precursor to the processing region, forming plasma effluents of the first cleaning precursor, and contacting the coating with the plasma effluents of the first cleaning precursor. The contacting may remove an exposed portion of the aluminum-containing byproduct. The first chamber cleaning operation and the third chamber cleaning operation may include providing a second cleaning precursor to the processing region, forming plasma effluents of the second cleaning precursor, and contacting the coating with the plasma effluents of the second cleaning precursor. The contacting may remove a portion of the coating to expose an embedded portion of the aluminum-containingbyproduct. The first chamber cleaning operation and the third chamber cleaning operation may include providing the first cleaning precursor to the processing region, forming plasma effluents of the first cleaning precursor, and contacting the coating with the plasma effluents of the first cleaning precursor. The contacting may remove the embedded portion of the aluminum-containing byproduct. The second chamber cleaning operation may include a reduction-oxidation reaction. The reduction-oxidation reaction may be repeated a plurality of times.

[0011] Such technology may provide numerous benefits over conventional systems and techniques. For example, the processes may reduce and / or eliminate embedded aluminum- containing byproduct. Additionally, the operations of embodiments of the present technology may prevent etching of aluminum-containing components, such as an aluminum-containing substrate support. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

[0013] FIG. 1 shows a schematic cross-sectional view of an exemplary processing chamber according to some embodiments of the present technology.

[0014] FIG. 2 shows exemplary operations in a cleaning method according to some embodiments of the present technology.

[0015] FIGS. 3A-3F show cross-sectional views of chambers being processed according to some embodiments of the present technology.

[0016] FIG. 4 shows exemplary operations in a cleaning method according to some embodiments of the present technology.

[0017] Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aidcomprehension and may not include all aspects or information compared to realistic representations, and may include exaggerated material for illustrative purposes.

[0018] In the appended figures, similar components and / or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.DETAILED DESCRIPTION

[0019] Etching operations in semiconductor processing may be included to remove any number of materials from a substrate. For example, materials may be etched from a substrate to produce semiconductor structures, as well as to facilitate patterning or further removal of materials on a substrate. As one non-limiting example, etching operations may include removing an aluminum-containing material on a substrate. The aluminum-containing material removal may be performed in any number of ways, including by plasma-enhanced etching. Regardless of the mechanism, many etching operations not only remove material from the substrate being processed, but also deposit material or byproduct on one or more chamber components. For example, in a processing region, byproduct deposition may occur on a pedestal or support on which the substrate is seated, faceplates, or diffusers that may distribute materials into the processing region, chamber walls defining the processing region, and components defining exhaust pathways for materials and byproducts subsequent deposition. Some components may be provided with a coating to protect the underlying component material from plasma-enhanced species during processing. The byproduct may diffuse into the coating and become embedded within the coating.

[0020] Once the etching process is completed, the substrate may be removed from the processing region, and cleaning operations may be employed. Chamber cleaning may form a plasma of one or more precursors that may etch or otherwise remove residual materials formed on the chamber components in order to essentially reset the chamber prior to a subsequent processing operation, which may help maintain consistency wafer-to-wafer. However, these chamber cleaning operations may not successfully remove embedded byproduct material.

[0021] The present technology may overcome these limitations by performing cleaning operations that remove both surface byproduct as well as embedded byproduct material. Unlike conventional technologies, the present technology may first remove surface byproduct material then remove a portion of the coating to expose embedded byproduct material. Further cleaning operations may be performed to remove the previously embedded byproduct material. The present technology may also draw byproduct material from other locations in the semiconductor processing chamber such that the byproduct material may be treated and reduced or removed.

[0022] Although the remaining disclosure will routinely identify specific cleaning operations utilizing the disclosed technology', it will be readily understood that the systems and methods are equally applicable to other chambers, as well as processes as may occur in the described chambers. Accordingly, the technology should not be considered to be so limited as for use with these specific processes or chambers alone. The disclosure will discuss one possible system and chamber that may be used to perform cleaning operations according to embodiments of the present technology before additional details according to embodiments of the present technology are described.

[0023] FIG. 1 shows a cross-sectional view of an exemplary processing chamber 100 according to some embodiments of the present technology. The figure may illustrate an overview of a system incorporating one or more aspects of the present technology7, and / or which may be specifically configured to perform one or more operations according to embodiments of the present technology. Additional details of chamber 100 or methods performed may be described further below. Chamber 100 may be utilized to form film layers according to some embodiments of the present technology, although it is to be understood that the methods may similarly be performed in any chamber within which film formation may occur. The processing chamber 100 may include a chamber body 102, a substrate support 104 disposed inside the chamber body 102. and a lid assembly 106 coupled with the chamber body 102 and enclosing the substrate support 104 in a processing volume 120. The substrate support 104 may be or include an aluminum-containing material. A substrate 103 may be provided to the processing volume 120 through an opening 126, which may be conventionally sealed for processing using a slit valve or door. The substrate 103 may be seated on a surface 105 of the substrate support during processing. The substrate support 104 may be rotatable, as indicated by the arrow 145, along an axis 147, where a shaft 144 of thesubstrate support 104 may be located. Alternatively, the substrate support 104 may be lifted up to rotate as necessary during a deposition process.

[0024] A plasma profile modulator 111 may be disposed in the processing chamber 100 to control plasma distribution across the substrate 103 disposed on the substrate support 104. The plasma profile modulator 111 may include a first electrode 108 that may be disposed adjacent to the chamber body 102, and may separate the chamber body 102 from other components of the lid assembly 106. The first electrode 108 may be part of the lid assembly 106, or may be a separate sidewall electrode. The first electrode 108 may be an annular or ring-like member, and may be a ring electrode. The first electrode 108 may be a continuous loop around a circumference of the processing chamber 100 surrounding the processing volume 120, or may be discontinuous at selected locations if desired. The first electrode 108 may also be a perforated electrode, such as a perforated ring or a mesh electrode, or may be a plate electrode, such as, for example, a secondary gas distributor.

[0025] One or more isolators 110a, 110b, which may be a dielectric material such as a ceramic or metal oxide, for example aluminum oxide and / or aluminum nitride, may contact the first electrode 108 and separate the first electrode 108 electrically and thermally from a gas distributor 112 and from the chamber body 102. The gas distributor 112 may define apertures 118 for distributing process precursors into the processing volume 120. The gas distributor 112 may be coupled with a first source of electric power 142, such as an RF generator, RF power source, DC power source, pulsed DC power source, pulsed RF power source, or any other power source that may be coupled with the processing chamber. In some embodiments, the first source of electric power 142 may be an RF power source.

[0026] The gas distributor 112 may be a conductive gas distributor or a non-conductive gas distributor. The gas distributor 112 may also be formed of conductive and non-conductive components. For example, a body of the gas distributor 112 may be conductive while a face plate of the gas distributor 112 may be non-conductive. The gas distributor 112 may be powered, such as by the first source of electric power 142 as shown in FIG. 1, or the gas distributor 112 may be coupled with ground in some embodiments.

[0027] The first electrode 108 may be coupled with a first tuning circuit 128 that may control a ground pathway of the processing chamber 100. The first tuning circuit 128 may include a first electronic sensor 130 and a first electronic controller 134. The first electronic controller 134 may be or include a variable capacitor or other circuit elements. The firsttuning circuit 128 may be or include one or more inductors 132. The first tuning circuit 128 may be any circuit that enables variable or controllable impedance under the plasma conditions present in the processing volume 120 during processing. In some embodiments as illustrated, the first timing circuit 128 may include a first circuit leg and a second circuit leg coupled in parallel between ground and the first electronic sensor 130. The first circuit leg may include a first inductor 132A. The second circuit leg may include a second inductor 132B coupled in series with the first electronic controller 134. The second inductor 132B may be disposed between the first electronic controller 134 and anode connecting both the first and second circuit legs to the first electronic sensor 130. The first electronic sensor 130 may be a voltage or current sensor and may be coupled with the first electronic controller 134, which may afford a degree of closed-loop control of plasma conditions inside the processing volume 120.

[0028] A second electrode 122 may be coupled with the substrate support 104. The second electrode 122 may be embedded within the substrate support 104 or coupled with a surface of the substrate support 104. The second electrode 122 may be a plate, a perforated plate, a mesh, a wire screen, or any other distributed arrangement of conductive elements. The second electrode 122 may be a tuning electrode, and may be coupled with a second tuning circuit 136 by a conduit 146, for example a cable having a selected resistance, such as 50 ohms, for example, disposed in the shaft 144 of the substrate support 104. The second tuning circuit 136 may have a second electronic sensor 138 and a second electronic controller 140, which may be a second variable capacitor. The second electronic sensor 138 may be a voltage or current sensor, and may be coupled with the second electronic controller 140 to provide further control over plasma conditions in the processing volume 120.

[0029] A third electrode 124, which may be a bias electrode and / or an electrostatic chucking electrode, may be coupled with the substrate support 104. The third electrode may be coupled with a second source of electric power 150 through a filter 148. which may be an impedance matching circuit. The second source of electric power 150 may be DC power, pulsed DC power, RF bias power, a pulsed RF source or bias power, or a combination of these or other power sources. In some embodiments, the second source of electric power 150 may be an RF bias power.

[0030] The lid assembly 106 and substrate support 104 of FIG. 1 may be used with any processing chamber for plasma or thermal processing. In operation, the processing chamber100 may afford real-time control of plasma conditions in the processing volume 120. The substrate 103 may be disposed on the substrate support 104, and process gases may be flowed through the lid assembly 106 using an inlet 114 according to any desired flow plan. Inlet 114 may include deliver}' from a remote plasma source unit 116, which may be fluidly coupled with the chamber, as well as a bypass 117 for process gas deliver}' that may not flow through the remote plasma source unit 116 in some embodiments. Gases may exit the processing chamber 100 through an outlet 152. Electric power may be coupled with the gas distributor 112 to establish a plasma in the processing volume 120. The substrate may be subjected to an electrical bias using the third electrode 124 in some embodiments.

[0031] Upon energizing a plasma in the processing volume 120, a potential difference may be established between the plasma and the first electrode 108. A potential difference may also be established between the plasma and the second electrode 122. The electronic controllers 134, 140 may then be used to adjust the flow properties of the ground paths represented by the two tuning circuits 128 and 136. A set point may be delivered to the first tuning circuit 128 and the second tuning circuit 136 to provide independent control of deposition rate and of plasma density uniformity from center to edge. In embodiments where the electronic controllers may both be variable capacitors, the electronic sensors may adjust the variable capacitors to maximize deposition rate and minimize thickness non-uniformity independently.

[0032] Each of the tuning circuits 128, 136 may have a variable impedance that may be adjusted using the respective electronic controllers 134. 140. Where the electronic controllers 134, 140 are variable capacitors, the capacitance range of each of the variable capacitors, and the inductances of the first inductor 132A and the second inductor 132B, may be chosen to provide an impedance range. This range may depend on the frequency and voltage characteristics of the plasma, which may have a minimum in the capacitance range of each variable capacitor. Hence, when the capacitance of the first electronic controller 134 is at a minimum or maximum, impedance of the first tuning circuit 128 may be high, resulting in a plasma shape that has a minimum aerial or lateral coverage over the substrate support. When the capacitance of the first electronic controller 134 approaches a value that minimizes the impedance of the first tuning circuit 128, the aerial coverage of the plasma may grow to a maximum, effectively covering the entire working area of the substrate support 104. As the capacitance of the first electronic controller 134 deviates from the minimum impedance setting, the plasma shape may shrink from the chamber walls and aerial coverage of thesubstrate support may decline. The second electronic controller 140 may have a similar effect, increasing and decreasing aerial coverage of the plasma over the substrate support as the capacitance of the second electronic controller 140 may be changed.

[0033] The electronic sensors 130, 138 may be used to tune the respective circuits 128, 136 in a closed loop. A set point for current or voltage, depending on the type of sensor used, may be installed in each sensor, and the sensor may be provided with control software that determines an adjustment to each respective electronic controller 134, 140 to minimize deviation from the set point. Consequently, a plasma shape may be selected and dynamically controlled during processing. It is to be understood that, while the foregoing discussion is based on electronic controllers 134, 140, which may be variable capacitors, any electronic component with adjustable characteristic may be used to provide tuning circuits 128 and 136 with adjustable impedance.

[0034] FIG. 2 shows exemplary operations in a method 200 of treating a chamber according to some embodiments of the present technology. The method may be performed in a variety7of processing chambers, including processing chamber 100 described above. Method 200 may include one or more operations prior to the initiation of the method, including front end processing, polishing, cleaning, deposition, etching, or any other operations that may be performed prior to the described operations. Method 200 may include a number of optional operations, which may or may not be specifically associated with some embodiments of methods according to the present technology. For example, many of the operations are described in order to provide a broader scope of the structural formation, but are not critical to the technology, or may be performed by alternative methodology as will be discussed further below.

[0035] Method 200 may involve optional operations to develop the semiconductor structure to a particular fabrication operation. Although in some embodiments method 200 may be performed on a base structure, in some embodiments the method may be performed subsequent other material formation or removal. For example, any number of deposition, masking, or removal operations may be performed to produce any transistor, memory, or other structural aspects on a substrate. The substrate may be disposed on a substrate support, which may be positioned within a processing region of a semiconductor processing chamber. The operations may be performed in the same chamber in which aspects of method 200 may be performed, and one or more operations may also be performed in one or more chamberson a similar platform as a chamber in which operations of method 200 may be performed, or on other platforms. Method 200 describes the operations shown schematically in FIGS. 3A- 3F, the illustrations of which will be described in conjunction with the operations of method 200. It is to be understood that FIGS. 3A-3F illustrate only partial schematic views, and a component may contain any number of materials or features having aspects as illustrated in the figures.

[0036] As illustrated in FIG. 3A, a coating 310 may be disposed on one or more components 305 of the semiconductor processing chamber. The one or more components 305 may be or include a chamber wall or a substrate support or any other component present in a semiconductor processing chamber. The coating 310 may be, for example, a silicon- containing material or a silicon-and-oxy gen-containing material that is resistant to plasma species that may otherwise corrode or erode the component 305.

[0037] At operation 205, method 200 may include providing one or more etchant precursors to a processing region of the semiconductor processing chamber. As previously discussed, a substrate may be disposed within the processing region of the semiconductor processing chamber. The one or more etchant precursors may be provided through a gas distributor, such as gas distributor 112, defining apertures, such as apertures 118. for distributing process precursors into the processing region or processing volume. The one or more etchant precursors may include a halogen-containing precursor, such as a fluorine- containing precursor. The fluorine-containing precursor may be or include diatomic fluorine (F2), hydrogen fluoride (HF), nitrogen trifluoride (NF3). phosphorus trifluoride(PF3). sulfur hexafluoride (SF6), carbon tetrafluoride (CF4), fluoroform(CHF3), or other fluorine- containing materials used or useful in semiconductor processing. The one or more etchant precursors may or may not include delivery of additional precursors, such as carrier gases.

[0038] At operation 210, method 200 may include etching an aluminum-containing material on the substrate. During method 200, aluminum-containing byproduct from the etching may be exhausted from the processing region. However, at least a portion of the aluminum-containing byproduct may also re-deposit on one or more components of the semiconductor processing chamber, such as on and / or within coating 310. Depending on the etchant precursors provided to the semiconductor processing chamber at operation 205, various aluminum-containing byproducts may be deposited. For example, if the etchant precursors include fluorine, an aluminum-and-fluorine-containing byproduct may bedeposited. It is contemplated that the etchant precursors may include any number of constituents and. therefore, the byproduct may also include any number of constituents.

[0039] The etching of aluminum-containing material at operation 210 may be performed at a variety of temperatures and processes. Depending on the material to be formed, the process conditions may be modified to etching aluminum-containing material, such as aluminum- and-oxygen-containing material or aluminum-and-nitrogen-containing material. During operation 210, a plasma power may be provided to generate plasma effluents of the one or more etchant precursors. The application of plasma power may increase an etch rate of the aluminum-containing material and / or may increase uniformity of a feature being etched.

[0040] As illustrated in FIG. 3B, subsequent the etching at operation 210, the coating 310 may include an embedded aluminum-containing byproduct 315 and / or a surface aluminum- containing byproduct 320. Additionally, in embodiments, an aluminum-and-carbon- containing byproduct 325 may also form on the coating 310. The carbon may be present from other material layers present on the substrate being etched at operation 210. However, it is also contemplated that the aluminum-and-carbon-containing byproduct 325 may not be present depending on the materials being etched and / or present during the etching at operation 210.

[0041] In embodiments where aluminum-and-carbon-containing byproduct 325 is present, one or more preliminary cleaning precursors may be provided to the processing region of the semiconductor processing chamber. The one or more preliminary cleaning precursors may include a chlorine-containing precursor, a bromine-containing precursor, and / or an oxy gencontaining precursor. The chlorine-containing precursor may include one or more chlorine- containing materials such as a fluorocarbon, atomic chlorine (Cl), diatomic chlorine (CI2), an interhalogen fluoride, such as bromine trichloride (BrCh) or chlorine trifluoride (CIF3), boron trichloride (BCI3), carbon tetrachloride (CCI4), or silicon tetrachloride (S1CI4). or any other chlorine-containing material. The bromine-containing precursor may include one or more of hydrogen bromide (HBr), diatomic bromine (Bn), or any other bromine-containing material. The oxygen-containing precursor may include one or more of diatomic oxygen (O2), water or steam (H2O), nitrous oxide (N2O), hydrogen peroxide (H2O2), or any other oxy gen-containing material. In one exemplary embodiment, the one or more preliminary cleaning precursors may include Ch and O2 or Ch and HBr.

[0042] Plasma effluents of the preliminary cleaning precursor(s) may or may not be formed. The aluminum-and-carbon-containing byproduct 325 may be contacted with the preliminary cleaning precursor(s) or plasma effluents thereof. As illustrated in FIG. 3C, the one or more preliminary cleaning precursors may interact with the aluminum-and-carbon- containing byproduct 325 to volatilize the aluminum-and-carbon-containing byproduct 325 and expose the aluminum-containing byproduct 320.

[0043] At operation 215. method 200 may include providing one or more first cleaning precursors to the semiconductor processing chamber. The one or more first cleaning precursors may include a chlorine-containing precursor. The chlorine-containing precursor may include one or more chlorine-containing materials such as a fluorocarbon, atomic chlorine (Cl), diatomic chlorine (Ch), an interhalogen fluoride, such as bromine trichloride (BrCh) or chlorine trifluoride (CIF3), boron trichloride (BCh), carbon tetrachloride (CCh), or silicon tetrachloride (SiCU). In one exemplary embodiment, the one or more first cleaning precursors may include Ch and BCh.

[0044] In embodiments where the first cleaning precursor comprises Ch and BCh, a flow rate of each precursor may be greater than or about 50 seem, and may be greater than or about 75 seem, greater than or about 100 seem, greater than or about 125 seem, greater than or about 150 seem, greater than or about 175 seem, greater than or about 200 seem, or more. As such, a flow rate ratio of BCh to Ch may be greater than or about 1 :4, and may be greater than or about 1:3, greater than or about 1:2, greater than or about 3:2, greater than or about 1 : 1 , or more.

[0045] At operation 220, method 200 may include forming plasma effluents of the first cleaning precursor(s). For example, when the one or more cleaning precursors include a chlorine-containing precursor, operation 220 may include forming a chlorine-containing plasma from the chlorine-containing precursor in the processing region. The plasma effluents of the chlorine-containing precursor, or other cleaning precursor(s). may be generated by applying an RF power to the processing region. Alternatively or additionally, the chlorine- containing precursor may contact excited species present in the processing region and / or being purged from the processing region, such as excited species of an inert material, which may in turn excite the one or more first cleaning precursors thereby generating a plasma from the one or more first cleaning precursors in the processing region.

[0046] Plasma effluents of the first cleaning precursor(s) may be formed at a plasma power greater than or about 1,000 W. Higher plasma power may generate additional radicals of the first cleaning precursor(s) and may result in a more efficient cleaning. Accordingly, plasma effluents of the first cleaning precursor(s) may be formed at a plasma power greater than or about 1,250 W, greater than or about 1,500 W, greater than or about 1,750 W, greater than or about 2,000 W, or more. However, high plasma power may damage the semiconductor processing chamber or components thereof. As such, plasma effluents of the first cleaning precursor(s) may be formed at a plasma power less than or about 3,500 W, less than or about 3,000 W, less than or about 2,500 W, or less.

[0047] In embodiments, an inert precursor, such as argon (Ar) or helium (He), may be provided with the first cleaning precursor to stabilize the plasma effluent without diluting the precursors. A flow rate of the inert precursor may be greater than 10 seem, and may be greater than or about 20 seem, greater than or about 30 seem, greater than or about 40 seem, greater than or about 50 seem, or more.

[0048] At operation 225, method 200 may include contacting the coating 310, such as the silicon-containing material, on the one or more components 305 of the semiconductor processing chamber with the one or more first cleaning precursors or the plasma effluents thereof. As illustrated in FIG. 3D, at operation 225, method 200 may include removing at least a portion of the coating 310, or silicon-containing material, on the one or more components 305 of the semiconductor processing chamber with the one or more first cleaning precursors, such as the chlorine-containing precursor, or plasma effluents thereof. The one or more first cleaning precursors may interact with the aluminum-containing byproduct 320 to volatilize the aluminum-containing byproduct 320. For example, the chlorine-containing precursor, or plasma effluents thereof, may interact with the aluminum-containing material to yield volatile BChF and AIF2CI. for example. Chlorine and fluorine may continue to interact and may transform AIF3 to volatile AlCh. The volatiles may then be purged from the chamber to remove the exposed aluminum-containing byproduct 320 from the chamber and / or chamber components. The aluminum-containing byproduct 320 removed may not include or may be selective to aluminum-containing material present on the substrate. In embodiments, the substrate may be removed prior to the one or more first cleaning precursors being provided to the processing region.

[0049] At operation 230. method 200 may include providing one or more second cleaning precursors to the semiconductor processing chamber. In embodiments, method 200 may include halting a flow of the first cleaning precursor(s) prior to providing the second cleaning precursor(s). The one or more second cleaning precursors may include a fluorine-containing precursor. The fluorine-containing precursor may include one or more fluorine-containing materials such as a fluorocarbon, atomic fluorine (F), diatomic fluorine (F2), an interhalogen fluoride, such as bromine trifluoride (BF3) or chlorine trifluoride (CIF3), nitrogen trifluoride (NF3), sulfur hexafluoride (SF3), xenon difluoride (XF2), or carbon tetrafluoride (CF4). In embodiments, the fluorine-containing precursor may include hydrogen and may be, for example, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), HF-pyridine, tetrafluorohydrazine (N2F4), tetramehtylammonium fluoride ((CH3)4NF), tetra-n-butylammonium fluoride ((C4Hg)4NF), N2H5F, N2H5F2, or hydrazinium fluorides.

[0050] At operation 235, method 200 may include generating a plasma from the second cleaning precursors in the processing region. For example, when the one or more second cleaning precursors include a fluorine-containing precursor, operation 235 may include generating a fluorine-containing plasma from the fluorine-containing precursor in the processing region. The plasma effluents of the fluorine-containing precursor, or other cleaning precursor(s), may be generated by applying an RF power to the processing region. Alternatively or additionally, the fluorine-containing precursor may contact excited species present in the processing region and / or being purged from the processing region, such as excited species of an inert material, which may in turn excite the one or more second cleaning precursors thereby generating a plasma from the one or more first cleaning precursors in the processing region.

[0051] At operation 240, method 200 may include contacting the coating 310, such as the silicon-containing material, on the one or more components 305 of the semiconductor processing chamber with the one or more second cleaning precursors or the plasma effluents thereof. As illustrated in FIG. 3E, at operation 240, method 200 may include removing at least a portion of the coating 310, or silicon-containing material, on the one or more components 305 of the semiconductor processing chamber with the one or more second cleaning precursors, such as the fluorine-containing precursor. The one or more cleaning precursors may interact with the silicon-containing material to volatilize the silicon- containing material. For example, the fluorine-containing precursor may interact with thesilicon-containing material to yield silicon tetrafluoride (SiF4) and oxygen or nitrogen gaseous byproduct. The volatiles may then be purged from the chamber to remove the silicon-containing material of the coating 310 from the chamber and / or chamber components. The coating 310, or silicon-containing material, removed may expose an embedded portion of aluminum-containing byproduct 315. As previously discussed, in some embodiments, the substrate may be removed prior to the one or more first and / or second cleaning precursors being provided to the processing region, and the removal of silicon-containing material of the coating 310 may not impact the substrate being processed.

[0052] As shown in FIG. 2, method 200 may include repeating operations 215-225 and optionally operations 230-245 for a number of cycles. As illustrated in FIG. 3F, by repeating operations 215-225 and optionally operations 230-245, embedded aluminum-containing byproduct 315 in the coating 310 may be removed. Additionally, a portion of the coating 310 below the embedded aluminum-containing byproduct 315 may also be removed to further reduce and / or eliminate embedded aluminum-containing byproduct 315. While any number of cycles of operations 215-225 and optionally operations 230-245 may be repeated, the embedded aluminum-containing byproduct 315 may only be present as one layer. Therefore, only two cycles of two cycles may be needed to reduce and / or eliminate embedded aluminum-containing byproduct 315.

[0053] As also shown in FIG. 2, operations 205-240 may be repeated for a number of cycles. In embodiments, the coating 310 may be refreshed or replenished prior to operation 205. For example, additional coating 310, such as the silicon-containing material, may be deposited prior to the processing of another substrate or group of substrates. Once the coating 310 is reformed, operations 205-240 may be repeated to etch another aluminum- containing material then to remove aluminum-containing byproduct from the coating 310.

[0054] Process conditions may impact the operations performed in method 200. Each of the operations of method 200 may be performed during a constant temperature in embodiments, while in some embodiments the temperature may be adjusted during different operations. In some embodiments of the present technology, method 200 may be performed at substrate, pedestal, and / or chamber temperatures less or about 100 °C, and may be performed at temperatures less than or about 95 °C, less than or about 90 °C, less than or about 85 °C. less than or about 80 °C. less than or about 75 °C. less than or about 70 °C. less than or about 65 °C, less than or about 60 °C, less than or about 55 °C, less than or about 50°C, less than or about 45 °C, less than or about 40 °C, or lower. The temperature may also be maintained at any temperature within these ranges, within smaller ranges encompassed by these ranges, or between any of these ranges. While higher temperature may increase a rate of the cleaning process, reduced temperatures may increase control of the cleaning process. Thus, by tuning or adjusting temperature, the reaction rate can be selected. In embodiments, the temperature may be maintained at a temperature at which aluminum-containing material may be etched, reducing downtime and increasing throughput. Accordingly, in some embodiments, the temperature may be maintained between about 30 °C and about 90 °C.

[0055] The pressure within the semiconductor processing chamber may also affect the operations performed. In embodiments, the pressure may be maintained at less than about 500 mTorr. Accordingly, the pressure may be maintained at less than or about 450 mTorr. less than or about 400 mTorr, less than or about 375 mTorr. less than or about 350 mTorr, less than or about 325 mTorr, less than or about 300 mTorr, less than or about 275 mTorr, less than or about 250 mTorr, less than or about 225 mTorr, less than or about 200 mTorr, less than or about 150 mTorr, less than or about 100 mTorr. less than or about 75 mTorr, less than or about 50 mTorr, less than or about 40 mTorr, less than or about 30 mTorr, less than or about 20 mTorr, less than or about 10 mTorr, less than or about 5 mTorr, or less. The pressure may also be maintained at any pressure within these ranges, within smaller ranges encompassed by these ranges, or between any of these ranges. Accordingly, in some embodiments, the pressure may be maintained between about 1 Torr and about 10 Torr. At increased pressures, plasma effluents may accumulate in the upper chamber or upper portions of the processing region. Similarly, at reduced pressures plasma effluents may accumulate in the lower chamber or lower portions of the processing region. Hence, for the cleaning process, pressure may be selected or adjusted to target cleaning of specific areas of the semiconductor processing chamber.

[0056] FIG. 4 shows exemplary operations in a method 400 of treating a chamber according to some embodiments of the present technology. The method may be performed in a variety of processing chambers, including processing chamber 100 described above. Method 400 may include one or more operations prior to the initiation of the method, including front end processing, polishing, cleaning, deposition, etching, or any other operations that may be performed prior to the described operations. Method 400 may include a number of optional operations, which may or may not be specifically associated with some embodiments of methods according to the present technology. For example, many of theoperations are described in order to provide a broader scope of the structural formation, but are not critical to the technology, or may be performed by alternative methodology as will be discussed further below.

[0057] Method 400 may involve optional operations to develop a semiconductor structure to a particular fabrication operation. Although in some embodiments method 400 may be performed on a base structure, in some embodiments the method may be performed subsequent other material formation or removal. For example, any number of deposition, masking, or removal operations may be performed to produce any transistor, memory, or other structural aspects on a substrate. The substrate may be disposed on a substrate support, which may be positioned within a processing region of a semiconductor processing chamber. The operations may be performed in the same chamber in which aspects of method 400 may be performed, and one or more operations may also be performed in one or more chambers on a similar platform as a chamber in which operations of method 400 may be performed, or on other platforms.

[0058] Method 400 may be a reduction-oxidation reaction to reduce, oxidize, and then etch aluminum-containing byproduct, such as aluminum-and-fluorine-containing byproduct. At operation 405, method 400 may include purging a processing region of the semiconductor processing chamber. The purging may bring an aluminum-and-fluorine-containing byproduct present in other areas of the semiconductor processing chamber to the processing region. For example, aluminum-and-fluorine-containing byproduct may be present in downstream regions, such as an exhaust line, but may still impact subsequent processing if not treated. Accordingly, the purging at operation 405 may bring the aluminum-and-fluorine-containing byproduct to the processing region to where it may be treated and removed.

[0059] At operation 410, method 400 may include providing a hydrogen-containing precursor to the processing region. The hydrogen-containing precursor may be any hydrogen-containing material that may reduce aluminum-and-fluorine-containing material. For example, the hydrogen-containing precursor may be diatomic hydrogen (H2).

[0060] Plasma effluents of the hydrogen-containing precursor may be formed at operation 415. In embodiments, plasma effluents of the hydrogen-containing precursor may be formed at less than or about 1,500 W, and may be formed at less than or about 1,400 W, less than or about 1,300 W, less than or about 1,200 W, or less. Increased source plasma powers may introduce plasma with higher density. Additionally, a bias power may be applied whileforming plasma effluents of the hydrogen-containing precursor. The bias power, which may be provided at 13 MHz, may be provided at less than or about 250 W, and may be provided at less than or about 225 W, less than or about 200 W, less than or about 175 W, less than or about 150 W, less than or about 125 W, less than or about 100 W, less than or about 90 W, less than or about 80 W, less than or 70 W, or less. Increased bias powers may provide higher energy’ ions in the plasma effluents. Thus, by adjusting source plasma / bias power, the reaction rate in the reduction operation of the cleaning process may be tuned.

[0061] Method 400 may include contacting the aluminum-and-fluorine-containing byproduct with the plasma effluents of the hydrogen-containing precursor at operation 420. The contacting may reduce the aluminum-and-fluorine-containing by product to an aluminum-containing material.

[0062] After reducing the aluminum-and-fluorine-containing byproduct to an aluminum- containing material, method 400 may include providing an oxy gen-containing precursor to the processing region at operation 425. In embodiments, method 400 may include halting a flow of the hydrogen-containing precursor prior to providing the oxygen-containing precursor to the processing region. The oxy gen-containing precursor may be any oxygen-containing material that may’ reduce aluminum-containing material. For example, the oxygen-containing precursor may be diatomic oxygen (Ch).

[0063] Plasma effluents of the oxy gen-containing precursor may be formed at operation 430. In embodiments, plasma effluents of the oxygen-containing precursor may be formed at less than or about 1,200 W, and may be formed at less than or about 1,100 W, less than or about 1,000 W, less than or about 900 W, less than or about 800 W, or less. Additionally, a bias power may be applied while forming plasma effluents of the hydrogen-containing precursor. The bias power, which may be provided at 13 MHz, may be provided at less than or about 500 W, and may be provided at less than or about 450 W, less than or about 400 W. less than or about 375 W, less than or about 350 W. less than or about 325 W, less than or about 300 W, or less. Similar to the reduction operations, by adjusting source plasma / bias power, the reaction rate in the oxidation operation of the cleaning process may be tuned.

[0064] In embodiments, the bias power may be pulsed while forming plasma effluents of the oxygen-containing precursor. For example, the bias power may be pulsed at a frequency of greater than or about 500 Hz, and may be pulsed at a frequency of greater than or about 600 Hz, greater than or about 700 Hz, greater than or about 800 Hz, greater than or about 900Hz, greater than or about 1,000 Hz, or more. Additionally, a duty cycle, or on time, of the bias power may be between about 10% and about 90%, such as between about 20% and about 80%, between about 30% and about 70%, or between about 40% and about 60%.

[0065] Method 400 may include contacting the aluminum-containing material with the plasma effluents of the oxy gen-containing precursor at operation 435. The contacting may oxidize the aluminum-containing material to form an aluminum-and-oxygen-containing material.

[0066] After oxidizing the aluminum-containing material to form an aluminum-and- oxygen-containing material, method 400 may include providing an etchant precursor to the processing region at operation 440. In embodiments, method 400 may include halting a flow of the oxygen-containing precursor prior to providing the etchant precursor to the processing region. The etchant precursor may be a halogen-containing precursor, such as a chlorine- containing precursor, a bromine-containing precursor, or a fluorine-containing precursor, or any etchant material that may etch aluminum-and-oxygen-containing material. For example, the etchant precursor comprises boron trichloride (BCh) and diatomic chlorine (Ch). In embodiments, the etchant precursor may further include hydrogen bromine (HBr).

[0067] Plasma effluents of the etchant precursor may be formed at operation 445. In embodiments, plasma effluents of the etchant precursor may be formed at less than or about 1,200 W, and may be formed at less than or about 1,100 W, less than or about 1,000 W, less than or about 900 W, less than or about 800 W, or less. Additionally, a bias power may be applied while forming plasma effluents of the etchant precursor. The bias power, which may be provided at 13 MHz, may be provided at less than or about 500 W, and may be provided at less than or about 450 W, less than or about 400 W, less than or about 375 W, less than or about 350 W, less than or about 325 W, less than or about 300 W, less than or about 250 W, or less. Similar to the reduction and oxidation operations, by adjusting source plasma / bias power, the reaction rate in the etching operation of the cleaning process may be tuned.

[0068] Method 400 may include contacting the aluminum-and-oxygen-containing material with the plasma effluents of the etchant precursor at operation 450. The contacting may form volatile material comprising an aluminum-and-chlorine-containing material. After forming the volatile material comprising an aluminum-and-chlorine-containing material, method 400 may include pumping the aluminum-and-chlorine-containing material from the processing region.

[0069] As shown in FIG. 4, method 400 may include repeating operations 405-450 for a number of cycles. By repeating operations 405-450 aluminum-containing byproduct may be further reduced and / or removed from the semiconductor processing chamber. Operations 405-450 may be repeated for any number of cycles, such as two cycles, three cycles, four cycles, five cycles, ten cycles, or more.

[0070] Method 400 may be performed at any of the temperatures and / or pressures previously discussed with regard to method 200.

[0071] Embodiments of the present technology may combine method 200 and method 400 to clean a semiconductor processing chamber. For example, a cleaning method may include performing the operations of method 200, followed by one or more cycles of the operations of method 400, and again followed by the operations of method 200. As such, operations 205-240 of method 200 may first be performed as a first chamber cleaning operation to remove aluminum-containing byproduct within a coating disposed on one or more components of a semiconductor processing chamber. Then, operations 405-450 of method 400 may be performed as a second chamber cleaning operation to remove aluminum-and- fluorine-containing particles from the semiconductor processing chamber. Operations 405- 450 of method 400 may be repeated a plurality of cycles. Finally, operations 205-240 of method 200 may be performed again as a third chamber cleaning operation to remove aluminum-containing byproduct within the coating disposed on one or more components of a semiconductor processing chamber. During this cleaning method, operations 205-240 of method 200 and operations 405-450 of method 400 may include any of the features previously discussed.

[0072] Conventional technologies may suffer from embedded aluminum-containing byproduct, such as aluminum-and-fluorine-containing byproduct, that may contaminate substrates being processed and / or lead to uncontrolled etching operations using fluorine- containing precursors. During subsequent processing, the embedded aluminum-containing byproduct may become exposed or otherwise outgas from the coating, thus becoming present in the processing region. The present embodiments may overcome challenges associated with conventional technologies by performing a variety of cleaning operations to remove residual and / or embedded aluminum-containing byproduct. The present embodiments, as described, may successfully reduce and / or eliminate aluminum-containing byproduct, such asaluminum-and-fluorine-containing byproduct, that may not be removed using conventional technologies.

[0073] In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology7. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

[0074] Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology. Additionally, methods or processes may be described as sequential or in steps, but it is to be understood that the operations may be performed concurrently, or in different orders than listed.

[0075] Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0076] As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a precursor” includes a plurality of such precursors, and reference to “the material” includes reference to one or more materials and equivalents thereof known to those skilled in the art, and so forth.

[0077] Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, butthey do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups.

Claims

CLAIMS:

1. A cleaning method comprising: providing one or more etchant precursors to a processing region of a semiconductor processing chamber, wherein a substrate is disposed on a substrate support within a processing region of the semiconductor processing chamber; etching an aluminum-containing material on the substrate, wherein the etching introduces an aluminum-containing byproduct to a coating disposed on one or more components of the semiconductor processing chamber; providing a first cleaning precursor to the processing region; forming plasma effluents of the first cleaning precursor; contacting the coating with the plasma effluents of the first cleaning precursor, wherein the contacting removes an exposed portion of the aluminum-containing byproduct; providing a second cleaning precursor to the processing region; forming plasma effluents of the second cleaning precursor; contacting the coating with the plasma effluents of the second cleaning precursor, wherein the contacting removes a portion of the coating to expose an embedded portion of the aluminum-containing byproduct; providing the first cleaning precursor to the processing region; forming plasma effluents of the first cleaning precursor; and contacting the coating with the plasma effluents of the first cleaning precursor, wherein the contacting removes the embedded portion of the aluminum-containing byproduct.

2. The cleaning method of claim 1 , wherein the one or more etchant precursors comprises a fluorine-containing precursor.

3. The cleaning method of claim 1, wherein the substrate support comprises an aluminum-containing material.

4. The cleaning method of claim 1, wherein the substrate further comprises a carbon-containing material.

5. The cleaning method of claim 1, wherein the aluminum-containing byproduct comprises an aluminum-and-fluorine-containing byproduct.

6. The cleaning method of claim 1, wherein the coating comprises a silicon-and-oxy gen-containing material.

7. The cleaning method of claim 1, wherein the first cleaning precursor comprises one or more chlorine-containing precursors.

8. The cleaning method of claim 1, wherein the first cleaning precursor comprises boron trichloride (BCh) and diatomic chlorine (Ch).

9. The cleaning method of claim 1 , further comprising: halting a flow of the first cleaning precursor prior to providing the second cleaning precursor.

10. The cleaning method of claim 1, wherein the second cleaning precursor comprises one or more fluorine-containing precursors.

11. A cleaning method comprising: i) purging a processing region of a semiconductor processing chamber to bring an aluminum-and-fluorine-containing byproduct to the processing region; ii) providing a hydrogen-containing precursor to the processing region; iii) forming plasma effluents of the hydrogen-containing precursor; iv) contacting the aluminum-and-fluorine-containing byproduct with the plasma effluents of the hydrogen-containing precursor, wherein the contacting reduces the aluminum-and-fluorine-containing byproduct to an aluminum-containing material; v) providing an oxy gen-containing precursor to the processing region; vi) forming plasma effluents of the oxy gen-containing precursor; vii) contacting the aluminum-containing material with the plasma effluents of the oxy gen-containing precursor, wherein the contacting oxidizes the aluminum-containing material to form an aluminum-and-oxy gen-containing material; viii) providing an etchant precursor to the processing region; ix) forming plasma effluents of the etchant precursor; and x) contacting the aluminum-and-oxygen-containing material with the plasma effluents of the etchant precursor, wherein the contacting forms volatile material comprising an aluminum-and-chlorine-containing material.

12. The cleaning method of claim 11, further comprising: xi) pumping the aluminum-and-chlorine-containing material from the processing region.

13. The cleaning method of claim 11, further comprising: cyclically repeating operations i) through xi) a plurality of cycles.

14. The cleaning method of claim 11, wherein the hydrogen-containing precursor comprises diatomic hydrogen (H2).

15. The cleaning method of claim 11, wherein the oxygen-containing precursor comprises diatomic oxygen (O2).

16. The cleaning method of claim 11, wherein the etchant precursor comprises boron trichloride (BCk) and diatomic chlorine (CI2).

17. A cleaning method comprising: i) performing a first chamber cleaning operation to remove aluminum- containing byproduct within a coating disposed on one or more components of a semiconductor processing chamber; ii) performing a second chamber cleaning operation to remove aluminum-and- fluorine-containing particles from the semiconductor processing chamber; and iii) performing a third chamber cleaning operation to remove aluminum- containing byproduct within the coating disposed on one or more components of a semiconductor processing chamber.

18. The cleaning method of claim 17, wherein the first chamber cleaning operation and the third chamber cleaning operation comprise: providing a first cleaning precursor to the processing region: forming plasma effluents of the first cleaning precursor; contacting the coating with the plasma effluents of the first cleaning precursor, wherein the contacting removes an exposed portion of the aluminum- containing byproduct; providing a second cleaning precursor to the processing region; forming plasma effluents of the second cleaning precursor;contacting the coating with the plasma effluents of the second cleaning precursor, wherein the contacting removes a portion of the coating to expose an embedded portion of the aluminum-containing byproduct; providing the first cleaning precursor to the processing region; forming plasma effluents of the first cleaning precursor; and contacting the coating with the plasma effluents of the first cleaning precursor, wherein the contacting removes the embedded portion of the aluminum- containing byproduct.

19. The cleaning method of claim 17, wherein the second chamber cleaning operation comprises a reduction-oxidation reaction.

20. The cleaning method of claim 19, wherein the reduction-oxidation reaction is repeated a plurality of times.

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