Aluminum fluoride etch from aluminum-containing components

Abstract

A method of treating an aluminum fluoride or an aluminum oxyfluoride includes providing a fluorine-containing species into a processing chamber in which one or more components are located, moving the one or more components out of the processing chamber, and cleaning the one or more components with an etching composition. The one or more components include aluminum, an aluminum alloy, or an aluminum-containing material.

Description

[0001] Incorporated by Reference The PCT Application Table, which is a part of this application, is concurrently filed with the specification. Each of the applications listed in the concurrently filed PCT Application Table from which this application claims benefit or priority is incorporated by reference in its entirety and for all purposes. BACKGROUND

[0002] In semiconductor device manufacturing processes, various materials are deposited on the interior surfaces of a processing chamber or on the surfaces of components in the processing chamber to form wall deposits. The wall deposits can be a source of contamination for substrates in subsequent operations and can increase in thickness with the number of operation repetitions. The wall deposits can be removed from the interior surfaces of the processing chamber or from the surfaces of the components in the processing chamber.

[0003] The background description provided herein is for the purpose of generally presenting the context of the disclosure. The work of the presently named inventors, to the extent the work is described in this background section, as well as aspects of the description that can not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY

[0004] One aspect relates to a method of cleaning an aluminum fluoride or aluminum oxyfluoride, wherein the method comprises providing a fluorine-containing substance into a processing chamber in which one or more components are located, removing the one or more components from the processing chamber; and cleaning the one or more components with an etching composition, wherein the one or more components comprise aluminum, an aluminum alloy, or an aluminum-containing material.

[0005] In some embodiments, cleaning the one or more components comprises etching the aluminum fluoride or aluminum oxyfluoride from a surface of the one or more components.

[0006] In some embodiments, cleaning the one or more components comprises separating the aluminum fluoride or aluminum oxyfluoride from a surface of the one or more components.

[0007] In some embodiments, the one or more components comprise a pedestal, a showerhead, or a showerhead-pedestal.

[0008] In some embodiments, the etching composition comprises a hydroxyl-containing solution comprising potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a combination thereof.

[0009] In some embodiments, the concentration of the hydroxyl-containing solution is about 0.1% to about 45% weight / volume.

[0010] In some embodiments, the concentration of the hydroxyl-containing solution is about 0.5% to about 30% weight / volume.

[0011] In some embodiments, the hydroxyl-containing solution has a concentration of about 1% to about 20% weight / volume.

[0012] In some embodiments, the hydroxyl-containing solution has a concentration of about 1.5% to about 10% weight / volume.

[0013] In some embodiments, the hydroxyl-containing solution has a concentration of about 2% to about 7% weight / volume.

[0014] In some embodiments, the one or more components are cleaned for a time of about 0.1 to about 45 minutes.

[0015] In some embodiments, the one or more components are cleaned for a time of about 1 to about 30 minutes.

[0016] In some embodiments, the one or more components are cleaned for a time of about 1 to about 10 minutes.

[0017] In some embodiments, the one or more components are cleaned for a time of about 5 to about 25 minutes.

[0018] In some embodiments, the one or more components are cleaned for a time of about 8 to about 20 minutes.

[0019] In some embodiments, the one or more components are cleaned for a time of about 10 to about 15 minutes.

[0020] In some embodiments, the fluorine-containing species comprises a nitrogen fluoride plasma.

[0021] The method further comprises depositing a film on a substrate in the processing chamber prior to providing the fluorine-containing species into the processing chamber.

[0022] The method further comprises removing the substrate from the processing chamber after depositing the film.

[0023] The method further comprises providing the one or more components into the processing chamber after cleaning the one or more components with the etching composition.

[0024] Another aspect relates to a method of etching in a processing chamber, wherein the method comprises exposing a surface of a component comprising aluminum fluoride or aluminum oxyfluoride to a fluorine-containing species, wherein the surface of the component comprises aluminum, an aluminum alloy, or an aluminum-containing material; and exposing the aluminum fluoride or aluminum oxyfluoride to an etching composition, wherein the etching composition comprises a hydroxyl-containing solution.

[0025] In some embodiments, the component comprises a pedestal, a showerhead, or a showerhead-pedestal.

[0026] In some embodiments, exposing the surface of the component to the fluorine-containing substance includes forming the aluminum fluoride or aluminum oxyfluoride on the surface of the component.

[0027] In some embodiments, exposing the aluminum fluoride or aluminum oxyfluoride to the etching composition includes immersing the component in the etching composition.

[0028] In some embodiments, exposing the surface of the component to the etching composition includes immersing the component in the etching composition.

[0029] In some embodiments, the fluorine-containing substance includes a nitrogen fluoride plasma.

[0030] The method further includes exposing the surface of the component to a precursor prior to providing the fluorine-containing substance, thereby forming a silicon-containing film on the surface of the component.

[0031] The method further includes disposing the one or more components in the processing chamber after exposing the aluminum fluoride to the etching composition.

[0032] In some embodiments, the etching composition includes potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a combination thereof.

[0033] In some embodiments, the etching composition has a concentration of about 0.1% to about 45% weight / volume.

[0034] In some embodiments, the etching composition has a concentration of about 0.5% to about 30% weight / volume.

[0035] In some embodiments, the etching composition has a concentration of about 1% to about 20% weight / volume.

[0036] In some embodiments, the etching composition has a concentration of about 1.5% to about 10% weight / volume.

[0037] In some embodiments, the etching composition has a concentration of about 2% to about 7% weight / volume.

[0038] In some embodiments, the component is exposed for about 0.1 to about 45 minutes.

[0039] In some embodiments, the component is exposed for about 1 to about 30 minutes.

[0040] In some embodiments, the component is exposed for about 1 to about 10 minutes.

[0041] In some embodiments, the component is exposed for about 5 to about 25 minutes.

[0042] In some embodiments, the component is exposed for about 8 to about 20 minutes.

[0043] In some embodiments, the component is exposed for about 10 to about 15 minutes.

[0044] Another aspect relates to a method of cleaning a component, wherein the method comprises: providing a component comprising an aluminum-containing surface; and cleaning the component using a hydroxyl-containing composition.

[0045] In some embodiments, cleaning the component comprises soaking the component in the hydroxyl-containing composition.

[0046] In some embodiments, the component comprises a pedestal, a showerhead, or a showerhead-pedestal.

[0047] In some embodiments, the hydroxyl-containing composition comprises potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a combination thereof.

[0048] In some embodiments, the concentration of the hydroxyl-containing solution is about 0.1% to about 45% weight / volume.

[0049] In some embodiments, the concentration of the hydroxyl-containing solution is about 0.5% to about 30% weight / volume.

[0050] In some embodiments, the concentration of the hydroxyl-containing solution is about 1% to about 20% weight / volume.

[0051] In some embodiments, the concentration of the hydroxyl-containing solution is about 1.5% to about 10% weight / volume.

[0052] In some embodiments, the concentration of the hydroxyl-containing solution is about 2% to about 7% weight / volume.

[0053] Another aspect relates to an apparatus comprising: a processing chamber comprising one or more aluminum-containing components inside the processing chamber; a first gas source fluidly coupled with the processing chamber; a second gas source fluidly coupled with the processing chamber; a plasma source fluidly coupled with the processing chamber; and a controller configured to: (a) cause a precursor in the processing chamber to form a film on a substrate; and (b) cause a fluorine-containing species inside the processing chamber.

[0054] In some embodiments, the one or more components are made of aluminum, an aluminum alloy, or an aluminum-containing material.

[0055] In some embodiments, the one or more components comprise a pedestal, a showerhead, or a showerhead-pedestal.

[0056] In some embodiments, the film comprises silicon oxide, silicon nitride, doped or undoped polysilicon, or doped or undoped silicon carbide.

[0057] In some embodiments, the fluorine-containing substance comprises a fluorine- containing source gas, a fluorine-containing plasma, or a mixture thereof.

[0058] In some embodiments, the fluorine-containing source gas comprises nitrogen trifluoride (NF3), molecular fluorine (F2), carbon tetrafluoride (CF4), carbon hexafluoride (C2F6), xenon difluoride (XeF2), fluoromethane (CH3F), difluoromethane (CH2F2), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8), sulfur hexafluoride (SF6), or a combination thereof.

[0059] In some embodiments, the plasma source comprises a remote plasma source.

[0060] These and other aspects are further described below with reference to the figures. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 is a flow chart of an exemplary method of cleaning a surface of one or more components in a process chamber, in accordance with some embodiments.

[0062] FIG. 2 is a flow chart of an exemplary method of cleaning a component, in accordance with some embodiments.

[0063] FIGS. 3A-3E are scanning electron micrograph images showing etching of aluminum fluoride from a component surface as a function of etching time, in accordance with some embodiments.

[0064] FIG. 4 is a schematic diagram showing the size range and number of aluminum fluoride particles on a substrate backside before and after cleaning a showerhead- pedestal underneath the substrate, in accordance with some embodiments.

[0065] FIGS. 5A and 5B show block diagrams of exemplary substrate processing systems, in accordance with some embodiments.

[0066] FIG. 6 shows a schematic diagram of an exemplary processing system that can be used to perform the methods described herein. DETAILED DESCRIPTION

[0067] In the following description, numerous specific details are set forth to provide a thorough understanding of the implementations. The disclosed implementations can be practiced without the specific details, or with variations upon these details, in some instances. In other instances, well-known processing operations have not been described in detail in order not to unnecessarily obscure the disclosed implementations.

[0068] Terminology The term "acyl" or "alkanoyl" as used interchangeably herein denotes a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms in linear, branched, cyclic configurations, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen, attached to a parent molecular group through a carbonyl group as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, wherein R is hydrogen, aliphatic, or aromatic, as defined herein.

[0069] "Alkanoyloxy" means an alkanoyl group as defined herein attached to a parent molecular group through an oxy group as defined herein. This group is exemplified by acetyloxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, wherein R is hydrogen, aliphatic, or aromatic, as defined herein.

[0070] "Aliphatic" means a hydrocarbon group of at least one carbon atom up to 50 carbon atoms (C 1-50 ), such as 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), and which comprises alkanes (or alkyl groups), alkenes (or alkenyl groups), alkynes (or alkynyl groups), including cyclic versions thereof, and further including straight- chain and branched-chain versions, as well as all stereo and positional isomers. The aliphatic group is unsubstituted or substituted, for example, with a functional group as described herein. For example, the aliphatic group can be substituted with one or more substituent groups, such as those described herein for alkyl groups.

[0071] "Aliphatic-carbonyl" means an aliphatic group coupled to or which can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0072] "Aliphatic-carbonyloxy" means an aliphatic group coupled to or which can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0073] "Aliphatic-oxy" means an aliphatic group coupled or couplable to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, an aliphatic-oxy is -O-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0074] "Aliphatic-oxycarbonyl" means an aliphatic group coupled or couplable to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, an aliphatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0075] "Alkyl-aryl," "alkenyl-aryl," and "alkynyl-aryl" mean and refer to an alkyl, alkenyl, or alkynyl group, respectively, coupled or couplable (or attached) to a parent molecular group through an aryl group, as defined herein. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl can be substituted with one or more substituents, as described herein for alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have from 7 to 16 carbons (C 7-16 alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 1-6 alkyl-C 4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups have from 7 to 16 carbons (C 7-16 alkenyl-aryl), as well as those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 alkenyl-C 4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups have from 7 to 16 carbons (C 7-16 alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 alkynyl-C 4-18 aryl). In some embodiments, an alkyl-aryl is -L-R, wherein L is an aryl or arylene group, as defined herein, and R is an alkyl group, as defined herein. In some embodiments, an alkenyl-aryl is -L-R, wherein L is an aryl or arylene group, as defined herein, and R is an alkenyl group, as defined herein. In some embodiments, an alkynyl-aryl is -L-R, wherein L is an aryl or arylene group, as defined herein, and R is an alkynyl group, as defined herein.

[0076] "Alkenyl" means an unsaturated monovalent hydrocarbon having at least two carbon atoms to 50 carbon atoms (C 2-50 ) (e.g., two to 25 carbon atoms (C 2-25 ), or two to ten carbon atoms (C 2-10 )) and at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. The alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 alkyl groups having one or more double bonds. The alkenyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to a parent molecular group or between a parent molecular group and another substituent. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substituents, as described herein for alkyl groups. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0077] "Alkoxy" means -OR, wherein R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkoxy groups.

[0078] "Alkoxyalkyl" means an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbon (C 2-12 alkoxyalkyl groups, as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C 1-6 alkoxy-C 1-6 alkyl groups). In some embodiments, the alkoxyalkyl group is -L-O-R, wherein L and R are each independently an alkyl group, as defined herein.

[0079] "Alkoxycarbonyl" means -C(O)-OR, where R is an optionally substituted aliphatic group, as described herein. In particular embodiments, the alkoxycarbonyl is -C(O)-Oak, where Ak is an alkyl group, as defined herein. The alkoxycarbonyl can be substituted or unsubstituted. For example, the alkoxycarbonyl can be substituted with one or more substituent groups, as described herein for alkyl groups. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkoxycarbonyl.

[0080] "Alkyl" means a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C 1-50 ) (e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), where the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), t-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), t-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., divalent), which is formed by removing one or more hydrogens to form an appropriate linkage to a parent molecule group or between a parent molecule group and another substituent. For example, the alkyl group can be substituted with one, two, three, or (in the case of alkyl groups having two or more carbons) four substituents, the substituents being independently selected from the group consisting of: (1) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl); (2) C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl); (3) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6alkyl); (4) amino (e.g., -NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, halo heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, wherein L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehydo (e.g., -C(O)H); (11) C 3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, wherein R is heterocyclyl as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is heterocyclyl as defined herein); (16) hydroxyl (e.g., -OH); (17) N -protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 thioalkyl (e.g., -S-R, wherein R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 , wherein R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 4-18 aryl); (23) -C(O)NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 4-18 aryl); (24) -SO2R 1, where R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b) C 4-18 Aryl and (c) C 4-18 -Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (25) -SO2NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); and (26)-NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) N -Protective group, (c)C 1-6 Alkyl, (d)C 2-6 alkenyl, (e) C 2-6 alkynyl group, (f) C 4-18 Aryl, (g) C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl group, where R is C 4-18 Aryl), (h) C 3-8 cycloalkyl groups, and (i) C 3-8 cycloalkyl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 3-8 The alkyl group is a cycloalkyl group, wherein in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C10. 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 Or C 1-24 alkyl.

[0081] “Alkylene,” “alkenylene,” or “alkynylene” mean, respectively, the polyvalent (e.g., divalent) version of an alkyl, alkenyl, or alkynyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, the alkylene group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkylene. In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkenylene or alkynylene. The alkylene, alkenylene, or alkynylene group can be branched or unbranched. The alkylene, alkenylene, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group can be substituted with one or more substituent groups, as described herein for alkyl groups.

[0082] “Alkylsulfinyl” means an alkyl group, as defined herein, attached through a -S(O)- group to the parent molecular group. In some embodiments, the unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 alkylsulfinyl. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0083] “Alkylsulfinylalkyl” means an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is C 2-12 or C 2-24 alkylsulfinylalkyl (e.g., C 1-6 alkylsulfinyl-C 1-6 alkyl, or C 1-12 alkylsulfinyl-C 1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, where L and R are each independently an alkyl group, as defined herein.

[0084] “Alkylsulfonyl” means an alkyl group as defined herein linked to the parent molecular group through a -SO2- group. In some embodiments, an unsubstituted alkylsulfonyl is a C 1-6 or C 1-12 alkylsulfonyl. In other embodiments, an alkylsulfonyl is -SO2-R, where R is an optionally substituted alkyl (e.g., an optionally substituted C 1-12 alkyl, haloalkyl, or perfluoroalkyl) as described herein.

[0085] “Alkylsulfonylalkyl” means an alkyl group as defined herein substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl is a C 2-12 or C 2-24 alkylsulfonylalkyl (e.g., a C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, an alkylsulfonylalkyl is -L-SO2-R, where L and R are each independently an alkyl group as defined herein.

[0086] “Alkynyl” means an unsaturated monovalent hydrocarbon having at least two carbon atoms to 50 carbon atoms (C 2-50 ) (e.g., two to 25 carbon atoms (C 2-25 ), or two to ten carbon atoms (C 2-10 ) and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from the removal of one hydrogen atom from one carbon atom of a parent alkynyl hydrocarbon. Alkynyl groups can be branched, straight-chain or cyclic (e.g., cycloalkynyl). An exemplary alkynyl includes an optionally substituted C 2-24 alkyl group having one or more triple bonds. Alkynyl groups can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or multivalent (e.g., divalent), by the removal of one or more hydrogens to form an appropriate linkage to a parent molecular group or between a parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, an alkynyl group can be substituted with one or more substituents as described herein for alkyl groups.

[0087] “Ambient temperature” means a temperature ranging from 16 °C to 26 °C, such as a temperature from 19 °C to 25 °C or from 20 °C to 25 °C.

[0088] “Amide” means -C(O)NR 1 R 2or -NHCOR 1 wherein R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein.

[0089] "Amino" means -NR 1 R 2 wherein R 1 and R 2 each independently is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof, as defined herein; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein. In particular embodiments, R 1 and R 2 each independently is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted siloxy. In particular embodiments, R 1 and R 2 together can form an optionally substituted heterocyclyl, as defined herein.

[0090] "Aminoalkyl" means an alkyl group as defined herein substituted with an amino group, as defined herein. In some embodiments, the aminoalkyl is -L-NR 1 R 2 wherein L is an alkyl group, as defined herein, and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein. In other embodiments, the aminoalkyl is -L-C(NR 1 R 2 )(R 3 )-R 4 wherein L is a covalent bond or an alkyl group, as defined herein; R 1 and R 2each independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein; or R 1 with R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein; and R 3 with R 4 each independently H or alkyl, as defined herein.

[0091] "Aminooxy" means an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 wherein R 1 with R 2 each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted siloxy, or any combination thereof, as defined herein; or R 1 with R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein. In particular embodiments, R 1 with R 2 each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted siloxy.

[0092] "Aromatic" means a cyclic, conjugated group or moiety of 5 to 15 ring atoms (unless otherwise specified), either monocyclic (e.g., phenyl) or multiple, fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized system of π electrons. Typically, the number of out-of-plane π electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted with functional groups as described herein, for example. For example, an aromatic group can be substituted with one or more substituent groups as described herein for alkyl and / or aryl groups.

[0093] "Aromatic-carbonyl" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the aromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0094] "Aromatic-carbonyloxy" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the aromatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0095] "Aromatic-oxy" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, the aromatic-oxy is -O-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0096] "Aromatic-oxycarbonyl" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0097] "Aryl" means a group containing at least five carbon atoms to 15 carbon atoms (C 5-15 )(e.g., five to ten carbon atoms (C 5-10) aromatic carbocyclyl having a single ring or multiple condensed rings, which condensed rings can or can not be aromatic, provided that the point of attachment to the remainder of the compound disclosed herein is through an atom of the aromatic carbocyclyl group. Aryl groups can be substituted with one or more groups other than hydrogen (e.g., aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof). Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic moiety having at least one heteroatom incorporated in the ring of the aromatic moiety. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Also included within the term aryl is the term non-heteroaryl, which defines a group containing an aromatic moiety and no heteroatoms. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with one, two, three, four, or five substituents, independently selected from the group consisting of: (1) C 1-6 alkanoyl (e.g., -C(O)-R, where R is C 1-6 alkyl); (2) C 1-6 alkyl; (3) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl); (4) C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-O-R, where L and R are each independently C 1-6 alkyl); (5) C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl); (6) C 1-6 alkylsulfinyl-C 1-6 alkyl (e.g., -L-S(O)-R, where L and R are each independently C 1-6 alkyl); (7) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl); (8) C 1-6 alkylsulfonyl-C 1-6 alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein); (11) C 1-6Aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 wherein L 1 is C 1-6 alkyl; L 2 is a covalent bond or C 1-6 alkyl; R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl as defined herein; R 3 and R 4 are each independently H or C 1-6 alkyl); (12) heteroaryl; (13) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 4-18 aryl); (14) aroyl (e.g., -C(O)-R, wherein R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 azidoalkyl (e.g., -L-N3, wherein L is C 1-6 alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-C 1-6 alkyl (e.g., -L-C(O)H, wherein L is C 1-6 alkyl); (20) C 3-8 cycloalkyl; (21) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 3-8 cycloalkyl); (22) halogen; (23) C 1-6 haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 wherein L 1 is C 1-6 alkyl; L 2 is a covalent bond or C 1-6 alkyl; X is fluorine, bromine, chlorine, or iodine; and R 1 and R2 Each independently is H or C 1-6 (24) Alkyl group; (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein); (25) Heterocyclic oxygen group (e.g., -OR, where R is a heterocyclic group as defined herein); (26) Heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (27) Hydroxyl group (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L) 1 -OH or -L 2 -C(OH)(R 1 )-R 2 L 1 C 1-6 Alkyl; L 2 It is covalent or alkyl; and R 1 With R 2 Each independently represents H or C as defined in this article. 1-6 (29) alkyl; (30) nitro; (30) C 1-6 Nitroalkyl (e.g., -L) 1 -NO or -L 2 -C(NO)(R 1 )-R 2 L 1 C 1-6 Alkyl; L 2 It is covalent or alkyl; and R 1 With R 2 Each independently represents H or C as defined in this article. 1-6 Alkyl); (31) N - Protected amino groups; (32) N -Protective amino-C 1-6 Alkyl group; (33) oxo group (e.g., =O); (34) C 1-6 Thioalkyl groups (e.g., -SR, where R is C) 1-6 Alkyl); (35) Thio-C 1-6 Alkoxy-C 1-6 Alkyl groups (e.g., -LSR, where L and R are each independently C). 1-6 Alkyl); (36)-(CH2) r CO2R 1 Where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (37)-(CH2) r CONR 1 R 2 , where r is an integer from 0 to 4, and R 1 With R 2 Each of the following groups can be selected independently: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (38)-(CH2) r SO2R 1 , where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b) C 4-18 Aryl and (c)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4 and R 1 With R 2 Each of the following groups can be selected independently: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4 and R 1 With R 2 Each of the following groups can be selected independently: (a) hydrogen, (b) N -Protective group, (c) C 1-6 Alkyl, (d)C 2-6 alkenyl, (e) C 2-6 alkynyl group, (f) C 4-18aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), where in one embodiment no two groups are bound to the nitrogen atom through a carbonyl or sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, where n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, where n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, where R is aryl); (45) cycloalkyloxy (e.g., -O-R, where R is cycloalkyl); (46) cycloalkylalkyloxy (e.g., -O-L-R, where L is alkyl and R is cycloalkyl); and (47) arylalkyloxy (e.g., -O-L-R, where L is alkyl and R is aryl). In particular embodiments, unsubstituted aryl is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 aryl.

[0098] "Aryl-alkyl," "aryl-alkenyl," and "aryl-alkynyl" mean an aryl group as defined herein coupled or couplable (or attached) to a parent molecular group, through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl groups can be substituted or unsubstituted. For example, the aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl groups can be substituted with one or more substituent groups, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbons (C 7-16 aryl-alkyl), and those having an aryl group with 4 to 18 carbons and an alkyl group with 1 to 6 carbons (i.e., C 4-18 aryl-C 1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbons (C 7-16 aryl-alkenyl), and those having an aryl group with 4 to 18 carbons and an alkenyl group with 2 to 6 carbons (i.e., C4-18 Aryl-C 2-6 Alkenyl). Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbons (C). 7-16 Aryl-alkynyl), and those having an aryl group with 4 to 18 carbons and an alkynyl group with 2 to 6 carbons (i.e., C). 4-18 Aryl-C 2-6 (Alkynyl). In some embodiments, the aryl-alkyl group is -LR, where L is an alkyl or alkylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkenyl group is -LR, where L is an alkenyl or alkenyl group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -LR, where L is an alkynyl or alkynyl group as defined herein, and R is an aryl group as defined herein.

[0099] "Arylene" means the polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylenes include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 Or C 6-10 Aryl groups. Aryl groups can be branched or unbranched. Aryl groups can also be substituted or unsubstituted. For example, aryl groups can be substituted with one or more substituents, as described herein with respect to aryl groups.

[0100] "Arylalkoxy" means an aryl-alkyl group as defined herein that is attached to a parent molecule group by an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group as defined herein and R is an aryl group as defined herein.

[0101] "Aryloxy" refers to -OR, where R is an aryl group that is optionally substituted as described herein. In some embodiments, the unsubstituted aryloxy group is C. 4-18 Or C 6-18 Aryloxy group. In other embodiments, R is an aryl group optionally substituted with an alkyl, alkanoyl, amino, hydroxyl, or similar group.

[0102] "Aryloxy" means an ary! group as defined herein attached through an oxy group. In some embodiments, an unsubstituted aryloxy group is C6-Ci0aryl-O-. In other embodiments, an aryloxy group is -O-R, wherein R is an aryl group as defined herein. 5-19 Aryloxy. In other embodiments, an aryloxy group is -O-R, wherein R is an aryl group as defined herein.

[0103] "Aryloyl" means an aryl group as defined herein attached through a carbonyl group. In some embodiments, an unsubstituted arylcarbonyl group is C6-Ci0aryl-C(O)-. In other embodiments, an arylcarbonyl group is -C(O)-R, wherein R is an aryl group as defined herein. 7-11 Aryloyl or C 5-19 Aryloyl. In other embodiments, an arylcarbonyl group is -C(O)-R, wherein R is an aryl group as defined herein.

[0104] "Aryloyloxy" means an arylcarbonyl group as defined herein attached through an oxy group. In some embodiments, an unsubstituted arylcarbonyloxy group is C6-Ci0aryl-C(O)O-. In other embodiments, an arylcarbonyloxy group is -OC(O)-R, wherein R is an aryl group as defined herein. 5-19 Aryloyloxy. In other embodiments, an arylcarbonyloxy group is -OC(O)-R, wherein R is an aryl group as defined herein.

[0105] "Azo" means a -N=N- group.

[0106] "Azo" means a -N=N- group.

[0107] "Azo" means a -N=N- group.

[0108] "Carbamoyl" means an amino group as defined herein attached through a carbonyl group. In some embodiments, a carbamoyl group is -C(O)NR 1 R 2 group, wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, as defined herein, or any combination thereof; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein.

[0109] "Carbamoyloxy" means a carbamoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. In some embodiments, the carbamoyloxy group is -OC(0)NR 1 R 2 group, wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof, as defined herein; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein.

[0110] "Carbonimidoyl" means a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted arylalkyl, optionally substituted siloxy, or any combination thereof, as defined herein.

[0111] "Carbonyl" means a -C(O)- group, which can also be represented as >C=0.

[0112] "Carboxyl" means a -CO2H group or a salt thereof.

[0113] "Catalyst" means a compound that is present in small amounts relative to the reactants and is capable of catalyzing a synthetic reaction, as would be readily understood by a person of ordinary skill in the art. In some embodiments, the catalyst can comprise a transition metal coordination complex.

[0114] "Cyanato" means an -OCN group.

[0115] "Cyano" means a -CN group.

[0116] "Cycloaliphatic" means a cyclic aliphatic group, as defined herein.

[0117] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, wherein R is a cycloalkyl group, as defined herein.

[0118] "Cycloalkylalkoxy" means -O-L-R, where L is alkyl or alkylene as defined herein, and R is cycloalkyl as defined herein.

[0119] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of three to eight carbons (unless otherwise specified), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1. heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group can be substituted with one or more groups, including those described herein for alkyl groups. Additionally, a cycloalkyl group can include one or more double and / or triple bonds.

[0120] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group as defined herein.

[0121] "Disilanyl" means a group containing a Si-Si bond. In some embodiments, a disilanyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 - or -SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 and R S5 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0122] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0123] "Electron-donating group" means a functional group capable of donating at least a portion of its electron density to a ring to which it is directly attached, such as by resonance.

[0124] "Electron-withdrawing group" means a functional group capable of accepting electron density from a ring to which it is directly attached, for example, through inductive electron withdrawal.

[0125] "Halo" means F, CI, Br, or I.

[0126] "Haloaliphatic" means an aliphatic group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced with a halogen atom (e.g., fluorine, bromine, chlorine, or iodine).

[0127] "Haloalkyl" means an alkyl group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced with a halogen atom (e.g., fluorine, bromine, chlorine, or iodine). In one independent embodiment, a haloalkyl group can be a -CX3group, where each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, a haloalkyl group is -L-X, where L is an alkyl group as defined herein and X is fluorine, bromine, chlorine, or iodine. In other embodiments, a haloalkyl group is -L-C(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine, or iodine; and R 1 and R 2 are each independently H or an alkyl group as defined herein.

[0128] "Haloheteroaliphatic" means a heteroaliphatic group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced with a halogen atom (e.g., fluorine, bromine, chlorine, or iodine).

[0129] "Heteroaliphatic" means an aliphatic group as defined herein that contains at least one heteroatom to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. A heteroaliphatic group can be unsubstituted or substituted, for example, with a functional group described herein. For example, a heteroaliphatic group can be substituted with one or more substituent groups, such as those described herein for an alkyl group.

[0130] "Heteroaliphatic-carbonyl" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0131] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0132] "Heteroaliphatic-oxy" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, the heteroaliphatic-oxy is -O-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0133] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0134] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" mean, respectively, an alkyl, alkenyl, or alkynyl group as defined herein, which contains at least one heteroatom, up to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0135] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" mean, respectively, a polyvalent (e.g., divalent) version of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, as described herein.

[0136] "Heteroaromatic" means an aromatic group as defined herein including at least one heteroatom to 20 heteroatoms (e.g., one to 15 heteroatoms, or one to 5 heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. The heteroaromatic group is unsubstituted or substituted with, for example, functional groups described herein. For example, the heteroaromatic group can be substituted with one or more substituent groups as described herein for alkyl and / or aryl groups.

[0137] "Heteroaromatic-carbonyl" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the heteroaromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0138] "Heteroaromatic-carbonyloxy" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0139] "Heteroaromatic-oxy" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, the heteroaromatic-oxy is -O-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0140] "Heteroaromatic-oxycarbonyl" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the heteroaromatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0141] "Heteroaryl" means an aromatic group containing at least one heteroatom up to six heteroatoms (e.g., one to four heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, where the condensed rings can or can not be aromatic and / or contain heteroatoms, provided the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups can be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclyl groups as defined herein that are aromatic, i.e., that contain 4n+2 π electrons within a single or multiple ring system.

[0142] "Heteroarylene" means a polyvalent (e.g., divalent) version of a heteroaryl group as described herein.

[0143] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particularly disclosed embodiments, a heteroatom does not include a halogen atom, e.g., when valence restrictions do not permit.

[0144] "Heterocyclyl" means a 5-, 6-, or 7-membered ring (unless otherwise specified) containing one, two, three, or four heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, or halogen). A 5-membered ring has zero to two double bonds, while a 6-membered ring and a 7-membered ring have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings are fused with one, two, or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring (e.g., indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothiophenyl, and the like). Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl,thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0145] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein.

[0146] "Heterocyclyloyl" means a heterocyclyl group as defined herein attached through a carbonyl group to the parent molecular group. In some embodiments, a heterocyclyloyl group is -C(O)-R, wherein R is a heterocyclyl group as defined herein.

[0147] "Hydrazino" means -NR 1 -NR 2 R 3 wherein R 1 , R 2 and R 3each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof, as defined herein; or wherein R 1 in combination with R 2 or R 2 in combination with R 3 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein. In some embodiments, R 1 , R 2 and R 3 are each independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In particular embodiments, R 2 and R 3 together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl group.

[0148] “Hydroxyl” means -OH.

[0149] “Hydroxyalkyl” means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group can be attached to a single carbon atom of the alkyl group, exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, a hydroxyalkyl group is -L-OH, wherein L is an alkyl group, as defined herein. In other embodiments, a hydroxyalkyl group is -L-C(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group, as defined herein, and R 1 and R 2 are each independently H or alkyl, as defined herein.

[0150] “Imidoyl” means a group including a carbonimidoyl group. In some embodiments, an imidoyl group is C(NR 1 )R 2 , wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof, as defined herein. In other embodiments, an imidoyl group is -C(NR 1 )H, C(NR 1 )RAk , or C(NR N1 )R Ar , wherein R 1 is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, or optionally substituted siloxy as defined herein; R Ak is optionally substituted alkyl or optionally substituted aliphatic; R Ar is optionally substituted aryl or optionally substituted aromatic.

[0151] “Imino” means an -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In particular embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0152] “Isocyanato” means an -NCO group.

[0153] “Isocyano” means an -NC group.

[0154] “Ketone” means -C(O)R or a compound comprising such a group, wherein R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. Examples of ketones can include R 1 C(O)R, wherein R and R 1 are each independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0155] “Nitro” means an -NO2 group.

[0156] “Nitroalkyl” means an alkyl group as defined herein substituted with one to three nitro groups. In some embodiments, the nitroalkyl is -L-NO2, wherein L is an alkyl group as defined herein. In other embodiments, the nitroalkyl is -L-C(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2each independently H or alkyl as defined herein.

[0157] “Oxo” means an =0 group.

[0158] “Oxy” means -O-.

[0159] “Perfluoroalkyl” means an alkyl group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, a perfluoroalkyl group is -(CF2)n-CF3, where n is an integer from 0 to 10. n CF3, where n is an integer from 0 to 10.

[0160] “Perfluoroalkoxy” means an alkoxy group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. In some embodiments, a perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0161] “Salt” means an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes a cationic or anionic compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, nontoxic salts are described in Berge S. M. et al., “Pharmaceutical salts,” J. Pharm. Sci. 66:1-19 (1977), which is incorporated herein by reference in its entirety. In some embodiments, a salt is a pharmaceutically acceptable salt. J. Pharm. Sci.January; 66(1): 1-19; and in "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. Salts can be prepared in situ during the final isolation and purification of the compounds of the disclosure, or separately by reacting the free base group with a suitable organic acid (thus giving an anionic salt) or by reacting the free acid group with a suitable metal or organic salt (thus giving a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmoate, pamoate, phosphate, phosphate, phthalate, p-toluenesulfonate, salicylate, succinate, sulfate, tartrate, tannate, tartrate, teoclate, and tosylate. Representative cationic salts include ammonium, calcium, choline, diethylamine, diethanolamine, lithium, magnesium, potassium, sodium, and zinc.laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts such as alkali or alkaline earth, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metals, e.g., aluminum, bismuth, iron, and zinc; and nontoxic ammonium, quaternary ammonium, and amino cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium,Iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium). Optionally substituted furanium, Optionally substituted thiophenium, Optionally substituted imidazolium, Optionally substituted pyrazolium, Optionally substituted isothiazolium, Optionally substituted triazolium, Optionally substituted tetrazolium, Optionally substituted furazanium, Optionally substituted pyridinium, Optionally substituted pyrimidinium, Optionally substituted pyrazine Pyrazinium, optionally substituted triazinium, optionally substituted tetraazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, any Selectively substituted piperazinium, selectively substituted piperidinium, selectively substituted morpholinium, selectively substituted azepanium, selectively substituted azepinium, selectively substituted indolium, selectively substituted isoindolium, selectively substituted indolizinium, selectively substituted indazolium, and selectively substituted benzimidazolium.Optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium.

[0162] "Silyl" refers to SiR 1 R 2 R 3 or -SiR 1 R 2 - Group. In some embodiments, R 1 R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In a particular embodiment, R 1 R 2 and R 3 Each of the following is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silicon-based group is Si(R). a (OR) b (NR2) c Each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; a + b + c = 3. In a particular embodiment, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0163] "Silyloxy" refers to -OR, where R is an optionally substituted silicon group, as described herein. In some embodiments, the silyloxy group is -O-SiR. 1 R 2 R 3 , where R 1 R 2 and R 3each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, R 1 , R 2 , and R 3 each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the siloxy group is -0-Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each > 0; a+b+c = 3. In particular embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0164] "Sulfinyl" means a -S(O)- group.

[0165] "Sulfo" means a -S(O)2OH group.

[0166] "Sulfonyl" or "sulfonate" means a -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0167] "Thioalkyl" means an alkyl group as defined herein attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, where R is an alkyl group as defined herein.

[0168] "Thiol" means an -SH group.

[0169] It will be understood by those skilled in the art that the above provided definitions are not intended to include impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, and the like). Such impermissible substitution patterns will be readily understood by those skilled in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted, unless otherwise indicated therein.

[0170] The terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art understand that the term "partially fabricated integrated circuit" can refer to a semiconductor wafer during any of the many stages of integrated circuit fabrication performed thereon. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm or 300 mm or 450 mm. Examples of wafer materials include silicon (Si), gallium arsenide (GaAs), and silicon germanium (SiGe). In addition to semiconductor wafers, other workpieces that can utilize the disclosed embodiments include various articles of manufacture, such as printed circuit boards, magnetic recording media, magnetic recording sensors, mirrors, optical elements, display devices or components (e.g., backplanes for pixelated display devices, flat panel displays, micro-mechanical devices, and the like). The workpieces can have various shapes, sizes, and materials.

[0171] A "semiconductor device manufacturing operation" as used herein is an operation performed during semiconductor device manufacturing. Typically, an entire manufacturing process includes multiple semiconductor device manufacturing operations, each of which is performed in its own semiconductor manufacturing tool, such as a plasma reactor, an electroplating bath, a chemical mechanical planarization tool, a wet etch tool, and the like. Categories of semiconductor device manufacturing operations include subtractive processes, such as etch processes and planarization processes, and additive processes, such as deposition processes (e.g., physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), electrochemical deposition, electroless deposition). In the context of etch processes, a substrate etch process includes a process that etches a mask layer, or more generally includes a process that etches any material layer that is present deposited on and / or otherwise retained on a substrate surface. Such an etch process can etch a stack of layers in the substrate.

[0172] In the present disclosure, the terms "deposit" and "form" are used interchangeably. Also, the terms "layer," "film," and "thin film" are also used interchangeably. Those of ordinary skill in the art understand that, due to decreasing feature sizes in semiconductor devices, "form" a "layer" at any of the many stages of integrated circuit fabrication can refer to "deposit" a "film" or "thin film" by one of various film-forming methods, such as CVD, PECVD, ALD, or PEALD.

[0173] In the present disclosure, the terms "clean," "etch," and "remove" are used interchangeably. In the context of an etch process, those of ordinary skill agree that etching material from an interior surface of a process chamber is equivalent to "cleaning" or "removing" material from the interior surface of the process chamber, thereby leaving the interior surface free of the material.

[0174] Introduction.

[0175] Semiconductor device manufacturing operations can involve a variety of deposition processes by which various films are deposited to form integrated circuits and related devices by a variety of methods including physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD). One result of the deposition processes is that the various materials not only deposit on the substrates on which the various materials are to be deposited, but also on the surfaces of the components in the processing chamber or the interior surfaces of the processing chamber where the deposition processes occur. One or more of the components in the processing chamber can include a showerhead or a susceptor. The processing chamber can also include a component that can act as both a showerhead and a susceptor (or hereinafter referred to as a "showerhead-susceptor") inside the processing chamber. The showerhead-susceptor can be a susceptor that involves backside deposition. Backside deposition can be defined as forming one or more layers on the backside of a substrate, which is opposite the frontside of the substrate where at least a portion of an electronic device is typically formed. In many applications, a backside layer can be deposited to compensate for wafer (i.e., substrate) bowing, which can be caused by a variety of factors, such as, but not limited to, depositing thick films or high stress films on the frontside of the substrate. The backside layer can be formed from any of a variety of possible materials, including, but not limited to, an amorphous silicon layer. During backside deposition, the substrate can be positioned in a processing chamber having a showerhead and a bottom showerhead (which can be a showerhead-susceptor), with a substrate holder used to hold and support the substrate between the top and bottom showerheads.

[0176] Gaseous precursors or other reactive gases can be provided from a precursor source or source gas supply apparatus through a plurality of passages that pass through the showerhead-susceptor. Thus, during deposition, deposits of the various materials form on the interior surfaces of the processing chamber, including on the interior walls of the processing chamber or the surfaces of one or more components (i.e., parts) in the processing chamber, and the deposited materials can accumulate over time, forming films or causing particles of the deposited materials to flake off. In addition, the deposited materials can dissolve, flake off, thermally desorb, or evaporate through subsequent processes in the processing chamber, which can contaminate substrates being processed in the processing chamber or features formed on the substrates. For example, the deposited materials can flake off in particle form from the surfaces of the components and fall on the substrates during substrate processing. This contamination is one of the reasons that leads to low throughput or yield, as the chamber can need to be frequently maintained or cleaned to prevent contamination; in addition or alternatively, the contamination can also lead to reliability issues in the devices formed on the substrates. The accumulated materials need to be removed periodically to avoid contamination of the processing chamber.

[0177] One method of removing contaminants (e.g., wall deposits) deposited on surfaces of a process chamber can be to introduce a plasma including a fluorine (F) species. The plasma can include one or more species generated by excitation of a gas, and can be referred to as a plasma initiating species or a plasma species. The term "plasma" can refer to one or more plasma initiating species or plasma species or any other species formed in the plasma. For example, a radical can be one or more species generated in the plasma, and can be referred to as a plasma initiating species. A radical can be referred to as an atomic radical or a radical species. For example, a hydrogen radical can also be referred to as a hydrogen atomic radical or a hydrogen radical species. In some embodiments, all or substantially all or a substantial portion of the hydrogen atomic radicals can be in a ground state, e.g., at least about 90% or about 95% of the hydrogen atomic radicals proximate to a substrate can be in a ground state.

[0178] In some embodiments, the plasma can include radicals, positive ions, electrons, charged neutrons, other plasma species, or combinations thereof. In some embodiments, the fluorine-containing species includes a fluorine-containing source gas (including fluorine atoms), a fluorine-containing plasma (e.g., radicals, positive ions, electrons, charged neutrons, and other plasma species), or combinations thereof. In an example, the fluorine-containing species can include a fluorine-containing source gas, a fluorine-containing radical, a positive ion, an electron, a charged neutron, a plasma, or combinations thereof. For example, the fluorine-containing species can include a plasma of one or more fluorine-containing source gases, such as a nitrogen trifluoride (NF3) plasma.

[0179] For this type of cleaning, one or more source gases (e.g., cleaning gases) can be supplied to a plasma source, including a nitrogen trifluoride (NF3) plasma, molecular fluorine (F2), carbon tetrafluoride (CF4), carbon hexafluoride (C2F6), xenon difluoride (XeF2), fluoromethane (CH3F), difluoromethane (CH2F2), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8), sulfur hexafluoride (SF6), and combinations thereof, as well as other fluorine-containing compounds (i.e., fluorine-containing reactants). The plasma source can be an inductively coupled plasma reactor, a capacitively coupled plasma reactor, a microwave plasma reactor, a direct current plasma reactor, or a laser-generated plasma reactor. A plasma generated from the plasma source can include one or more radicals and flow into the process chamber to remove accumulated material deposited on interior surfaces of the process chamber. For example, the fluorine-containing species (e.g., NF3 plasma) can react with silicon (Si) in silicon-containing deposits on interior surfaces of the process chamber or one or more component surfaces, thereby generating volatile silicon tetrafluoride (SiF4).

[0180] The processing chamber can include an inner surface of the processing chamber or one or more components (e.g., a pedestal, a showerhead, or a showerhead-pedestal) made of a metal such as aluminum, an aluminum alloy, or an aluminum-containing material. The fluorine-containing species can react with silicon (Si) in the silicon-containing deposits, thereby removing the silicon-containing deposits from the inner surface of the processing chamber. The fluorine-containing species can also react with aluminum in the aluminum-containing components, forming aluminum fluoride (AIF x ) (e.g., tri-aluminum fluoride, AIF3) or aluminum oxyfluoride (AIO x F y ). Introducing the fluorine-containing species (e.g., NF3plasma) into the processing chamber can produce a layer or particles of AIF x or AIO x F y on surfaces including aluminum (e.g., inner walls of the processing chamber or surfaces of the aluminum-containing components). After the inner chamber surfaces are periodically cleaned using the fluorine-containing species, the AIF x or AIO x F y may also be removed from the inner surfaces to avoid further contamination of substrates in subsequent semiconductor manufacturing processes.

[0181] Process flow Figure 1 A flowchart 100 illustrating an exemplary method of cleaning a surface of one or more components in a processing chamber according to some embodiments is shown. In optional operation 110, a substrate can be provided in a processing chamber having an inner surface and a space for placing the substrate for processing (e.g., deposition or etching) can be defined. For example, the substrate can be transferred by a substrate transfer module (e.g., a robotic arm unit) into the interior of the processing chamber to provide a clean, pressurized environment to minimize the risk of contamination of the substrate being processed as the substrate is transferred from outside the processing chamber to inside the processing chamber. In some embodiments, the substrate can include one or more features formed on the substrate. For example, the one or more features can be one or more partially fabricated integrated circuits. In some embodiments, a substrate can be provided without any features. Prior to optional operation 110, the substrate can be cleaned to remove any undesired layers deposited on the substrate. The processing chamber can also include one or more components disposed in the interior of the processing chamber. The components can include a pedestal, a showerhead, or a showerhead-pedestal, and can be mechanically coupled to other components in the processing chamber. In some embodiments, the inner surface of the processing chamber or a surface of one or more components (e.g., any one or more of a pedestal, a showerhead, or a showerhead-pedestal, etc.) can include aluminum, an aluminum alloy, or an aluminum-containing material.

[0182] In optional operation 120, precursors and reactants can be provided into a processing chamber for deposition of a layer on a substrate. The precursors can be silicon-containing precursors described herein and can be deposited in one or more features on a substrate to form a silicon-containing layer, such as a silicon oxide, a silicon nitride, doped or undoped amorphous silicon, doped or undoped silicon carbide, or combinations thereof. The silicon-containing layer can be formed on a front or front side of a substrate, or the silicon-containing layer can be formed on a backside of the substrate. The “front side” of a substrate can refer to a surface of a substrate used to partially fabricate a semiconductor device. In some embodiments, the “front side” of a substrate faces upward or toward a showerhead disposed above the substrate. In some embodiments, a silicon-containing layer is formed on a backside of a substrate. For example, one or more silicon-containing layers can be formed on a backside of a substrate to offset warping of multiple layers deposited on a front side of the substrate. Operation 120 can also involve depositing another silicon-containing layer having a different chemical composition on top of the silicon-containing layer formed in operation 120. The silicon-containing layers can be deposited by any suitable deposition process, such as PVD, CVD, PECVD, ALD, or PEALD.

[0183] In some embodiments, deposition of a silicon-containing layer can be achieved by flowing one or more silicon-containing precursors into a processing chamber containing a substrate. The silicon-containing precursors are transported to a region above a surface of the substrate, where they are adsorbed onto the surface of the substrate and can be thermally decomposed or chemisorbed onto sites on the surface of the substrate to form a highly conformal silicon-containing layer. In some embodiments, forming a silicon-containing layer by CVD can involve controlling a deposition pressure in a range from about 0.1 Torr to about 40 Torr, or from about 0.5 Torr to about 20 Torr. A substrate temperature during deposition can be controlled to be from about 300 °C to about 700 °C, or from about 400 °C to about 650 °C. After deposition, a step coverage of the silicon-containing layer can be at least about 85%. In some embodiments, the step coverage can be at least about 90% or at least about 95%.

[0184] Without being bound by any theory, silicon-containing precursors having a low sticking coefficient can be able to produce highly conformal silicon layers. “Sticking coefficient” is a term used to describe the ratio of the number of adsorbed species (e.g., fragments or molecules) that stick to a surface to the total number of species that impinge on the surface during the same time period. The symbol S c Sometimes used to refer to sticking coefficient. S cThe value of the sticking coefficient is between 0 (meaning no sticking of any of the impacting species) and 1 (meaning all of the impacting species stick). A variety of factors affect the sticking coefficient, including the type of impacting species, the surface temperature, the surface coverage, the surface's structural details, and the kinetic energy of the impacting species. Certain species are intrinsically more "sticky" than others, making it more likely that they will adsorb to the surface each time they impact the surface. These more sticky species have a larger sticking coefficient (all other factors being equal). In some cases, the sticking coefficient of a precursor (under the relevant deposition conditions) can be about 0.05 or less, such as about 0.001 or less.

[0185] While thermal deposition or thermal decomposition can be used to deposit silicon-containing films, plasma deposition can be used in addition to or in place of thermal deposition or thermal decomposition. In an example, radicals can be generated in a plasma source and introduced into a process chamber during deposition. In some embodiments, a source gas (e.g., a hydrogen-containing gas) is introduced into the plasma source, and the plasma excites the hydrogen-containing gas, which can form excited hydrogen radicals. In some implementations, when the excited hydrogen radicals lose their energy or relax, the excited hydrogen radicals can become hydrogen radicals in a substantially lower energy state or ground state hydrogen radicals. Hydrogen radicals in a substantially lower energy state or ground state are capable of breaking Si-H and / or Si-Si bonds and generally preserve Si-O, Si-N, and / or Si-C bonds. In some implementations, process conditions can be provided such that the excited hydrogen radicals lose energy or relax to form substantially lower energy state or ground state hydrogen radicals.

[0186] The silicon-containing precursor and source gas of hydrogen radicals can be delivered with other species, including carrier gases. Exemplary carrier gases include, but are not limited to, argon (Ar), helium (He), neon (Ne), krypton (Kr), and xenon (Xe). The concentration of the carrier gas can be substantially greater than the concentration of the source gas. As used herein, "substantially greater than" with respect to the concentration of the carrier gas relative to the source gas can refer to a volume percentage that is at least three times greater. As an example, hydrogen gas can be provided in a helium carrier gas at a hydrogen concentration of about 1% to about 50%. The presence of the carrier gas helps to increase ionization of the source gas and reduce recombination. While lower pressures generally favor increased ionization of the source gas and reduced recombination, the presence of the carrier gas can have the same effect. Even at higher pressures, when a carrier gas (e.g., helium) is flowed with the source gas, a majority of the radicals can be generated with minimal recombination. Higher pressures in the process chamber during deposition can improve the conformality of the silicon-containing layer. Higher pressures in the process chamber can correspond to a pressure range of about 1 to about 10 Torr, or about 1 to about 5 Torr. The substrate temperature during deposition of the silicon-containing layer can be controlled to be about 100°C to about 400°C, or about 200°C to about 300°C.

[0187] In some embodiments, the silicon-containing precursor can be delivered to a processing region on a surface of a substrate. In some embodiments, depending on the parameters of depositing the silicon-containing layer, the silicon-containing precursor can also be delivered to other locations on the interior surfaces of the processing chamber and to surfaces of components other than the substrate on which the silicon-containing precursor should be deposited. For example, the silicon-containing precursor can deposit on the interior surfaces of the processing chamber, on surfaces of the susceptor, the showerhead, or the showerhead-susceptor, and can thus form a silicon-containing layer. Depending on the operations in the processing chamber, the silicon-containing material deposited on the interior surfaces of the processing chamber or on the surfaces of the components can have a composition including silicon, carbon, nitrogen, oxygen, or a combination thereof. The silicon-containing material can form a layer or tiny particles. As the number of substrates processed (e.g., deposited or etched) or the duration of the operations (e.g., deposition or etching) in the processing chamber increases, the thickness of the silicon-containing material formed on the interior surfaces also increases, which can lead to flaking and particle defects, and thus can become a source of contamination for the substrates in subsequent operations. For example, the silicon-containing material can sublimate and be re-delivered to another location in the chamber, and / or can re-deposit in features on the substrate. In another example, silicon-containing particles or flakes can fall to the floor of the processing chamber. The interior surfaces of the processing chamber, including the interior walls of the processing chamber or the surfaces of one or more components (i.e., parts) in the processing chamber, can be periodically cleaned after a certain number of substrates are processed or after a duration of the operations exceeds a certain period of time to remove the silicon-containing material from the interior surfaces of the processing chamber.

[0188] In some embodiments, after the silicon-containing layer is deposited on the interior surfaces of the processing chamber, one or more substrates in the processing chamber can be removed from the processing chamber. For example, the substrates can be transferred outside of the processing chamber by a substrate transfer module (e.g., a robot arm unit). In operation 130, a fluorine-containing species can be provided to the interior of the processing chamber for chamber cleaning, i.e., cleaning the silicon-containing layer deposited on the interior surfaces of the processing chamber, including the interior walls of the processing chamber or the surfaces of one or more components (i.e., parts) in the processing chamber, for a duration of time. As described above, the fluorine-containing species can include a fluorine-containing source gas, a fluorine-containing plasma (e.g., radicals, ions, charged neutrons, and other plasma), or a combination thereof. In an example, the fluorine-containing species, such as a nitrogen trifluoride (NF3) plasma, can react with silicon in the silicon-containing material, thereby generating silicon tetrafluoride (SiF4) byproducts, which are volatile and can be relatively easily removed from the interior of the processing chamber.

[0189] In some embodiments, in addition to the reaction between the silicon-containing material and the fluorine-containing species, aluminum-containing (e.g., aluminum, aluminum alloy, or other aluminum-containing material) components, such as the showerhead, the susceptor, the showerhead-susceptor, or the interior walls of the chamber, can also be exposed to the fluorine-containing species. In some embodiments, these components can have surfaces including aluminum, aluminum alloy, or other aluminum-containing materials. Upon contact of the aluminum-containing components with the fluorine-containing species, AlF x or AlO x F yByproducts. In an example, byproducts can include aluminum trifluoride (AlF3). The byproducts can include AlF3or AlO x F y AlF x may not be volatile, and can not be easily removed from the surface of the component. In some embodiments, the silicon-containing material on the interior surface of the processing chamber can be cleaned or removed in the form of silicon tetrafluoride or the like, while the AlF x or AlO x Fy can remain in condensed form, for example, in the form of a layer or particles on the interior surface of the processing chamber. The AlF3or AlO x F y may form on any surface of an aluminum-, aluminum alloy-, or aluminum-containing material exposed to the fluorine-containing species inside the processing chamber. For example, for a showerhead- pedestal that can be used for backside deposition, AlF x or AlO x F y may form not only on the exterior surface of the showerhead- pedestal, but also on the surfaces of the plurality of gas passages (e.g., holes) that pass through the showerhead- pedestal. The amount of AlF x or AlO x F y that forms on the surface of the component can depend on the parameters used to clean the interior surface of the processing chamber. For example, the longer the duration of the supply of the fluorine species (e.g., NF3plasma cleaning), the greater the amount of AlF x or AlO x F y (e.g., thicker layers, or larger or aggregated particles) that can be deposited on the interior surface of the processing chamber.

[0190] In some embodiments, the component removed in operation 140 can be mechanically and / or fluidly coupled to the processing chamber or other components in the processing chamber when in use in the processing chamber. For example, the component can include a pedestal, a showerhead, or a showerhead- pedestal.

[0191] In operation 140, the component having the layer or particles of AlF x or AlO x F y deposited on the surface can be removed from the processing chamber to clean the AlF x or AlO x F y from the surface. Prior to operation 140, the operation of the processing chamber can be interrupted or stopped. For example, prior to operation 140, the apparatus including the processing chamber can be not in operation or shut down. A vacuum pump fluidly coupled to the processing chamber can be configured to not be in operation, the processing chamber can not be at a low chamber pressure. In an example, the processing chamber can be at atmospheric pressure.

[0192] During operation 140, the component can be detached or separated from the processing chamber and transferred out of the processing chamber. For example, a transfer arm can be used to remove the component from the processing chamber.

[0193] Alternatively, in some embodiments, the component having the surface deposited AlF x or AlO x F y layer or particles can not be removed from the processing chamber. Rather, the etching operation according to some embodiments can be performed inside the processing chamber without removing the component out of the processing chamber.

[0194] In operation 150, the component having the AlF x or AlO x F y formed thereon can be exposed to one or more etching compositions for a period of time to remove the AlF x or AlO x F y from the surface of the component. In some embodiments, the etching composition can include a hydroxyl-containing composition, such as a hydroxyl-containing gas or plasma. The hydroxyl-containing composition can include a hydroxyl-containing alkaline composition, and can include potassium hydroxide (KOH), sodium hydroxide (NaOH), ammonium hydroxide (NH4OH), tetramethylammonium hydroxide (TMAH, C4H 13 NO), tetraethylammonium hydroxide (TEAH, C8H 21 NO), or combinations thereof. In some embodiments, the etching composition (e.g., the hydroxyl-containing composition) can be mixed with water or deionized water to form an etching composition solution. The etching composition solution can include a hydroxyl-containing solution having a concentration. In some embodiments, the concentration of the etching composition solution can be about 0.1 to about 45% weight / volume [%(W / V)], about 0.5 to about 30%(W / V), about 1 to about 20%(W / V), about 1.5 to about 10%(W / V), or about 2 to about 7%(W / V), which can include potassium hydroxide (KOH), sodium hydroxide (NaOH), ammonium hydroxide (NH4OH), tetramethylammonium hydroxide (TMAH, C4H 13 NO), tetraethylammonium hydroxide (TEAH, C8H 21 NO), or combinations thereof as described herein. In some embodiments, the etching composition solution can be contacted with the AlF x or AlO x F y formed on the component for about 0.1 to about 45 minutes, about 1 to about 30 minutes, about 1 to about 10 minutes, about 5 to about 25 minutes, about 8 to about 20 minutes, about 10 to about 20 minutes, or about 10 to about 15 minutes. The duration can depend on the AlF x or AlO xF y thickness or formation of AlF x or AlO x F y the condition of the surface (e.g., surface roughness, etc.) or other process conditions during operation 150.

[0195] It should be appreciated that any of the etching compositions and AlF x or AlO x F y The exposure time to the etching composition can be used in accordance with some embodiments to remove AlF x or AlO x F y from the surface of the component. For example, the AlF x (e.g., AlF3) or AlO x F y may be exposed to a potassium hydroxide solution having a concentration of about 1% to about 20% (W / V) for about 1 to about 30 minutes, about 1 to about 10 minutes, about 5 to about 25 minutes, about 8 to about 20 minutes, or about 10 to about 15 minutes. In another example, the AlF x (e.g., AlF3) or AlO x F y may be exposed to a potassium hydroxide solution having a concentration of 3% to 10% (W / V) for about 5 to 25 minutes. In another example, a sodium hydroxide solution having a concentration of about 1.5% to about 10% (W / V) can be used to soak for about 8 to about 20 minutes, or about 10 to about 15 minutes, to remove AlF x or AlO x F y . In some embodiments, the AlF x temperature of the etching composition solution during etching can be ambient temperature. In some embodiments, the temperature can be set or can be adjusted between about 0 to about 100 °C or about 10 to about 90 °C. In some embodiments, an ultrasonic frequency (e.g., greater than 20 KHz) can be applied to the component during at least a portion of the processing time period to improve the efficiency of the etching operation.

[0196] The AlF x or AlO x F yThe component can be removed from the etching composition solution after the component has been exposed to the etching composition solution (e.g., a hydroxyl-containing composition mixed with water) having a concentration for a certain amount of time. The component can then be rinsed using high purity deionized water to remove the etching composition (e.g., the hydroxyl-containing composition) that remains on the surface of the component. After rinsing, the component can be baked at a temperature of about 200 °C, about 80 to about 140 °C, or about 100 to about 110 °C for any suitable time, such as about 0.1 to about 8 hours, about 1 to about 6 hours, or about 3 to about 5 hours to remove the water that remains on the surface of the component. After exposure to the solution, rinsing, and baking, the component can be substantially free of AlF x or AlO x F y In one embodiment, the component can be considered substantially free of AlF x or AlO x F y when the amount of AlF x or AlO x F y in particulate form or other condensed form is less than the amount of AlF x or AlO x F y on a newly replaced component.

[0197] In operation 160, the component that is substantially free of AlF x may be considered "recovered" so that it can be used again in a processing chamber. This is different from replacing the component with a new component. For example, the component can be transferred to the interior of a processing chamber for reinstallation for a subsequent operation (e.g., deposition or etching). In some embodiments, the component or a package including one or more components can be reassembled to a processing chamber or another component in a processing chamber. Subsequently, the processing chamber can be operated to reach a vacuum level (i.e., vacuum degree) suitable for a subsequent operation (e.g., depositing a layer or etching a layer). In some embodiments, a substrate can be transferred to the processing chamber before or after reaching a pressure range required for the operation such as deposition, and a chemical precursor for depositing a silicon-containing layer and a reactant for depositing a layer can be provided. In another example, a substrate can be transferred to the processing chamber for etching at least a portion of a feature on the substrate.

[0198] FIG. 2 shows a flowchart 200 of an exemplary method of cleaning a surface of a component, according to some embodiments. In operation 210, a component having a surface containing aluminum can be provided. In some embodiments, the surface can include aluminum, an aluminum alloy, or other aluminum-containing material. In some embodiments, the surface can include aluminum, an aluminum alloy, an aluminum fluoride (e.g., aluminum trifluoride), an aluminum oxyfluoride, or a combination thereof. The component can include a showerhead, a susceptor, a showerhead-susceptor, or any other component or part related to operation of a processing chamber.

[0199] In optional operation 220, a fluorine-containing substance can be provided to the component surface, thereby forming AlF x or AlO x F y The fluorine-containing substance can include a fluorine-containing plasma as described herein. For example, the fluorine-containing substance can include a plasma of one or more fluorine-containing gases, such as a nitrogen trifluoride (NF3) plasma.

[0200] In operation 230, the component can be exposed to an etching composition solution. In some embodiments, the component can be soaked in the etching composition solution to etch aluminum fluoride or aluminum oxyfluoride that can be present on the component surface. The etching composition solution can include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a combination thereof. In some embodiments, the concentration of the etching composition solution can be about 0.1% to about 45% weight by volume [%(W / V)], about 0.5% to about 30%(W / V), about 1% to about 20%(W / V), about 1.5% to about 10%(W / V), or about 2% to about 7%(W / V). In addition to soaking, the etching composition solution can be provided to the component surface in a vapor phase by atomizing the etching composition solution at an elevated temperature, for example, about 10°C to about 90°C.

[0201] FIGS. 3A-3E are scanning electron microscope (SEM) images showing the etching of AlF x from the component surface over time, according to some embodiments. FIGS. 3A-3E show a cross-sectional area of an aluminum-containing component (e.g., a showerhead-substrate) 310. The black area 330 in the lower portion of the images in FIGS. 3A-3F corresponds to carbon used to prepare the SEM sample. The component, having a surface coated with a layer of AlF x 320, was soaked in a potassium hydroxide (KOH) solution having a concentration of 1.5% to 10%(W / V) for varying amounts of time. Chemical element analysis using an energy dispersive spectrometer (EDS, Hitachi, Japan) confirmed the presence of the AlF x layer 320. Both quantitative and qualitative analysis indicated that the layer 320 included AlF x (including AlF3). FIG. 3A is an image taken prior to soaking the sample in the KOH solution (soak time = 0 minutes), and FIGS. 3B-3E are images taken at 2 minute increments after the start of the soak. That is, FIG. 3B is an image of the sample after 2 minutes of soaking, FIG. 3C is an image of the sample after 4 minutes of soaking, FIG. 3D is an image of the sample after 6 minutes of soaking, and FIG. 3E is an image of the sample after 8 minutes of soaking.

[0202] FIG. 3A shows that prior to the etching operation, the component surface had a layer of AlF xLayer 320. FIG. 3B shows that no significant changes were observed in the AlF x 320 after immersing the component in the KOH solution for up to about 2 minutes. FIG. 3C shows that after immersing in the KOH solution for about 4 minutes, a gap 340 (e.g., darker line) formed along the boundary between the component 310 and the AlF x 320. In some embodiments, during the immersion, the KOH solution can have loosened or dissolved the AlF x . In some embodiments, the KOH solution can also have penetrated the boundary between the AlF x 320 and the component 310, the AlF x formed on the boundary, and loosened the adhesion between the AlF x and the component aluminum-containing surface. FIG. 3D shows that after immersing in the KOH solution for about 6 minutes, the AlF x layer was removed from the surface of the component 310. After the KOH fully penetrated the gap 340 between the component and the AlF x , the adhesion of the AlF x layer can be further eased enough to completely separate the AlF x layer from the aluminum-containing component surface. The loss of adhesion of the AlF x to the component surface can involve separating at least a portion of the AlF x layer from the component surface, which can be similar to peeling, where the layer to be removed is detached from an underlying substrate or underlying layer. FIG. 3E shows that after removing the AlF x from the component, no further changes were observed, and the peeling of the AlF x was confirmed to be irreversible.

[0203] In some embodiments, any of the hydroxyl-containing solutions described herein having a concentration range can be used to etch AlF x or AlO x F y from a component surface. The chemical composition and concentration of the hydroxyl-containing solution can be a parameter when etching AlF x or AlO x F y from a component surface. For example, the concentration of the hydroxyl-containing solution can be inversely proportional to the time to etch AlF x or AlO x F y . A hydroxyl-containing solution having a lower concentration can lengthen the time to etch AlF x or AlO x F y from a component surface. A hydroxyl-containing solution having a higher concentration can over-etch the component. For example, a hydroxyl-containing solution having a concentration of about 60% (W / V) or higher can etch away an aluminum-containing component, depending on the duration or immersion temperature.

[0204] In addition to the SEM images taken for each step of the etching operation with respect to soak time, the removal of AlF x may also be confirmed by measuring the surface profile of the component with AlF x deposited thereon as a function of soak time. For example, the showerhead- pedestal samples in FIGS. 3A-3C show that there is a layer of about 4 to about 10 microns thick on the component. For the showerhead-pedestal samples in FIGS. 3D-3E, the surface profile does not show that there is an additional layer on the component. These profile studies can further confirm the observation that AlF x has been substantially removed by the KOH solution as shown by the SEM images taken sequentially with respect to soak time.

[0205] FIG. 4 is a chart illustrating the size range and number of AlF x particles on a showerhead-pedestal before and after a cleaning operation according to some embodiments. The horizontal axis of the chart in FIG. 4 shows the size range of AlF x particles in arbitrary units. The size range of AlF x particles increases from left to right. The vertical axis of the chart shows the relative number of AlF x particles on the surface of the showerhead-pedestal in logarithmic units. Each set of bars includes three bars, namely a reference bar (empty bar), a pre-cleaning bar (dashed bar), and a post-cleaning bar (hatched bar). The height of the bar referred to as “reference” in each set of bars corresponds to the number of AlF x particles on the as-manufactured showerhead-pedestal surface, which is used as a reference, for comparison with the number of AlF x particles measured after chamber cleaning with a fluorine-containing substance, and the number of AlF x particles measured after a cleaning operation described in some embodiments. The height of the dashed bar referred to as “pre-cleaning” corresponds to the number of AlF x particles on the surface of the showerhead-pedestal after a certain number of substrates have been processed (e.g., etch deposition) for a certain amount of time and exposed to a fluorine-containing substance for cleaning the interior surfaces of the processing chamber. The height of the hatched bar referred to as “post-cleaning” corresponds to the number of AlF x particles on the surface of the showerhead-pedestal after the showerhead-pedestal has been soaked in an etching composition solution (e.g., a hydroxyl-containing solution) for a certain amount of time as described herein.

[0206] To determine the size range and number of AlF x particles on the showerhead-pedestal at various stages, the showerhead-pedestal with AlF x particles was vibrated at high frequency in a liquid medium to dislodge the AlF xParticles were separated from the showerhead- pedestal. Deionized water (resistivity up to about 2 million ohm-cm, MOhm-cm) or ultrapure water (resistivity up to about 18.2 MOhm-cm) can be used as the liquid medium. The AlF x particles dispersed in the liquid medium were analyzed by light scattering to measure the AlF x particles and the number of particles. Figure 4 shows that the number of AlF x particles on the showerhead- pedestal increased after the showerhead- pedestal was exposed to the fluorine-containing species during chamber cleaning with the fluorine-containing species, as compared to the showerhead- pedestal at the completion of fabrication. Such an increase is due to the AlF x particles produced by the reaction between aluminum on the surface of the showerhead- pedestal and the fluorine-containing species. According to some embodiments, after cleaning the showerhead- pedestal with a hydroxyl-containing solution, the number of AlF x particles decreased by more than 99% as compared to the number of particles on the showerhead- pedestal after chamber cleaning. The decrease in the number of AlF x particles was observed for all size ranges of AlF x particles. In some embodiments, for most size ranges measured, the number of AlF x particles after cleaning was comparable to, or even less than, the number of AlF x particles on the showerhead- pedestal at the completion of fabrication. Figure 4 shows that the cleaning operation using the etching compositions described herein can effectively remove AlF x particles from aluminum-containing components exposed to fluorine-containing species. In addition, the decrease in the number of AlF x particles can allow the showerhead- pedestal to be removed from a processing chamber, cleaned according to embodiments of the present application, and re-installed in the processing chamber for additional use without affecting substrate contamination during operation, which can advantageously reduce the manufacturing or operating cost of a processing chamber in a device, such as a deposition device or an etching device.

[0207] device.

[0208] Figure 5A is a block diagram showing a substrate processing system 532 for performing processing on a substrate (e.g., a wafer) 502, according to some embodiments. As shown, the substrate processing system can include a processing chamber 534. A central column can be configured to support a pedestal on which a wafer 502 is being processed, e.g., a film is being formed on a top surface of the substrate 502 or a backside of the substrate 502. According to some embodiments disclosed herein, the pedestal can be referred to as a showerhead- pedestal 506. A showerhead 536 can be disposed on the showerhead- pedestal 506.

[0209] In some embodiments, the showerhead 536 can be electrically coupled to a power source 538 through a matching network 540 for powering the plasma. The power source 538 can be controlled by a control module 542, such as a controller. In some embodiments, the showerhead- pedestal 506 can be powered instead of the showerhead 536. The control module 542 can be configured to operate the substrate processing system 532 by executing process inputs and controls of a particular process recipe. Depending on whether the top surface of the substrate 502 or the bottom surface of the substrate 502 is to receive a deposited film, the controller module 542 can set various operating inputs for the process recipe, such as power levels, timing parameters, process gases, mechanical movement of the substrate 502, and / or height of the substrate 502 relative to the showerhead- pedestal 506.

[0210] In some embodiments, the plasma energy can be controlled by controlling one or more of the chamber pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 538 and matching network 540 can operate at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable RF power range can be about 50 Watts (W) - 1,000 W or 100 W - 500 W per station. Also, the RF power source 538 can provide RF power at any suitable frequency. In some embodiments, the RF power source 538 can be configured to control high frequency and low frequency RF power sources independently of one another. Example low frequency RF frequencies can include, but are not limited to, frequencies less than 1 MHz, or between 50 kHz and 600 kHz. Example high frequency RF frequencies can include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. In some embodiments, a high frequency of 13.56 MHz or about 27 MHz can be provided. It should be appreciated that any suitable parameter can be adjusted intermittently or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power can be intermittently pulsed relative to a continuously powered plasma to reduce ion bombardment of the substrate surface.

[0211] In some embodiments, the center post can also include lift pins that are controlled by a lift pin controller. These lift pins can be used to lift the substrate 502 from the showerhead- pedestal 506 to allow an end effector (not shown) to pick up a wafer and lower the substrate 502 after it has been placed by the end effector. The end effector can also place the substrate 502 over the spacer 544. As will be described below, the spacer 544 can be sized to provide a controlled separation of the substrate 502 between the top surface of the showerhead 536 (facing the wafer) and the top surface of the showerhead- pedestal 506 (facing the wafer).

[0212] In some embodiments, the substrate processing system 532 can further include a first gas supply source connected to a first gas manifold 546 of the first gas source 548 (e.g., gas chemicals supplied from a facility and / or inert gases). For example, the gas chemical supply source can include one or more silicon-containing precursors (described herein) and one or more carrier gases. Examples of carrier gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), deuterium (D2), hydrogen (H2), and nitrogen (N2). In another example, one or more fluorine-containing species can be fluidly coupled to the first gas supply source, including the first gas manifold 546 connected to the first gas source 548. The fluorine-containing species includes a fluorine-containing source gas, a fluorine-containing plasma (e.g., radicals, ions, charged neutrals), or mixtures thereof. The fluorine-containing source gas can include nitrogen trifluoride (NF3), molecular fluorine (F2), carbon tetrafluoride (CF4), carbon hexafluoride (C2F6), xenon difluoride (XeF2), fluoromethane (CH3F), difluoromethane (CH2F2), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8), sulfur hexafluoride (SF6), a fluorine-containing plasma, or mixtures thereof. In some embodiments, the one or more fluorine-containing species can be generated from a plasma source (e.g., a remote plasma source) that can be fluidly coupled to the first gas supply source including the first gas manifold 546. Depending on the process being performed on the top surface of the substrate 502, the control module 542 can control the delivery of the first gas source 548 through the first gas manifold 546. The selected gas can then flow into the showerhead 536 and be distributed in a volume of space defined between the face of the showerhead 536 facing the substrate 502 (when the substrate is positioned on the pedestal) and the substrate 502. In some embodiments, the one or more gas and / or liquid sources can be provided in the form of a fine mist by an atomizer without the need to heat the one or more gas and / or liquid sources to a high temperature. In some embodiments, the one or more gas and / or liquid sources can be further diluted by one or more solvents or liquids designed to be suitable for atomization. Vaporization can be a direct injection vaporizer, a flow-through vaporizer, or both.

[0213] In some embodiments, the substrate processing system 532 may further include a second gas supply source, comprising a second gas manifold 550 connected to a second gas source 552 (e.g., a gaseous chemical and / or inert gas supplied from the facility). For example, the gaseous chemical supply source may include one or more silicon-containing precursors (described herein) and one or more carrier gases. Examples of carrier gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), deuterium (D2), hydrogen (H2), and nitrogen (N2). In another example, one or more fluorinated substances may be fluidly coupled to the first gas supply source, including coupling to a first gas manifold 546 connected to the first gas source 548. Fluorinated substances include fluorinated source gases, fluorinated plasmas (e.g., free radicals, ions, charged neutral particles), or mixtures thereof. Fluorine-containing source gases may include nitrogen trifluoride (NF3), molecular fluorine (F2), carbon tetrafluoride (CF4), carbon hexafluoride (C2F6), xenon difluoride (XeF2), fluoromethane (CH3F), difluoromethane (CH2F2), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8), sulfur hexafluoride (SF6), fluorine-containing plasma, or mixtures thereof. In some embodiments, one or more fluorine-containing substances may be generated from a plasma source (e.g., a remote plasma source) that may be fluidly coupled to a first gas supply source including a first gas manifold 546. Depending on the processing performed on the bottom surface of substrate 502, control module 542 may control the delivery of the second gas source 552 via second gas manifold 550. The selected gas can then flow into the nozzle-base 506 and be distributed within the space defined between the substrate 502 and the surface of the nozzle-base 506 facing the back or lower side (back side) of the substrate 502 when the wafer is positioned above the spacer 544. The spacing provided by the spacer 544 optimizes deposition on the back side of the substrate 502 and reduces deposition above the top surface of the substrate 502. In some embodiments, when the deposition target is the back side of the substrate 502, an inert gas can flow through the nozzle 536 across the top surface of the substrate 502, which can push the reactant gas away from the top surface and allow the reactant gas supplied from the nozzle-base 506 to be directed to the back side of the substrate 502.

[0214] Furthermore, the gas may or may not be premixed. Appropriate valves and mass flow control mechanisms can be employed to ensure the correct gas delivery during the deposition and plasma treatment phases of the process. The process gas can exit chamber 534 via an outlet. A vacuum pump (e.g., a first- or second-stage mechanical dry pump and / or a turbomolecular pump) can extract the process gas and maintain an appropriate low pressure within the reactor via a dead-loop flow limiting device (e.g., a throttle valve or pendulum valve).

[0215] In some embodiments, the substrate processing system 532 can also include an atomizer and / or vaporizer, each fluidly coupled to the interior of the processing chamber, and one or more sources of etching composition solution. The etching composition solution can include one or more hydroxyl-containing solutions. The one or more hydroxyl-containing solutions can be pre-diluted to a certain concentration or mixed with other liquid media (e.g., deionized water or ultrapure water) before being delivered to the processing chamber. The atomizer can be provided as a finned sprayer that does not need to be heated to a high temperature to deliver the etching composition solution into the processing chamber for cleaning the interior walls of the processing chamber or one or more components in the processing chamber. In some embodiments, the etching composition solution described herein with a certain concentration can be heated by one or more heating components at a certain temperature. The heated etching composition solution can be delivered to the interior of the processing chamber by a vaporizer. The vaporizer can be a direct injection vaporizer, a flow vaporizer, or both.

[0216] In some embodiments, the carrier ring 554 can surround an outer region of the showerhead- pedestal 506. When the top surface of the substrate 502 is being processed, e.g., when material is being deposited thereon, the carrier ring 554 can be configured to be positioned above a carrier ring support region, which is a sunken step of the wafer support region in the center of the showerhead-pedestal 506. The top surface of the carrier ring 554 can be approximately coplanar with the top surface of the substrate 502. The carrier ring 554 can include an outer edge side (e.g., outer radius) of its disk structure and a wafer edge side (e.g., inner radius) of its disk structure that is closest to where the substrate 502 is located. The wafer edge side of the carrier ring 554 can also include a plurality of contact support structures or “tabs” that can be configured to elevate the substrate 502 when the carrier ring 554 is held by the spacer 544. The carrier ring 554 can include a number of tabs selected from a range that supports the substrate 502 during processing. Additional details regarding the tab embodiments will follow.

[0217] FIG. 5B is a block diagram illustrating another substrate processing system 532 for performing processing on a substrate 502, according to some embodiments. In some embodiments, a spider fork 556 can be used to lift and hold the carrier ring 554 at its processing height, e.g., to allow deposition on the backside of the substrate 502. Thus, the carrier ring 554 can be lifted along with the substrate 502. In some embodiments, the carrier ring 554 can be rotated to another station, e.g., in a multi-station system.

[0218] Broadly speaking, the embodiments disclosed herein are for systems that dynamically control deposition of PECVD films on a selected side (front side and / or back side) of a substrate. Some embodiments can include a dual gas flow electrode for defining a capacitively coupled PECVD system. The system can include a gas flow showerhead 536 and a showerhead-to- pedestal 506. In some embodiments, the gas flow pedestal (i.e., showerhead-to- pedestal) is a combination of a showerhead and a pedestal that enables deposition on the back side of a substrate. The electrode geometry is combined with features of the showerhead (e.g., gas mixing plenum, holes, hole pattern, gas shield baffle) and features of the pedestal. Examples of pedestal features include embedded controlled heaters, substrate lift mechanisms, ability to hold plasma confinement rings, and mobility. This enables the transport of the substrate and processing of the gases with or without RF power from the pedestal.

[0219] In some embodiments, the system can have a substrate lift mechanism that strictly controls the parallelism of the substrate with respect to the electrodes. In one example, this can be achieved by setting the lift mechanism (e.g., mandrel or lift pin mechanism) parallel to both electrodes and controlling the manufacturing tolerances. In another example, the lift can be achieved by raising the substrate lift components. This option can not allow for dynamic control of the side on which deposition occurs.

[0220] In some configurations, the lift mechanism can allow for dynamic control of the substrate position during processing (before plasma, during plasma, after plasma) to control the side of deposition, profile of deposition, and properties of the deposited film. The system can further allow for selective enabling / disabling of the flow of reactants on a side. One side can flow reactants and the other side can flow an inert gas to inhibit deposition and plasma.

[0221] In some embodiments, the gap between the sides of the substrate that do not need plasma / deposition can be strictly controlled. The distance of the gap can be controlled to inhibit plasma. If the distance is not controlled, the substrate can be susceptible to plasma damage. For example, the system can allow for a minimum gap of about 2 mm to about 0.5 mm, while in another embodiment about 1 mm to about 0.05 mm (limited by substrate bowing), and such a gap can be controlled. The gap can be controlled depending on the process conditions.

[0222] In some embodiments, the gas flow pedestal (i.e., showerhead-pedestal) can enable, but is not limited to: (a) thermal stabilization of the substrate to process temperature prior to processing; (b) selective design of the hole pattern on the showerhead-pedestal to selectively deposit films on different areas of the substrate backside; (c) attachable replaceable rings to achieve proper plasma confinement and hole pattern; (d) in-chamber stable substrate transfer mechanism for transferring the substrate out to another chamber or boat - e.g., lift pins, RF coupled features, minimal contact arrays; (e) implementation of gas mixing features, e.g., internal plenums, baffle and manifold line openings; and (f) compartmentalization in the gas flow pedestal (i.e., showerhead-pedestal) to enable selective gas flow to different areas of the substrate backside and control flow rates through flow controllers and / or multiple plenums.

[0223] In another embodiment, dynamic gap control using a substrate lift mechanism enables: (a) control of the distance from the deposition or reactant flow electrode to the side or middle of the substrate where deposition is desired, so that both sides can be deposited; and (b) a lift mechanism to dynamically control the distance during the process (before plasma, during plasma, after plasma) to control which side is deposited, the deposition profile, and the deposited film properties. In another embodiment, for deposition modes used to deposit on the substrate backside, film edge exclusion control is highly desired to avoid lithography related overlay issues. The lift mechanism used in this system is accomplished by the carrier ring 554, which has design features to shadow deposition on the edges. This specifies edge exclusion control by the design and shape of the carrier ring.

[0224] FIG. 6 is a schematic illustration of a processing system suitable for performing deposition processes according to embodiments. The system 600 includes a transfer module 603. The transfer module 603 provides a clean, pressurized environment to minimize the risk of contamination to substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 603 is a multi-station reactor 609 capable of performing ALD, processing, and CVD according to various embodiments. The multi-station reactor 609 can include multiple stations 611, 613, 615, and 617 that can perform operations sequentially according to the disclosed embodiments. Each of the multiple stations 611, 613, 615, and 617 can include a processing chamber. For example, the multi-station reactor 609 can be configured such that station 611 performs backside deposition of a poly-Si sublayer by PECVD or PEALD, station 613 performs backside deposition of an a-Si sublayer by PECVD or PEALD, station 615 performs first frontside deposition of a silicon-based film by PECVD or PEALD, and station 617 can perform second frontside deposition of a silicon-based film by PECVD or PEALD. The stations can include a heated pedestal or substrate support, one or more gas inlets, or a showerhead or a dispersion plate.

[0225] Returning to FIG. 6, one or more single- or multi-station modules 607 capable of performing plasma or chemical (non-plasma) pre-clean, other deposition operations, or etching operations can also be mounted on the transfer module 603. This module can also be used for various processes, for example, to prepare the substrate for a deposition process. The system 600 also includes one or more substrate source modules 601 in which substrates are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 619 can first move the substrate from the source module 601 to the load lock 621. Substrate transfer equipment (typically a robot arm unit) in the transfer module 503 can move the substrate from the load lock 621 to the modules mounted on the transfer module 603 and between these modules. The system 600 can also include one or more substrate source modules 601 in which substrates are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 619 can first move the substrate from the source module 601 to the load lock 621. Substrate transfer equipment (typically a robot arm unit) in the transfer module 603 can move the substrate from the load lock 621 to the modules mounted on the transfer module 603 and between these modules. In cases where the load lock 621 includes a remote plasma source, the substrate can be exposed to a remote plasma treatment to treat the surface of the substrate in the load lock prior to introducing the substrate into the processing chamber. The remote plasma generated from the remote plasma source can be supplied to each of the processing stations (described below) for cleaning the interior surfaces in accordance with the methods described herein. In some embodiments, the remote plasma source can be fluidly coupled with a first process gas supply (not shown here) to receive a process gas from the first process gas supply to generate a plasma, and to provide the generated plasma into the processing chamber. In other embodiments, the plasma can be generated directly in the processing chamber.

[0226] In various embodiments, a system controller 642 is employed to control the process conditions during deposition. The controller 642 will typically include one or more memory devices and one or more processors. The processors can include CPUs or computers, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0227] The controller 642 can control all activities of the deposition device. The system controller 642 runs system control software that includes sets of instructions for controlling timing, gas mix, chamber pressure, chamber temperature, substrate temperature, radio frequency (RF) power levels, substrate chuck or susceptor position, and other parameters of a particular process. In some embodiments, other computer programs stored on memory devices associated with the controller 642 can be used. For example, the system controller 642 can be designed to alternate deposition of a-Si sub-layers and poly-Si sub-layers by varying process parameters for a-Si deposition and poly-Si deposition (e.g., flow rates and durations of silicon-containing precursor and carrier gas, chamber temperature, substrate temperature, chamber pressure, RF frequency, and RF power).

[0228] Generally, there will be a user interface associated with the controller 642. The user interface can include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0229] The system control logic can be configured in any suitable manner. Generally, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry can be hard coded or provided as software. The instructions can be provided by "programming." Such programming is understood to include any form of logic, including hard coded logic in digital signal processors, application specific integrated circuits, and other devices having specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that can be executed on general purpose processors. The system control software can be coded in any computer- readable programming language.

[0230] The computer program code for carrying out operations for the process sequences of pulses of germanium-containing reducing agent, flow of hydrogen gas, and pulses of tungsten-containing precursor, as well as other processes, can be written in any conventional computer readable programming language such as assembly language, C, C++, Pascal, Fortran or others. Compiled object code or script is executed by processor to perform the tasks identified in the program.

[0231] Controller parameters relate to process conditions such as, for example, process gas composition and flow rate, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and can be entered using a user interface.

[0232] Signals for monitoring the process can be provided through analog and / or digital input connections of the system controller 642. Signals for controlling the process are output through analog and digital output connections of the apparatus 600.

[0233] The system software can be designed or configured in various ways. For example, a plurality of chamber component subroutines or control objects can be written to control the operation of the chamber components needed to perform a deposition process according to the disclosed embodiments. Examples of programs or program segments for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code. For example, the system software can be designed such that the programs or program segments include, by varying the flow rates and durations of the silicon-containing precursors and carrier gases for a-Si deposition and poly-Si deposition, temperature, chamber pressure, RF frequency, and RF power, to perform the alternating deposition of a-Si sub-layers and poly-Si sub-layers.

[0234] In some embodiments, the system controller 642 is part of a system, which can be part of the above-described examples. Such systems can include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (substrate

[0235] Broadly speaking, the controller can be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits can include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions can be instructions communicated via a variety of means, such as those stored in a memory and / or stored in a software storage unit. Examples of a memory and / or software storage unit include a non-transitory memory, a magnetic storage, an optical storage, a solid state storage, and the like. The various operations described herein can be implemented as a set of instructions executed by the controller. Such instructions can be stored in any non-transitory computer-readable storage medium, such as a storage device or memory associated with the controller. The instructions can be executable by the controller, the central processing unit (CPU), the digital signal processor (DSP), or any other device associated with the controller. In this way, the controller can be configured to perform the various operations described herein by executing the set of instructions.

[0236] In some implementations, the system controller 642 can be a part of, or coupled to, a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the system controller 642 can be in "the cloud" or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer can enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, change parameters of current processing, set processing steps to follow a current process, or start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which can include a local network or the Internet. The remote computer can include a user interface that enables a user to input or select parameters and / or settings, which are then transmitted over the network to the system. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters can be specific to a type of process to be performed, and a type of tool that the controller is configured to interface with or control. Thus as described above, the controller can be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be in a cluster of tools on a platfonn, where there can be one or more controllers on each tool and a master controller that communicates with the one or more controllers on the tools. The master controller can be central to a cluster of tools or it can be part of one of the tools. In some examples, the controller can be an integrated part of a tool and / or a process chamber on a tool.

[0237] An exemplary system can include, but is not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor

[0238] As described above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0239] The system controller 642 can include different programs. A substrate positioning program can include program code for controlling the chamber components used to load a substrate onto a susceptor or chuck and control the spacing between the substrate and other parts of the chamber, such as the gas inlets and / or the targets. A process gas control program can include code for controlling the gas composition, flow rate, pulse time, and optionally for flowing gas into the chamber prior to deposition to stabilize the pressure in the chamber. A pressure control program can include code for controlling the pressure in the chamber by adjusting, for example, a throttle valve in the exhaust system of the chamber. A heater control program can include code for controlling the current to the heating units used to heat the substrate. Alternatively, the heater control program can control the delivery of a heat transfer gas, such as helium, to the substrate chuck.

[0240] Examples of chamber sensors that can be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the susceptor or chuck. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain the desired process conditions.

[0241] The foregoing describes implementations of the present application implemented in single or multi-chamber semiconductor processing tools. The apparatus and processes described herein can be used in conjunction with lithographic patterning tools or processes, e.g., for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic cells, etc. Typically, though not necessarily, these tools / processes will be used or practiced in conjunction with one another at a common manufacturing facility. Lithographic patterning of a film typically includes some or all of the following steps, each of which enables a number of possible tools: (1) applying photoresist on a workpiece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hot plate or furnace or ultraviolet curing tool; (3) exposing the photoresist to visible or ultraviolet or X-rays using a tool such as a substrate stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern to an underlying film or workpiece by using a dry or plasma- assisted etching tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper.

[0242] In the foregoing description, numerous specific details are set forth to provide a thorough understanding of the implementations presented herein. The disclosed implementations can be practiced without the specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed implementations. While the disclosed implementations will be described in conjunction with the specific embodiments, it will be understood that the specific embodiment is not intended to limit the disclosed implementations.

[0243] While the foregoing implementations have been described in some detail for purposes of clarity, it will be apparent that certain changes and modifications can be made within the scope of the appended claims. Implementation of the various techniques discussed above can be accomplished with specialized hardware, software, or a combination of both. The various components described herein can be implemented as software modules or components that are compiled together or which execute within a framework that is established under an operating system. It will be appreciated that the software components can be loaded from storage media 110 to the memory elements 108 for execution by the processor 106. It will also be appreciated that software components can be written in a variety of computer-readable languages, including but not limited to LISP, Java, C++, Ruby, or Python. The software components can be stored on a variety of media, including but not limited to optical, magnetic, and semiconductor media. The various implementations described above can be implemented using any of the following technologies, including but not limited to: a Java Virtual Machine, a Common Language Runtime, a Microsoft.NET framework, a Linux® framework, a UNIX® framework, a Berkeley Software Distribution (BSD) framework, a Python framework, a Ruby framework, a Cocoa framework, or any other suitable framework.

[0244] Conclusions While the foregoing implementations have been described in some detail for purposes of clarity, it will be apparent that certain changes and modifications can be made within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatuses of the implementations of the present application. Accordingly, the present implementations are to be considered as illustrative and not restrictive, and the implementations are not to be limited to the details given herein.

Claims

1. A method of cleaning aluminum fluoride or aluminum oxyfluoride, the method comprising: providing a fluorine-containing species into a process chamber, one or more components located in the process chamber; removing the one or more components out of the process chamber; and cleaning the one or more components with an etching composition; wherein the one or more components comprise aluminum, an aluminum alloy, or an aluminum-containing material.

2. The method of claim 1, wherein cleaning the one or more components comprises etching away the aluminum fluoride or aluminum oxyfluoride from a surface of the one or more components.

3. The method of claim 1, wherein cleaning the one or more components comprises separating the aluminum fluoride or aluminum oxyfluoride from a surface of the one or more components.

4. The method of claim 1, wherein the one or more components comprise a pedestal, a showerhead, or a showerhead-pedestal.

5. The method of claim 1, wherein the etching composition comprises a hydroxyl-containing solution comprising potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a combination thereof.

6. The method of claim 5, wherein the concentration of the hydroxyl-containing solution is about 0.1% to about 45% weight / volume.

7. The method of claim 6, wherein the concentration of the hydroxyl-containing solution is about 2% to about 7% weight / volume.

8. The method of claim 1, wherein the cleaning time of the one or more components is about 0.1 to about 45 minutes.

9. The method of claim 1, wherein the fluorine-containing species comprises a nitrogen fluoride plasma.

10. The method of claim 1, further comprising: depositing a film on a substrate in the process chamber prior to providing the fluorine-containing species into the process chamber. ​

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