Low-k dielectric gap filling

Abstract

A silicon-containing layer is deposited in the one or more recessed features of the substrate. At least a portion of the silicon-containing layer may be exposed to an oxygen-containing species to form a silicon oxide. The portion of the silicon oxide may be etched.

Description

Incorporation by reference

[0001] The PCT application form is filed simultaneously with this specification as part of this application. Each application identified in the simultaneously filed PCT application form for which this application claims the benefit or priority thereof is incorporated herein by reference in its entirety and for all purposes. Background of the Invention

[0002] During the fabrication process of semiconductor devices, a dielectric material may be formed to fill the gaps between metal features. As the node size decreases, the size of the gaps between metal features also decreases. For high aspect ratio features, controlled gap filling can be particularly challenging.

[0003] The background description provided herein is for the purpose of generally presenting the background of the disclosure. The work of the currently named inventors within the scope described in this background art section and aspects of the specification that could not be determined to be prior art at the time of filing the application are neither expressly nor impliedly admitted to be prior art with respect to the disclosure. Summary of the Invention

[0004] One aspect relates to a method that includes: depositing a silicon-containing layer in one or more recessed features of a substrate; exposing at least a portion of the silicon-containing layer to an oxygen-containing substance, thereby forming a silicon-containing oxide portion in the silicon-containing layer; and at least partially etching the silicon-containing oxide portion.

[0005] In some embodiments, depositing the silicon-containing layer includes introducing a silicon-containing precursor to adsorb on the surface of the substrate and thermally decomposing it to form the silicon-containing layer.

[0006] In some embodiments, the silicon-containing layer includes silicon carbide, silicon carbon oxide, hydrogenated silicon carbon oxide, or silicon carbon oxynitride.

[0007] In some embodiments, the silicon-containing layer includes a conformal layer.

[0008] In some embodiments, the silicon-containing layer includes a pinched off layer.

[0009] In some embodiments, the oxygen-containing substance diffuses into the silicon-containing layer to a penetration depth.

[0010] In some embodiments, the oxygen-containing substance includes oxygen, ozone, hydrogen peroxide, oxygen-containing free radicals, their plasmas, or mixtures thereof.

[0011] In some embodiments, exposing the at least a portion of the silicon-containing layer includes converting the portion of the silicon-containing layer into the silicon-containing oxide portion.

[0012] In some embodiments, at least a portion of the silicon-containing layer is exposed to an oxygen-containing species at a pressure of from about 0.5 Torr to about 5 Torr.

[0013] In some embodiments, at least a portion of the silicon-containing layer is exposed to an oxygen-containing species at a pressure of from about 1 Torr to about 20 Torr.

[0014] In some embodiments, the portion of the silicon-containing oxide portion is etched by exposing the silicon-containing oxide portion to hydrogen fluoride.

[0015] In some embodiments, deposition, exposure, and at least partial etching are performed without breaking vacuum.

[0016] In some embodiments, the method further comprises repeating the deposition, exposure, and etching operations to at least partially fill or completely fill the one or more recessed features of the substrate with a silicon-containing gap-fill material.

[0017] In some embodiments, the one or more recessed features have an aspect ratio of from about 2:1 to about 6:1.

[0018] In another aspect, a method is provided that includes: conformally depositing a doped or undoped silicon carbide layer in one or more recessed features on a substrate; converting at least a portion of the doped or undoped silicon carbide layer to silicon oxide; and at least partially etching the silicon oxide.

[0019] In some embodiments, conformally depositing a doped or undoped silicon carbide layer includes introducing a silicon-containing precursor to adsorb on the surface of the substrate and thermally decomposing it and generating a plasma to form the doped or undoped silicon carbide layer.

[0020] In some embodiments, converting at least a portion of the doped or undoped silicon carbide layer to silicon oxide includes introducing an oxygen-containing species into the one or more recesses.

[0021] In some embodiments, converting at least a portion of the doped or undoped silicon carbide layer to silicon oxide includes removing carbon from the doped or undoped silicon carbide layer.

[0022] In some embodiments, the doped or undoped silicon carbide layer is converted to silicon oxide at a pressure of from about 0.5 Torr to about 5 Torr.

[0023] In some embodiments, at least a portion of the silicon-containing layer is exposed to an oxygen-containing species at a pressure of from about 1 Torr to about 20 Torr.

[0024] In some embodiments, the doped or undoped silicon carbide layer comprises silicon carbide, silicon carbon oxide, hydrogenated silicon carbon oxide, or silicon carbon oxynitride.

[0025] In some embodiments, the doped or undoped silicon carbide layer is deposited by chemical vapor deposition or plasma enhanced chemical vapor deposition.

[0026] In some embodiments, the oxygen-containing material comprises oxygen, ozone, hydrogen peroxide, oxygen-containing radicals, their plasmas, or mixtures thereof.

[0027] In some embodiments, the silicon oxide is etched by exposing the portion of the silicon oxide to hydrogen fluoride.

[0028] In some embodiments, the doped or undoped silicon carbide layer system is converted to silicon oxide at a pressure of about 1 Torr to about 20 Torr.

[0029] In some embodiments, the doped silicon carbide layer comprises one or more dopants comprising oxygen, nitrogen, or mixtures thereof.

[0030] In some embodiments, the method further comprises repeating conformal deposition, conversion, and at least partial etching to partially or fully fill one or more recessed features of the substrate with a silicon-containing gap fill material.

[0031] In some embodiments, the one or more recessed features have an aspect ratio of about 2:1 to about 6:1.

[0032] In another aspect, there is provided an apparatus comprising: one or more processing chambers, each processing chamber including a chuck; one or more gas inlets and associated reactant delivery systems for entering the processing chamber; and a controller having at least one processor and a memory, wherein the at least one processor is communicatively coupled with the memory, the at least one processor is at least operably connected to the reactant delivery system, and the memory stores computer-executable instructions for controlling the at least one processor to: provide a substrate to one of the one or more processing chambers; introduce a silicon-containing precursor to the one or more processing chambers; introduce the one or more oxygen-containing materials to the one or more processing chambers; expose the substrate to the oxygen-containing material; and expose the substrate to an etching chemical.

[0033] On the other hand, there is provided an apparatus including: one or more processing chambers, each processing chamber including a chuck; one or more gas inlets for entering the processing chamber and a related reactant delivery system; one or more remote plasma sources fluidly connected to the one or more processing chambers, the one or more gas inlets, and the related reactant delivery system; and a controller having at least one processor and a memory, wherein the at least one processor is communicatively connected to the memory, the at least one processor is operably connected to at least the reactant delivery system, and the memory stores computer-executable instructions for controlling the at least one processor to: provide a substrate to one of the one or more processing chambers; introduce a silicon-containing precursor to the one or more processing chambers; introduce one or more oxygen-containing radicals from the one or more remote plasma sources into the one or more processing chambers; expose the substrate to the oxygen-containing radicals at a pressure of about 1 Torr to about 20 Torr; and expose the substrate to an etching chemical.

[0034] As used herein, the term "about" means within + / - 10% of any designated value. When used herein, the term is used to modify any designated value, numerical range, or endpoints of one or more ranges.

[0035] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 FIG. is a flowchart of an exemplary method for depositing, oxidizing, and etching a silicon-containing layer in a feature of a substrate according to some embodiments.

[0037] Figures 2A - 2D FIG. is a cross-sectional schematic view of gap filling for features of an exemplary substrate according to some embodiments.

[0038] Figures 3A - 3D FIG. is a cross-sectional schematic view of gap filling for features of an exemplary substrate according to some embodiments.

[0039] Figures 4A - 4D FIG. is a cross-sectional schematic view of gap filling for features of an exemplary substrate according to some embodiments.

[0040] Figure 5 FIG. is a schematic view of an exemplary processing chamber according to some embodiments.

[0041] Figure 6 FIG. is a schematic view of an exemplary processing tool according to some embodiments.

[0042] Figure 7A FIG. is a schematic view of an exemplary processing apparatus according to some embodiments.

[0043] Figure 7B To show the Figure 7A schematic diagram of the light source arrangement of the exemplary processing device in

[0044] Figure 7C To show the Figure 7A schematic diagram of the light source arrangement of the exemplary processing device in

[0045] Figure 7D To show the Figure 7A schematic diagram of the base cross - section of the exemplary processing device in

[0046] Figure 7E To show the schematic diagram of the base cross - section of Figure 7D with additional features according to some embodiments Detailed Description

[0047] In the following description, numerous specific details are set forth to provide a thorough understanding of the described embodiments. The disclosed embodiments may be practiced in part or in whole without these specific details. In other instances, conventional processing operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Although specific embodiments will be used to illustrate the disclosed embodiments, it should be understood that they are not intended to limit the disclosed embodiments. Terms and Definitions

[0048] The terms "acyl" or "alkanoyl", which may be used interchangeably herein, denote a group or hydrogen of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms in a straight - chain, branched - chain, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, connected to the parent molecular group through a carbonyl as defined herein. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl and the like. In some embodiments, acyl or alkanoyl is -C(O)-R, where R is hydrogen, an aliphatic group or an aromatic group as defined herein.

[0049] "Alkanoyloxy" means an alkanoyl as defined herein connected to the parent molecular group through an oxy as defined herein. An example of such a group is acetoxy (-OAc or -OC(O)Me). In some embodiments, alkanoyloxy is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group as defined herein.

[0050] "Aliphatic" means having at least one carbon atom to 50 carbon atoms (C 1-50) having from 1 to 25 carbon atoms (C 1-25 ), or from 1 to 10 carbon atoms (C 1-10 ), and which includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), includes their cyclic forms, and further includes straight-chain and branched arrangements, as well as all stereoisomers and positional isomers. The aliphatic group is unsubstituted or substituted with a functional group such as those described herein. For example, the aliphatic group may be substituted with one or more substituent groups (such as the groups described herein for alkyl).

[0051] "Aliphatic-carbonyl" means an aliphatic group coupled to or couplable to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, aliphatic-carbonyl is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0052] "Aliphatic-carbonyloxy" means an aliphatic group coupled to or couplable to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, aliphatic-carbonyloxy is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0053] "Aliphatic-oxy" means an aliphatic group coupled to or couplable to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, aliphatic-oxy is -O-R, where R is an optionally substituted aliphatic group as defined herein.

[0054] "Aliphatic-oxycarbonyl" means an aliphatic group coupled to 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, aliphatic-oxycarbonyl is -C(O)O-R, where R is an optionally substituted aliphatic group as defined herein.

[0055] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" each mean and as defined herein an alkyl, alkenyl, or alkynyl group that is coupled or couplable (or linked) to a parent molecular group through an aryl group as defined herein. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl may be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl may be substituted with one or more substituents as described herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl has 7 to 16 carbons (C 7-16 alkyl-aryl), and those having an alkyl of 1 to 6 carbons and an aryl of 4 to 18 carbons (i.e., C 1-6 alkyl-C 4-18 aryl). Exemplary unsubstituted alkenyl-aryl has 7 to 16 carbons (C 7-16 alkenyl-aryl), and those having an alkenyl of 2 to 6 carbons and an aryl of 4 to 18 carbons (i.e., C 2-6 alkenyl-C 4-18 aryl). Exemplary unsubstituted alkynyl-aryl has 7 to 16 carbons (C 7-16 alkynyl-aryl), and those having an alkynyl of 2 to 6 carbons and an aryl of 4 to 18 carbons (i.e., C 2-6 alkynyl-C 4-18 aryl). In some embodiments, the alkyl-aryl is -L-R, where L is an aryl or arylene group as defined herein and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl is -L-R, where L is an aryl or arylene group as defined herein and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl is -L-R, where L is an aryl or arylene group as defined herein and R is an alkynyl group as defined herein.

[0056] "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 may be derived by removing a hydrogen atom from a carbon atom of a parent olefin. The alkenyl may be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C 2-24Alkyl. An alkenyl can be monovalent or polyvalent (e.g., divalent), formed by removing one or more hydrogens to form a suitable connection to the parent molecular group or a suitable connection between the parent molecular group and another substituent. An alkenyl can also be substituted or unsubstituted. For example, an alkenyl can be substituted with one or more substituents, as described herein for alkyl. Non-limiting alkenyls include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0057] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxys include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, trihaloalkoxy, such as trifluoromethoxy, and the like. An alkoxy can be substituted or unsubstituted. For example, an alkoxy can be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxys include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkoxy.

[0058] "Alkoxyalkyl" means an alkyl as defined herein substituted with an alkoxy as defined herein. Exemplary unsubstituted alkoxyalkyls include those having 2 to 12 carbons (C 2-12 alkoxyalkyl), and those having an alkyl with 1 to 6 carbons and an alkoxy with 1 to 6 carbons (i.e., C 1-6 alkoxy-C 1-6 alkyl). In some embodiments, an alkoxyalkyl is -L-O-R, where L and R are each independently an alkyl as defined herein.

[0059] "Alkoxycarbonyl" means -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, an alkoxycarbonyl is -C(O)-OAk, where Ak is an alkyl as defined herein. An alkoxycarbonyl can be substituted or unsubstituted. For example, an alkoxycarbonyl can be substituted with one or more substituent groups, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyls 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.

[0060] "Alkyl" means a saturated monovalent hydrocarbon having from at least one carbon atom to 50 carbon atoms (C 1-50 )(e.g., from 1 to 25 carbon atoms (C 1-25 ), or from 1 to 10 carbon atoms (C 1-10 ), where the saturated monovalent hydrocarbon can be derived by removing one hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). The alkyl can be branched, straight-chain, or cyclic (e.g., cycloalkyl). Exemplary alkyls include branched or unbranched saturated hydrocarbon groups having from 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl can also be substituted or unsubstituted. The alkyl can be monovalent or polyvalent (e.g., divalent), by removing one or more hydrogens to form a proper linkage to the parent molecular group or a proper linkage between the parent molecular group and another substituent. For example, the alkyl can be substituted with one, two, three, or (in the case of an alkyl having two or more carbons) four substituents, the substituents 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 1-6 alkyl); (4) amino (e.g., -NR 1 R 2 , where R 1 and R 2 each independently is 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 they are attached can form a heterocyclic group as defined herein); (5) aryl; (6) aryloxyalkyl (e.g., -O-L-R, where L is alkyl and R is aryl); (7) aroyl (e.g., -C(O)-R, where R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 Cycloalkyl; (12) halogen; (13) heterocyclic group (e.g., a 5-, 6- or 7-membered ring containing one, two, three or four non-carbon heteroatoms as defined herein); (14) heterocyclic oxy group (e.g., -O-R, where R is a heterocyclic group as defined herein); (15) heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (16) hydroxy group (e.g., -OH); (17) N-protected amino; (18) nitro group (e.g., -NO2); (19) oxo group (e.g., =O); (20) C 1-6 Thioalkyl (e.g., -S-R, where R is alkyl); (21) mercapto group (e.g., -SH); (22) -CO2R 1 , where 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, where L is C 1-6 alkyl and R is C 4-18 aryl); (23) -C(O)NR 1 R 2 , where R 1 and each of 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, where L is C 1-6 alkyl and R is C 4-18 aryl); (24) -SO2R 1 , where R 1 is selected from the group consisting of: (a) C 1-6 alkyl, (b) C 4-18 aryl and (c) 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); (25) -SO2NR 1 R 2 , where R 1 and each of 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 1-6Alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 and each of R 2 is independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (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 attached to the nitrogen atom through a carbonyl or sulfonyl group. The alkyl can be a primary, secondary, or tertiary alkyl substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 alkyl.

[0061] "Alkylene", "alkenylene", or "alkynylene" respectively mean the polyvalent (e.g., divalent) form of alkyl, alkenyl, or alkynyl as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene 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 2-24Alkylene. In other embodiments, the alkylene 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 can be branched or unbranched. The alkylene, alkenylene or alkynylene can also be substituted or unsubstituted. For example, the alkylene, alkenylene or alkynylene can be substituted with one or more substituent groups, as described herein for alkyl groups.

[0062] "Alkylsulfinyl" means an alkyl group as defined herein attached to the parent molecular group through an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl is C 1-6 or C 1-12 alkylsulfinyl. In other embodiments, the alkylsulfinyl is -S(O)-R, where R is an alkyl group as defined herein.

[0063] "Alkylsulfinylalkyl" means an alkyl group as defined herein substituted with an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl 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 is -L-S(O)-R, where L and R are each independently an alkyl group as defined herein.

[0064] "Alkylsulfonyl" means an alkyl group as defined herein attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl is C 1-6 or C 1-12 alkylsulfonyl. In other embodiments, the alkylsulfonyl is -SO2-R, where R is an optionally substituted alkyl group (e.g., as described herein, including an optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0065] "Alkylsulfonylalkyl" means an alkyl group as defined herein substituted with an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24Alkylsulfonylalkyl (e.g., C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, the alkylsulfonylalkyl is -L-SO2-R, where L and R are each independently an alkyl as defined herein.

[0066] "Alkynyl" means an unsaturated monovalent hydrocarbon having from at least two carbon atoms to 50 carbon atoms (C 2-50 )(e.g., from two to 25 carbon atoms (C 2-25 ), or from two to ten carbon atoms (C 2-10 )) and at least one carbon-carbon triple bond, where the unsaturated monovalent hydrocarbon may be derived by removing a hydrogen atom from one carbon atom of the parent alkyne. The alkynyl can be branched, straight-chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include optionally substituted C 2-24 alkyls having one or more triple bonds. The alkynyl can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. The alkynyl can be monovalent or polyvalent (e.g., divalent), by removing one or more hydrogens to form an appropriate linkage with the parent molecular group or an appropriate linkage between the parent molecular group and another substituent. The alkynyl can also be substituted or unsubstituted. For example, the alkynyl can be substituted with one or more substituents, as described herein for alkyl.

[0067] "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.

[0068] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or where R 1 and R 2 together with the nitrogen atom to which they are attached can form a heterocyclic group as defined herein.

[0069] "Amino" means -NR 1 R 2 , where 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; or where R1 With R 2 Together with the respective nitrogen atoms to which they are attached, they can form a heterocyclic group as defined herein. In certain embodiments, R 1 With 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 certain embodiments, R 1 With R 2 Can together with the respective nitrogen atoms to which they are attached form an optionally substituted heterocyclic group.

[0070] "Aminoalkyl" means an alkyl as defined herein substituted with an amino as defined herein. In some embodiments, aminoalkyl is -L-NR 1 R 2 , where L is an alkyl as defined herein, and R 1 With R 2 Each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof; or R 1 With R 2 Together with the respective nitrogen atoms to which they are attached can form a heterocyclic group as defined herein. In other embodiments, aminoalkyl is -L-C(NR 1 R 2 )(R 3 )-R 4 , where L is a covalent bond or alkyl as defined herein; R 1 With R 2 Each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof; or R 1 With R 2 Together with the respective nitrogen atoms to which they are attached can form a heterocyclic group as defined herein; and R 3 With R 4 Each independently is H or alkyl as defined herein.

[0071] "Aminooxy" means an oxy as defined herein substituted with an amino as defined herein. In some embodiments, aminooxy is -O-NR 1 R 2 , where R 1 With R 2Each 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 together with R 2 and the nitrogen atom to which each is attached may form a heterocyclic group as defined herein. In certain embodiments, R 1 and R 2 are 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.

[0072] "Aromatic" means a cyclic conjugated group or moiety having 5 to 15 (unless otherwise specified) ring atoms in a single ring (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); i.e., at least one ring and optionally multiple fused rings have a continuous and delocalized π-electron system. Generally, 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. The aromatic group is unsubstituted or substituted with functional groups such as those described herein. For example, the aromatic group may be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0073] "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, aromatic-carbonyl is -C(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0074] "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, aromatic-carbonyloxy is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0075] "Aromatic-oxy" means an aromatic group that is coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, aromatic-oxy is -O-R, where R is an optionally substituted aromatic group as defined herein.

[0076] "Aromatic-oxycarbonyl" means an aromatic group that is coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, aromatic-oxycarbonyl is -C(O)O-R, where R is an optionally substituted aromatic group as defined herein.

[0077] "Aryl" means an aromatic carbocyclic group containing at least five carbon atoms to 15 carbon atoms (C 5-15 )(e.g., five to ten carbon atoms (C 5-10 )) having a single ring or multiple fused rings, where the fused rings may or may not be aromatic, provided that the point of attachment to the remainder of the compound disclosed herein is through an atom of the aromatic carbocyclic group. Aryl may be substituted with one or more groups other than hydrogen (e.g., aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof). Exemplary aryls include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxyphenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. 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 is defined as a group containing an aromatic group and no heteroatoms. Aryl may be substituted or unsubstituted. Aryl may 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 1-6Alkyl (e.g., -L-S(O)-R, where L and R are each independently C 1-6 alkyl); (7) C 1-6 Alkylsulfonyl (such as -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, halogeteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 and R 2 together with the nitrogen atom to which they are attached may form a heterocyclic group as defined herein); (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where 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, halogeteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 and R 2 together with the nitrogen atom to which they are attached may form a heterocyclic group 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, where L is C 1-6 alkyl and R is C 4-18 aryl); (14) Aroyl (e.g., -C(O)-R, where R is aryl); (15) Azido (e.g., -N3); (16) Cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) Aldehyde (e.g., -C(O)H); (19) Aldehyde-C1-6 alkyl (e.g., -L-C(O)H, where L is C 1-6 alkyl); (20)C 3-8 cycloalkyl; (21)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); (22) halogen; (23)C 1-6 haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where 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 R 2 are each independently H or C 1-6 alkyl); (24) heterocyclic group (e.g., as defined herein, e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclic oxy group (e.g., -O-R, 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) hydroxy (-OH); (28)C 1-6 hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or alkyl; and R 1 and R 2 are each independently H or C 1-6 alkyl as defined herein); (29) nitro; (30)C 1-6 nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or alkyl; and R 1 and R 2 are each independently H or C 1-6 alkyl as defined herein); (31) N-protected amino; (32) N-protected amino-C1-6 alkyl; (33) oxo group (e.g., =O); (34) C 1-6 thioalkyl (e.g., -S-R, where R is C 1-6 alkyl); (35) thio-C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-S-R, 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 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, 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 where R 1 and R 2 are each 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, 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 where R 1 is selected from the group consisting of: (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) 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); (39) -(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4 and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C4-18 Aryl-C 1-6 alkyl (e.g., -L-R, 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 where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (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 attached 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) cycloalkoxy (e.g., -O-R, where R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L-R, where L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -O-L-R, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl is C 4-18 6 4-14 5 4-12 4 4-10 3 6-18 2 6-14 1 6-12 0 6-10 aryl.

[0078] "Aryl-alkyl", "aryl-alkenyl", and "aryl-alkynyl" mean an aryl as defined herein that is coupled or couplable (or linked) to a parent molecular group through an alkyl, alkenyl, or alkynyl, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl may be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl may be substituted with one or more substituent groups as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl has 7 to 16 carbons (C 7-16 aryl-alkyl), and those having an aryl with 4 to 18 carbons and an alkyl with 1 to 6 carbons (i.e., C 4-18 aryl-C 1-6 alkyl). Exemplary unsubstituted aryl-alkenyl has 7 to 16 carbons (C 7-16 aryl-alkenyl), and those having an aryl with 4 to 18 carbons and an alkenyl with 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkenyl). Exemplary unsubstituted aryl-alkynyl has 7 to 16 carbons (C 7-16 aryl-alkynyl), and those having an aryl with 4 to 18 carbons and an alkynyl with 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkynyl). In some embodiments, aryl-alkyl is -L-R, where L is an alkyl or alkylene as defined herein, and R is an aryl as defined herein. In some embodiments, aryl-alkenyl is -L-R, where L is an alkenyl or alkenylene as defined herein, and R is an aryl as defined herein. In some embodiments, aryl-alkynyl is -L-R, where L is an alkynyl or alkynylene as defined herein, and R is an aryl as defined herein.

[0079] "Arylene" means a polyvalent (e.g., divalent) form of an aryl as described herein. Exemplary arylenes include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, arylene is C 4-18 、C 4-14 、C 4-12 、C 4-10 、C 6-18 、C 6-14 、C 6-12 、or C 6-10Arylene. The arylene can be branched or unbranched. The arylene can also be substituted or unsubstituted. For example, the arylene can be substituted with one or more substituent groups, as described herein for aryl.

[0080] "Arylalkoxy" means an aryl-alkyl as defined herein attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy is -O-L-R, where L is an alkyl as defined herein and R is an aryl as defined herein.

[0081] "Aryloxy" means -OR, where R is an optionally substituted aryl as described herein. In some embodiments, the unsubstituted aryloxy is C 4-18 or C 6-18 aryloxy. In other embodiments, R is an aryl optionally substituted with alkyl, alkanoyl, amino, hydroxy, and the like.

[0082] "Aryloxycarbonyl" means an aryloxy as defined herein attached to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl is C 5-19 aryloxycarbonyl. In other embodiments, the aryloxycarbonyl is -C(O)O-R, where R is an aryl as defined herein.

[0083] "Aryloy" means an aryl attached to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aryloy is C 7-11 aryloy or C 5-19 aryloy. In other embodiments, the aryloy is -C(O)-R, where R is an aryl as defined herein.

[0084] "Aryloyloxy" means an aryloy as defined herein attached to the parent molecular group through an oxygen group. In some embodiments, the unsubstituted aryloyloxy is C 5-19 aryloyloxy. In other embodiments, the aryloyloxy is -OC(O)-R, where R is an aryl as defined herein.

[0085] "Azido" means the -N3 group.

[0086] "Azidoalkyl" means an azido attached to the parent molecular group through an alkyl as defined herein. In some embodiments, the azidoalkyl is -L-N3, where L is an alkyl as defined herein.

[0087] "Azo" means the -N=N- group.

[0088] "Carbamoyl" means an amino group attached to a parent molecular group through a carbonyl group as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 group, where 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 where R 1 and R 2 together with the nitrogen atom to which each is attached may form a heterocyclic group as defined herein.

[0089] "Carbamoyloxy" means a carbamoyl group as defined herein attached to a parent molecular group through an oxy group as defined herein. In some embodiments, carbamoyloxy is -OC(O)NR 1 R 2 group, where 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 where R 1 and R 2 together with the nitrogen atom to which each is attached may form a heterocyclic group as defined herein.

[0090] "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.

[0091] "Carbonyl" means a -C(O)- group, which may also be represented as >C=O.

[0092] "Carboxyl" means a -CO2H group or its anion.

[0093] "Catalyst" means a compound that is typically present in a small amount relative to the reactants and is capable of catalyzing a synthesis reaction, as will be readily understood by those skilled in the art. In some embodiments, the catalyst may comprise a transition metal coordination complex.

[0094] "Cyanato" means an -OCN group.

[0095] "Cyano" means a -CN group.

[0096] "Cycloaliphatic" means a cycloaliphatic group as defined herein.

[0097] "Cycloalkoxy" means a cycloalkyl group as defined herein that is attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy is -O-R, where R is a cycloalkyl group as defined herein.

[0098] "Cycloalkylalkoxy" means -O-L-R, where L is an alkyl or alkylene group as defined herein and R is a cycloalkyl group as defined herein.

[0099] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group having three to eight carbons (unless otherwise specified), such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, and the like. The cycloalkyl can also be substituted or unsubstituted. For example, the cycloalkyl can be substituted with one or more groups, including those described herein for alkyl groups. In addition, the cycloalkyl can include one or more double bonds and / or triple bonds.

[0100] "Cycloheteroaliphatic" means a cycloheteroaliphatic group as defined herein.

[0101] "Disilanyl" means a group containing an Si-Si bond. In some embodiments, the disilanyl is a -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 S5Each independently is H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino group.

[0102] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0103] "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, for example, by resonance.

[0104] "Electron-withdrawing group" means a functional group capable of accepting electron density from a ring to which it is directly attached, for example, by inductive electron withdrawal.

[0105] "Halo" means F, Cl, Br, or I.

[0106] "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 by halogen atoms (e.g., fluorine, bromine, chlorine, or iodine).

[0107] "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 by halogen atoms (e.g., fluorine, bromine, chlorine, or iodine). In an independent embodiment, the haloalkyl can be a -CX3 group, where each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, the haloalkyl is -L-X, where L is an alkyl group as defined herein and X is fluorine, bromine, chlorine, or iodine. In other embodiments, the haloalkyl 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.

[0108] "Haloheteroaliphatic" means a heteroaliphatic as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced by halogen atoms (e.g., fluorine, bromine, chlorine, or iodine).

[0109] "Heteroaliphatic" means an aliphatic group as defined herein that contains from at least one to 20 heteroatoms (e.g., from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms), the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. The heteroaliphatic group may be unsubstituted or substituted with, for example, functional groups as described herein. For example, the heteroaliphatic group may be substituted with one or more substituent groups, such as those described herein for alkyl groups.

[0110] "Heteroaliphatic-carbonyl" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, heteroaliphatic-carbonyl is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0111] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, heteroaliphatic-carbonyloxy is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0112] "Heteroaliphatic-oxy" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, heteroaliphatic-oxy is -O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0113] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, heteroaliphatic-oxycarbonyl is -C(O)O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0114] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" each mean an alkyl, alkenyl, or alkynyl as defined herein (which may be branched, straight-chain, or cyclic) containing from at least one to 20 heteroatoms (e.g., from 1 to 15 heteroatoms or from 1 to 5 heteroatoms), the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0115] "Heteroalkylene", "heteroalkenylene", and "heteroalkynylene" each mean a polyvalent (e.g., divalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl as described herein.

[0116] "Heteroaromatic" means an aromatic group as defined herein that includes from at least one to 20 heteroatoms (e.g., from one to 15 heteroatoms, or from one to 5 heteroatoms), the heteroatoms being 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 as described herein. For example, the heteroaromatic group may be substituted with one or more substituent groups as described herein for alkyl and / or aryl.

[0117] "Heteroaromatic-carbonyl" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, heteroaromatic-carbonyl is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0118] "Heteroaromatic-carbonyloxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, heteroaromatic-carbonyloxy is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0119] "Heteroaromatic-oxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, heteroaromatic-oxy is -O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0120] "Heteroaromatic-oxycarbonyl" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, heteroaromatic-oxycarbonyl is -C(O)O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0121] "Heteroaryl" means an aryl group containing at least one to six heteroatoms (e.g., one to four heteroatoms), the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the ring. Such heteroaryl can have a single ring or multiple fused rings, where the fused rings can be or can not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl. Heteroaryl 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 includes a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n + 2 π electrons within a single-ring or poly-ring system.

[0122] "Heteroarylene" means a polyvalent (e.g., divalent) form of a heteroaryl as described herein.

[0123] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particularly disclosed embodiments, for example when valence limitations do not permit, heteroatoms do not include halogen atoms.

[0124] "Heterocyclyl" means a 5-, 6- or 7-membered ring (unless otherwise specified) containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur or halogen). The 5-membered ring has zero to two double bonds, and the 6-membered and 7-membered rings have zero to three double bonds. The term "heterocyclyl" also encompasses bicyclic, tricyclic and tetracyclic groups, wherein any of the above heterocycles are fused to 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 heterocycle (e.g., indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothienyl 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.

[0125] "Heterocyclyloxy" means a heterocyclic group as defined herein attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -O-R, where R is a heterocyclic group as defined herein.

[0126] "Heterocyclyloyl" means a heterocyclic group as defined herein attached to the parent molecular group through a carbonyl group. In some embodiments, heterocyclyloyl is -C(O)-R, where R is a heterocyclic group as defined herein.

[0127] "Hydrazino" means -NR 1 -NR 2 R 3 where R 1 、R 2 and R 3Each independently selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof; or wherein R 1 and R 2 in combination or R 2 and R 3 in combination together with the nitrogen atom to which each is attached may form a heterocyclic 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 certain embodiments, R 2 and R 3 together with the nitrogen atom to which each is attached form an optionally substituted heterocyclic group.

[0128] "Hydroxyl" means -OH.

[0129] "Hydroxyalkyl" means an alkyl as defined herein substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group may be attached to a single carbon atom of the alkyl, examples of which are hydroxymethyl, dihydroxypropyl and the like. In some embodiments, the hydroxyalkyl is -L-OH, where L is an alkyl as defined herein. In other embodiments, the hydroxyalkyl is -L-C(OH)(R 1 )-R 2 , where L is a covalent bond or alkyl as defined herein, and R 1 and R 2 are each independently H or alkyl as defined herein.

[0130] "Imidoyl" means a group including carbonimidoyl. In some embodiments, the imidoyl is C(NR 1 )R 2 , where R 1 and R 2 are each independently selected from hydrogen as defined herein, 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. In other embodiments, the imidoyl 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.

[0131] "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 certain 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.

[0132] "Isocyanato" means an -NCO group.

[0133] "Isocyano" means an -NC group.

[0134] "Ketone" means -C(O)R or a compound containing 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, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0135] "Nitro" means an -NO2 group.

[0136] "Nitroalkyl" means an alkyl as defined herein substituted with one to three nitro groups. In some embodiments, nitroalkyl is -L-NO, where L is an alkyl as defined herein. In other embodiments, nitroalkyl is -L-C(NO)(R 1 )-R 2 , where L is a covalent bond or an alkyl as defined herein, and R 1 and R 2Each is independently H or alkyl as defined herein.

[0137] "Oxo" means the =O group.

[0138] "Oxy" means -O-.

[0139] "Perfluoroalkyl" means an alkyl as defined herein in which every hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyls include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl is -(CF2) n CF3, where n is an integer from 0 to 10.

[0140] "Perfluoroalkoxy" means an alkoxy as defined herein in which every hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy is -O-R, where R is a perfluoroalkyl as defined herein.

[0141] "Salt" means an ionic form of a compound or structure (e.g., any of the formulas, compounds, or compositions described herein) that contains a cationic or anionic compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge S.M. et al., "Pharmaceutical salts," J. Pharm. Sci. 1977 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 present disclosure or separately by reacting a free base group with a suitable organic acid (thus producing an anionic salt) or by reacting an acid group with a suitable metal or organic salt (thus producing 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, 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 metal salts or alkaline earth metal salts such as barium, calcium (such as calcium edetate), lithium, magnesium, potassium, sodium and the like; other metal salts such as aluminum, bismuth, iron and zinc; and non-toxic ammonium salts, quaternary ammonium salts and amino cations including but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine,Pyridinium and analogs. Other cationic salts include organic salts such as chloroprocain, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as 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 pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium,Optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0142] "Silyl" means -SiR 1 R 2 R 3 or -SiR 1 R 2 - group. In some embodiments, R 1 、R 2 and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 1 、R 2 and R 3 are 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 silyl group is Si(R) a (OR) b (NR2) c , where 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 certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0143] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy is -O-SiR 1 R 2 R 3 , where R 1 、R 2 and R 3 are each independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino group. In certain embodiments, R 1 、R 2 and R 3 are each independently H, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted aryloxy, an optionally substituted alkyl-aryl, an optionally substituted aryl-alkyl, or an optionally substituted amino group. In other embodiments, the silyloxy is -O-Si(R) a (OR) b (NR2) c , where each R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic or an optionally substituted heteroaromatic; a, b and c are each ≥ 0; a + b + c = 3. In certain embodiments, each R is independently H, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl.

[0144] "Sulfinyl" means the -S(O)- group.

[0145] "Sulfo" means the -S(O)2OH group.

[0146] "Sulfonyl" or "sulfonate" means the -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein.

[0147] "Thioalkyl" means an alkyl group as defined herein attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyls include C 1-6 thioalkyl. In some embodiments, the thioalkyl is -S-R, where R is an alkyl as defined herein.

[0148] "Thiol" means the -SH group.

[0149] Those skilled in the art will understand that the definitions provided above are not intended to include non - allowable substitution patterns (e.g., a methyl group substituted by five different groups and the like). Those skilled in the art can easily understand such non - allowable substitution patterns. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

[0150] The terms "semiconductor wafer", "wafer", "substrate", "wafer substrate", and "partially fabricated integrated circuit" may be used interchangeably. Those skilled in the art will understand that the term "partially fabricated integrated circuit" may refer to a semiconductor wafer during any one of many stages of integrated circuit fabrication 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, 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). Workpieces can have various shapes, sizes, and materials.

[0151] As used herein, "semiconductor device manufacturing operation" is an operation performed during semiconductor device manufacturing. Generally, the 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 etching tool, and the like. Categories of semiconductor device manufacturing operations include subtractive processes, such as etching processes and planarization processes, and additive processes, such as deposition processes (e.g., physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), electrochemical deposition, electroless deposition). In the context of an etching process, a substrate etching process includes the process of etching a mask layer, or more generally includes the process of etching any material layer that is currently deposited on and / or otherwise retained on the substrate surface. Such etching processes can etch a stack of layers in the substrate.

[0152] "Manufacturing equipment" refers to the equipment in which the manufacturing process is carried out. Manufacturing equipment typically has a processing chamber where the workpiece is placed during processing. Generally, in use, the manufacturing equipment performs one or more semiconductor device manufacturing operations. Examples of manufacturing equipment for semiconductor device manufacturing include deposition reactors, such as electroplating baths, physical vapor deposition reactors, chemical vapor deposition reactors, and atomic layer deposition reactors, and subtractive - process reactors, such as dry - etching reactors (e.g., chemical and / or physical etching reactors), wet - etching reactors, and ashers.

[0153] The substrate may include "features" or "trenches". As used herein, "feature" may refer to a non-planar structure, typically a surface that is processed during semiconductor device manufacturing operations. Examples of features (which may also be referred to as "negative features" or "recessed features") include trenches, holes, volumes, vias, gaps, recessed regions, and the like. These terms may be used interchangeably in the present invention. An example of a feature is a hole or via in a semiconductor substrate or an upper layer of the substrate. Another example is a trench in the substrate or layer. Features typically have an aspect ratio (depth to lateral dimension). A feature may be characterized by one or more of a narrow and / or recessed opening, a constriction within the feature, and a high aspect ratio. A feature having a high aspect ratio may have an aspect ratio of depth to lateral dimension equal to or greater than about 10:1, equal to or greater than about 15:1, equal to or greater than about 20:1, equal to or greater than about 25:1, equal to or greater than about 30:1, equal to or greater than about 40:1, equal to or greater than about 50:1, or equal to or greater than about 100:1. In various embodiments, the feature may have an underlying layer, such as a barrier layer or an adhesion layer. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, undoped silicon carbide, oxygen-doped silicon carbide, nitrogen-doped silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0154] Features of the substrate may have various types. In some embodiments, the feature may have straight sidewalls, positively sloped sidewalls, or negatively sloped sidewalls. In some embodiments, the feature may have sidewall topography or sidewall roughness, which may be the result of an etching process for forming the feature. In some embodiments, the feature may have a feature opening that is wider at the top of the feature than at the bottom, or the feature may have a feature opening that is wider at the bottom of the feature than at the top.

[0155] The fabrication of semiconductor devices generally involves forming one or more silicon-containing layers on a semiconductor substrate in an integrated manufacturing process. The silicon-containing layers can include doped or undoped silicon oxides, doped or undoped silicon nitrides, or doped or undoped silicon carbides. For example, the silicon-containing layers can include silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, hydrogenated silicon oxycarbide, silicon oxynitride, silicon carbonitride, and combinations thereof. The technology nodes in the integrated circuit manufacturing industry are continuously shrinking. With each technology node, the geometry of the devices also shrinks, and the pitch becomes smaller. The high aspect ratio gaps in these technology nodes may need to be filled with an insulating material, such as an insulating material with a low dielectric constant (low-k). Semiconductor integration operations may involve filling high aspect ratio gaps with a low-k dielectric material. Examples include the fabrication of shallow trench isolation, intermetal dielectric layers, passivation layers, and the like. In another example, when the device features are laterally shrunk, since the conductive materials are formed closer and closer, undesired conductive coupling may occur, which may result in parasitic capacitance, signal propagation delay, and signal crosstalk due to capacitive effects. A low-k material as the interlayer dielectric (ILD) of the conductive interconnects can reduce parasitic capacitance, signal delay, and signal crosstalk. Some applications, including fin field effect transistor (finFET) structures and dynamic random access memory (DRAM) bit structures, may involve depositing a low-k material as the sidewall spacer material.

[0156] Silicon carbide materials, including doped and undoped silicon carbide materials, can be used as insulating materials in integrated circuit applications, which not only have a low dielectric constant but also have improved step coverage, thermal stability, wet etch resistance, dry etch selectivity for oxides / nitrides, and high breakdown voltage. For example, the incorporation of oxygen atoms and / or nitrogen atoms can adjust the properties of the silicon carbide materials. In some embodiments, an oxygen-doped silicon carbide film can be used as an insulating material in integrated circuit applications, which provides a low dielectric constant, improved wet etch resistance (thus withstanding device integration operations), and increased dry etch selectivity for oxides / nitrides.

[0157] Forming high-quality doped silicon-containing thin films may have certain challenges, such as providing a film with excellent step coverage, low dielectric constant, and / or high breakdown voltage, etc. Once a silicon-containing layer with the desired properties and composition is formed, there may be additional challenges in conformally depositing the silicon-containing layer in high aspect ratio features. In the gap filling of high aspect ratio features, conformal deposition may be desirable. Semiconductor manufacturing processes generally involve gap filling processes for dielectric gap filling processes. Chemical vapor deposition (CVD) or atomic layer deposition (ALD) methods can be utilized to fill the features. Some deposition techniques may result in the formation of seams or voids within the features. In some cases, the presence of seams and / or voids in gap filling may lead to high resistance, contamination, loss of the filling material, performance degradation, and even device failure. Processing flow

[0158] Figure 1 FIG. 100 is a flow chart showing an exemplary method of depositing, oxidizing, and etching a silicon-containing layer in features of a substrate according to some embodiments. In operation 110, a substrate having one or more features may be provided into a processing chamber. In some embodiments, the substrate is transferred into the processing chamber. The feature may be a recessed feature, such as a trench formed between adjacent metal patterns. The feature may have an aspect ratio of about 2:1 to about 6:1.

[0159] In operation 120, a silicon-containing layer may be formed in the recessed features on the substrate. In some embodiments, the silicon-containing layer may be deposited to fill the recessed features. The silicon-containing layer may be doped or undoped silicon carbide. The doped silicon carbide may include one or more dopants, including oxygen, nitrogen, or a mixture thereof. The silicon-containing layer may include silicon carbide (SiC), silicon carbon oxide (SiOC), hydrogenated silicon carbon oxide (SiCOH), or silicon carbon oxynitride (SiOCN). The silicon-containing layer may be deposited by CVD, plasma-enhanced CVD (PECVD), ALD (thermal ALD), plasma-enhanced ALD (PEALD), or any suitable deposition technique. In some embodiments, the silicon-containing layer may be deposited by PECVD.

[0160] The thickness of the silicon-containing layer may depend on various deposition parameters, including but not limited to chamber pressure, chamber temperature, precursor flow rate, deposition time, or the like. For example, the deposition time may be controlled to obtain a silicon-containing layer having a desired thickness. In some embodiments, the deposition time may be about 2 to about 200 seconds, or about 3 to about 100 seconds, or about 5 to about 50 seconds. In some embodiments, the desired thickness of the silicon-containing layer may be less than about 1 nm, or about 1 to about 10 nm, or about 2 to about 6 nm.

[0161] For some embodiments, the deposition of the silicon-containing layer may be carried out by flowing one or more silicon-containing precursors into the processing chamber containing the substrate. The silicon-containing precursors are transported to the substrate surface, where they are adsorbed by the substrate and thermally decomposed to form a highly conformal silicon-containing layer. In some embodiments, forming the silicon-containing layer by CVD may involve controlling the deposition pressure in the range of about 0.1 Torr to about 40 Torr, or about 0.5 Torr to about 20 Torr. The substrate temperature during deposition may be controlled to be about 300 °C to about 700 °C, or about 400 °C to about 650 °C. After deposition, the step coverage of the silicon-containing layer may be at least about 85%. In some embodiments, the step coverage may be at least about 90% or at least about 95%.

[0162] According to some embodiments, the silicon-containing layer may be conformally deposited along the top surface, sidewalls, and bottom surface of the feature. The sidewalls may include upper sidewalls and lower sidewalls. "Upper" and "lower" are not specifically defined with respect to the depth from the top of the feature. Instead, "upper" and "lower" may refer to any relative position with respect to each other and may be at any depth. In one example, depending on the embodiment, the upper sidewall may refer to a depth ranging from about 0.1% to about 90% of the depth from the top of the feature, and the lower sidewall may refer to a depth ranging from about 90% to about 100% of the depth from the top of the feature. In another example, the upper sidewall may refer to a depth ranging from about 0.1% to about 30% of the depth from the top of the feature, and the lower sidewall may refer to a depth ranging from about 30% to about 100% of the depth from the top of the feature. In some embodiments, the upper sidewall and the lower sidewall may be defined by the penetration depth of an oxygen-containing material described herein. For example, the upper sidewall may refer to the depth in the silicon-containing layer starting from the top of the feature where the oxygen-containing material is adsorbed and diffused, and the lower sidewall may refer to the portion of the sidewall where no oxygen-containing material is present.

[0163] Without being limited to any theory, a silicon-containing precursor having a low sticking coefficient may be able to produce a highly conformal silicon layer. "Sticking coefficient" is a term used to describe the ratio of the number of adsorbed species (such as debris or molecules) that adsorb / attach to a surface to the total number of species that impinge on that surface during the same period of time. The symbol S c is sometimes used to refer to the sticking coefficient. The value of S c ranges between 0 (meaning no species attach) and 1 (meaning all impinging species attach). A variety of factors affect the sticking coefficient, including the type of impinging species, surface temperature, surface coverage, structural details of the surface, and the kinetic energy of the impinging species. Some species are inherently more "sticky" than others, making it more likely for them to adsorb to the surface each time they impinge on the surface. These stickier species have a larger sticking coefficient (all other factors being equal). In some cases, the sticking coefficient of the precursor (under the relevant deposition conditions) may be about 0.05 or less, such as about 0.001 or less.

[0164] In various embodiments, the silicon-containing precursor is silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In certain embodiments, the silicon-containing precursor includes a halosilane precursor. In certain embodiments, the silicon-containing precursor includes an aminosilane precursor.

[0165] The aminosilanes include at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogen, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), and substituted mono-, di-, tri-, and tetra-aminosilanes such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2, BTBAS), tert-butyl silylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamido)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. Further examples of aminosilanes are trisilylamine (N(SiH3)3). In one example, the silicon-containing precursor is DIPAS. In another example, the silicon-containing precursor is BTBAS.

[0166] The silicon-containing precursor may include one or more optionally substituted amino groups, thus providing non-limiting aminosilanes. In one embodiment, the precursor has the formula (R′) 4-x Si(NR″2) x , where: x is 1, 2, 3, or 4; each R′ is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanoxy, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally two of the R″s together with the nitrogen atom to which they are attached may form an optionally substituted heterocyclic group.

[0167] In another embodiment, the precursor has the formula (R″2N) x (R′) 3-x Si-L-Si(R′)3-x (NR″2) x , wherein: Each x is independently 0, 1, 2, or 3; L is a linker, such as a covalent bond, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an oxy group (-O-), an imino group or a silyl group; Each R′ is independently H, an aliphatic group, an aliphatic-carbonyl group, an aliphatic-carbonyloxy group, an aliphatic-oxy group, an aliphatic-oxycarbonyl group, a heteroaliphatic group, a heteroaliphatic-carbonyl group, a heteroaliphatic-carbonyloxy group, a heteroaliphatic-oxy group, a heteroaliphatic-oxycarbonyl group, an aromatic group, an aromatic-carbonyl group, an aromatic-carbonyloxy group, an aromatic-oxy group, an aromatic-oxycarbonyl group, a heteroaromatic group, a heteroaromatic-oxy group, an amino group, a hydrazino group, an azido group, a hydroxy group, a silyl group, a siloxy group, a cyanoxy group, an isocyanato group, a cyano group or an isocyano group, any of which may be optionally substituted; and Each R″ is independently H, an aliphatic group, a heteroaliphatic group, an aromatic group, a heteroaromatic group or an amino group, any of which may be optionally substituted; or optionally two of the R″s together with the nitrogen atom to which they are attached may form an optionally substituted heterocyclic group.

[0168] In certain embodiments, L is an optionally substituted imino group, such as -NR-, where R is H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group. In other embodiments, L is an optionally substituted silyl group, such as -SiR2-, where each R is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group.

[0169] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L contains a carbon atom or a heteroatom). In yet another embodiment, x is 0; and / or L includes an optionally substituted aliphatic group, an optionally substituted alkylene group, an optionally substituted alkenylene group, an optionally substituted alkynylene group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkylene group, an optionally substituted heteroalkenylene group, an optionally substituted heteroalkynylene group, an optionally substituted aromatic group, an optionally substituted arylene group, an optionally substituted heteroaromatic group, an optionally substituted heteroarylene group, an oxy group (-O-), an imino group or a silyl group.

[0170] In certain embodiments, at least one R′ or R″ is not H. The precursor can have any useful combination of R′ groups attached to one or more silicon atoms and the amino group (NR″2).

[0171] In some embodiments, R′ is H, an optionally substituted amino group (e.g., -NR2), an aliphatic-oxy group (e.g., an alkoxy group or -OR), an aliphatic-carbonyl group (e.g., an alkanoyl group or -C(O)R), an aliphatic-carbonyloxy group (e.g., an alkanoyloxy group or -OC(O)R), an aliphatic-oxycarbonyl group (e.g., an alkoxycarbonyl group or -C(O)OR), a silyl group (e.g., -SiR3), an aliphatic-oxy-silyl group (e.g., an alkoxysilyl group or -Si(R) a (OR) b )、an aminosilyl group (e.g., -Si(R) a (NR2) b ), a siloxy group (e.g., -O-SiR3), an aliphatic-oxy-siloxy group (e.g., an alkoxysiloxy group or -O-Si(R) a (OR) b ), an aminosiloxy group (e.g., -O-Si(R) a (NR2) b ), an aromatic group (e.g., an aryl group), an aromatic-oxy group (e.g., an aryloxy group or -OR), a hydroxy group (-OH), a formyl group (-C(O)H), and the like. In certain embodiments, each R is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted aryl group, and an optionally substituted heteroaromatic group; a ≥ 0; b ≥ 1; and a + b = 3. In some embodiments, two R groups may together with the nitrogen atom to which they are attached form an optionally substituted heterocyclic group. In other embodiments, each R is independently H, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group.

[0172] In other embodiments, R″ is H, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted alkyl group, an optionally substituted silyl group, or an optionally substituted siloxy group. In some embodiments, R″ is an optionally substituted alkyl group (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is -SiR′3, -SiR3, -Si(R′) a (OR) b , -Si(R) a (OR) b , -Si(R′) a (NR2) b , -Si(R) a (NR2) b , -Si(R′) a (OR) b (NR2)c ,-Si(R) a (OR) b (NR2) c , -O-SiR′3, -O-SiR3, -O-Si(R′) a (OR) b , -O-Si(R) a (OR) b , -O-Si(R′) a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R′) a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c , wherein each R′ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanoxy, isocyanato, cyano or isocyano, any of which may optionally be substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3 or a + b = 3 (if c is absent). In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0173] The precursor may include at least one R′ group attached to a silicon atom. In one embodiment, the precursor has the formula (R′)(H) 3-x Si(NR″2) x , where R′ and R″ can be any of those described herein, and where x is 1, 2, or 3. In another embodiment, the precursor has the formula (R′)(H)2Si(NR″2), where R′ and R″ can be any of those described herein. In one embodiment, the precursor has the formula (R′)(H)Si(NR″2)2, where R′ and R″ can be any of those described herein. In another embodiment, the precursor has the formula (R′)2(H)Si(NR″2), where R′ and R″ can be any of those described herein. In yet another embodiment, the precursor has the formula (R′)2Si(NR″2)2, where R′ and R″ can be any of those described herein. In one embodiment, the precursor has the formula (R′)3Si(NR″2), where R′ and R″ can be any of those described herein.

[0174] The precursor may not have an R′ group attached to the silicon atom. In one embodiment, the precursor has the formula (H) 4-x Si(NR″2) x , where each R″ may independently be any of those described herein, and where x is 1, 2, 3, or 4. In another embodiment, the precursor has the formula Si(NR″2) x , where each R″ may independently be any of those described herein. In a particular embodiment, each R″ is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0175] The precursor may include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has the formula (H)3Si(NR″2) or (H)2Si(NR″2)2 or (H)Si(NR″2)3, where each R″ may independently be any of those described herein. In a particular embodiment, each R″ is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may optionally be substituted.

[0176] The precursor may include a heterocyclic group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, where Het is an optionally substituted heterocyclic group including at least one nitrogen atom. In a particular embodiment, the precursor has the formula where the heterocyclic group may optionally be substituted (e.g., with any of the substituents described herein, such as substitution for an alkyl group), where n is 1, 2, 3, 4, or 5. In one embodiment, the formula has the formula R′3Si-Het, where Het is an optionally substituted heterocyclic group including at least one nitrogen atom, and each R′ may independently be any of those described herein. In a particular embodiment, the precursor has the formula where the heterocyclic group may optionally be substituted (e.g., with any of the substituents described herein, such as substitution for an alkyl group); each R′ may independently be any of those described herein; and where n is 1, 2, 3, 4, or 5.

[0177] In some instances, the precursor may have two or more silicon atoms, where the precursor may include an Si-Si bond. In a particular embodiment, the precursor has the formula (R″2N) x (R′) 3-x Si-Si(R′) 3-x (NR″2) x, wherein R′ and R″ can be any of those described herein. In one embodiment, the precursor has the formula (R″2N)(R′)2Si-Si(R′)2(NR″2), wherein R′ and R″ can be any of those described herein. In another embodiment, the precursor has the formula (R″2N)2(R′)Si-Si(R′)(NR″2)2, wherein R′ and R″ can be any of those described herein. In yet another embodiment, the precursor has the formula (R″2N)3Si-Si(NR″2)3, wherein each R″ can independently be any of those described herein.

[0178] The precursor can include different groups attached to the silicon atoms. In one example, the precursor has the formula (R″2N) x (R′) 3-x Si-SiH3, wherein R′ and R″ can be any of those described herein.

[0179] A linker can be present between the two silicon atoms. In one example, the precursor has the formula (R″2N) x (R′) 3-x Si-NR-Si(R′) 3-x (NR″2) x , wherein R′ and R″ can be any of those described herein, and wherein R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another example, the precursor has the formula (R″2N) x (H) 3-x Si-NR-Si(H) 3-x (NR″2) x , wherein R, R′ and R″ can be any of those described herein.

[0180] The precursor can include a combination of R′ groups and a linker having a heteroatom. In one example, the precursor has the formula (R′)3Si-NR-Si(R′)3, wherein R and R′ can be any of those described herein. In another example, the precursor has the formula (R′)3Si-L-Si(R′)3, wherein L and R′ can be any of those described herein. In a particular embodiment, L is an oxy group (—O—), an optionally substituted imino group (e.g., —NR—), or an optionally substituted silyl group (e.g., —SiR2—).

[0181] The precursor can include any useful combination of R′ and NR″2 groups in combination with two silicon atoms. In one example, the precursor has the formula (R″2N)(R′)2Si-L-Si(R′)2(NR″2) x , wherein L, R′ and R″ can be any of those described herein.

[0182] The precursor may include a heterocyclic group that includes silicon and nitrogen atoms. In one embodiment, the precursor has the formula wherein R′ and R″ can be any of those described herein, and wherein n is 1, 2, 3, or 4.

[0183] In another embodiment, the precursor has the formula wherein R′ and R″ can be any of those described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor has the formula wherein each R″ can independently be any of those described herein; and wherein n is 1, 2, 3, or 4. In another embodiment, the precursor has the formula wherein R′ and R″ can be any of those described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor has the formula wherein R″ can independently be any of those described herein; and wherein n is 1, 2, 3, or 4.

[0184] In any of the precursors herein, two R″s together with the nitrogen atoms to which they are attached can form an optionally substituted heterocyclic group.

[0185] The precursor may include any of the following, for example (R Ak )Si(NH2)(NR Ak 2)2, (R Ak )Si(NR Ak 2)3, (R Ak )2Si(NHR Ak 2)2, (R Ak )(H)Si(NHR Ak )2, (R Ak )3Si(NR Ak 2), (R Ak )3Si(NHR Ak ), H2Si(NHR Ak 2)2, (R Ak )(H)Si(NR Ak 2)2, HSi(NH2)(NR Ak 2)2, HSi(NR Ak 2)3, Si(NR Ak 2)4, (R′)(H)Si(NR″2)2, (R′)2Si(NR Ak 2)2, (R′)2Si(N[SiH3]2)2, (R′)2Si(N[SiR″3]2)2, or (R′)3Si(NHR Ak)。In some embodiments, each of R′ and R″ can independently be any of those described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In certain embodiments, R Ak is methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu), and the like.

[0186] Non-limiting examples of the precursors include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]); dimethylaminodimethylsilane (SiMe2H[NMe2]); dimethylaminotrimethylsilane (SiMe3[NMe2]); dimethylamino diethylsilane (SiHEt2[NMe2]); dimethylamino triethylsilane (SiEt3[NMe2]); ethylmethylamino dimethylsilane (SiHMe2[NMeEt]); ethylmethylamino trimethylsilane (SiMe3[NMeEt]); ethylmethylamino diethylsilane (SiHEt2[NMeEt]); ethylmethylamino triethylsilane (SiEt3[NMeEt]); diethylamino methylsilane (SiH2Me[NEt2]); diethylamino ethylsilane (SiH2Et[NEt2]); ethylamino trimethylsilane (SiMe3[NHEt]); diethylamino dimethylsilane (SiHMe2[NEt2]); diethylamino diethylsilane (SiHEt2[NEt2]); diethylamino trimethylsilane (SiMe3[NEt2]); diethylamino triethylsilane (SiEt3[NEt2]); isopropylamino dimethylsilane (SiHMe2[NHiPr]); isopropylamino trimethylsilane (SiMe3[NHiPr]); isopropylamino diethylsilane (SiHEt2[NHiPr]); isopropylamino triethylsilane (SiEt3[NHiPr]); diisopropylamino trimethylsilane (SiMe3[NiPr2]); diisopropylamino silane (SiH3[NiPr2], C6H 17NSi or DIPAS); diisopropylaminomethylsilane (SiH2Me[NiPr2]); diisopropylaminodimethylsilane (SiHMe2[NiPr2]); diisopropylaminodiethylsilane (SiHEt2[NiPr2]); diisopropylaminotriethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]); tert-butylaminodimethylsilane (SiHMe2[NHtBu]); tert-butylaminotrimethylsilane (SiMe3[NHtBu]); tert-butylaminodiethylsilane (SiHEt2[NHtBu]); tert-butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl); N-propylisopropylaminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N-ethylcyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], where Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], where Py is pyrrolyl); pyrrolidinyltrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolidinyl); piperidinyltrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], where Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], where Im is imidazolyl); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino)methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2);Bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); Bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2); Bis(diethylamino)silane (SiH2[NEt2]2, C8H; 22 N2Si or BDEAS); Bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); Bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); Bis(diethylamino)diethylsilane (SiEt2[NEt2]2); Bis(isopropylamino)dimethylsilane (SiMe2[NHiPr]2); Bis(isopropylamino)diethylsilane (SiEt2[NHiPr]2); Bis(isopropylamino)methylvinylsilane (SiMeVi[NHiPr]2); Bis(diisopropylamino)silane (SiH2[NiPr2]2); Bis(diisopropylamino)dimethylsilane (SiMe2[NiPr2]2); Bis(diisopropylamino)diethylsilane (SiEt2[NiPr2]2); Bis(diisopropylamino)methylvinylsilane (SiMeVi[NiPr2]2); Bis(methylamino)silane (SiH2[NHMe]2); Bis(sec-butylamino)silane (SiH2[NHsBu]2); Bis(sec-butylamino)methylsilane (SiHMe[NHsBu]2); Bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); Bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS); Bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); Bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2); Bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); Bis(1-imidazolyl)dimethylsilane (SiMe2[Im]2, where Im is the imidazolyl group); Tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS); Tris(dimethylamino)phenylsilane (SiPh[NMe2]3); Tris(dimethylamino)methylsilane (SiMe[NMe2]3); Tris(dimethylamino)ethylsilane (SiEt[NMe2]3); Tris(ethylmethylamino)silane (SiH[NEtMe]3); Tris(diethylamino)silane (SiH[NEt2]3); Tris(isopropylamino)silane (SiH[NHiPr]3, C9H 25N3Si or TIPAS); tris(dimethylamino)silylamide (Si[NMe2]3[NH2]); tetrakis(dimethylamino)silane (Si[NMe2]4); tetrakis(ethylmethylamino)silane (Si[NEtMe]4); tetrakis(diethylamino)silane (Si[NEt2]4); 1,2 - diethyl - tetrakis(diethylamino)disilane ([Et2N]2EtSi - SiEt[NEt2]2); 1,2 - dimethyl - tetrakis(dimethylamino)disilane ([Me2N]2MeSi - SiMe[NMe2]2); 1,2 - dimethyl - tetrakis(diethylamino)disilane ([Et2N]2MeSi - SiMe[NEt2]2); hexakis(methylamino)disilane ([MeHN]3Si - Si[NHMe]3); hexakis(ethylamino)disilane ([EtHN]3Si - Si[NHEt]3); hexakis(dimethylamino)disilazane (Me2N - Si[NMe2]2 - Si[NMe2]2 - NMe2) and analogs.

[0187] In some embodiments, the silane precursor is a halosilane precursor. A halosilane precursor is defined as a precursor having at least one halogen - containing atom and at least one silicon atom. Halogens include chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane precursor comprises a structure of formula (I): Si(X)4, wherein at least one X comprises a halogen atom.

[0188] For example, the halosilane is silicon tetrachloride or tetrachlorosilane (SiCl4). Another example of the chemical formula of a halosilane is Si n X y H z , where X is a halogen, H is hydrogen; n is an integer greater than or equal to 1 and equal to the number of Si atoms in the molecule; in some embodiments, y is from about 1 to about 4, and z is 4 - y. Other examples include, but are not limited to, SiHCl3, SiH2Cl2, and SiH3Cl.

[0189] Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes, and fluorosilanes. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane (DCS), monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert - butylchlorosilane, di - tert - butylchlorosilane, chloroisopropylsilane, chlorosecond - butylsilane, tert - butyldimethylchlorosilane, hexyldimethylchlorosilane, hexachloroethylsilane (HCDS), and analogs.

[0190] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is an organosilicon-containing precursor.

[0191] In some embodiments, the halosilane precursor (e.g., in formula (I)) has at least one optionally substituted C 1-2 haloalkyl. Non-limiting haloaliphatic groups include -CX y H 3-y , where y is 1, 2 or 3, where each X is independently a halogen (F, Cl, Br or I); -CX z H 2-z CX y H 3-y , where z is 0, 1 or 2, where y is 0, 1, 2 or 3, where each X is independently a halogen (F, Cl, Br or I), where at least one of z or y is not 0; or -CH2CX y H 3-y , where y is 1, 2 or 3, where each X is independently a halogen (F, Cl, Br or I). Other non-limiting haloalkyls include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI) and the like. In certain embodiments, the C 1-2 haloalkyl includes β-haloethyl. Still other haloaliphatic groups include C 1-4 haloalkyl, C 2-4 haloalkenyl and C 2-4 haloalkynyl.

[0192] In addition to the silicon-containing precursor, the processing region above the substrate may include a plasma species, such as one or more radical species, which may be in a substantially low energy state. One or more radicals may include hydrogen radicals, nitrogen radicals, oxygen radicals, amine radicals, carbon radicals, or combinations thereof. Radicals may also be referred to as atomic radicals or radical species. For example, a hydrogen radical may also be referred to as a hydrogen atom radical or a hydrogen radical species. In some embodiments, all or substantially all or most of the hydrogen atom radicals may be in the ground state. For example, at least about 90% or 95% of the hydrogen atom radicals adjacent to the substrate may be in the ground state.

[0193] Radicals can be generated in a plasma source and introduced into the processing chamber. In some embodiments, when an excited hydrogen atom radical loses its energy or relaxes, the excited hydrogen atom radical can become a hydrogen atom radical in a substantially low energy state or a ground state hydrogen atom radical. Hydrogen atom radicals in a substantially low energy state or in the ground state are capable of breaking Si-H and / or Si-Si bonds and generally preserving Si-O, Si-N, and / or Si-C bonds. In some implementations, the processing conditions can be provided such that the excited hydrogen atom radicals lose energy or relax to form hydrogen atom radicals in a substantially low energy state or in the ground state.

[0194] The source gases of the silicon-containing precursor and hydrogen radicals can be delivered together with other substances (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 significantly greater than the concentration of the source gas. As used herein, "significantly greater" with respect to the concentration of the carrier gas relative to the source gas can mean at least three times greater in volume percentage. As an example, hydrogen gas can be provided at a hydrogen concentration of about 1% to about 50% in a helium carrier gas. The presence of the carrier gas helps to increase the ionization of the source gas and reduce recombination. Although 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 the carrier gas (such as helium) flows with the source gas, most of the radicals can be generated with minimal recombination. Higher pressures in the processing chamber during deposition can improve the conformality of the silicon-containing layer. Higher pressures in the processing 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.

[0195] In operation 130, a portion of the silicon-containing layer is exposed to an oxygen-containing material to form a silicon oxide-containing portion of the silicon-containing layer. In some embodiments, the exposed surface of the silicon-containing layer is exposed to the oxygen-containing material. Examples of the oxygen-containing material include oxygen-containing gases such as ozone, oxygen, hydrogen peroxide, oxygen-containing radicals, their plasmas, or mixtures thereof. The oxygen-containing radicals may include oxygen-containing materials generated by a plasma. In one example, ozone, oxygen, or hydrogen peroxide may be provided by one or more gases supplied to the processing chamber. In another example, the oxygen radicals may be provided by a remote plasma (such as an oxygen plasma) generated in a remote plasma source (separate from the processing chamber). In some embodiments, the remote plasma source may be used to generate an oxygen plasma. In another example, the oxygen radicals may be generated in the processing chamber that houses the substrate, such as in the processing region above the substrate.

[0196] The oxygen-containing material may adsorb onto the silicon-containing layer in the recessed feature. Once adsorbed, the oxygen-containing material may diffuse into the silicon-containing layer. The diffusion of the oxygen-containing material may occur in any direction. In some examples, when the oxygen-containing material is provided from above the feature (e.g., provided from a remote plasma source located upstream of the processing chamber, where the exposed surface of the substrate including the feature faces the showerhead above the substrate and the plasma material is delivered through the showerhead), at least a portion of the oxygen-containing material may be received by the top surface of the recessed feature and may diffuse in a downward direction toward the substrate surface, while some of the oxygen-containing material may diffuse in a horizontal direction, or may diffuse in any direction in which the oxygen-containing material enters the silicon-containing layer. The diffusion of the oxygen-containing material may continue until a point of penetration depth is reached. The penetration depth may vary according to the processing parameters. A key parameter may be the chamber pressure during the oxidation step in operation 130. In some embodiments, the chamber pressure during the partial oxidation of the silicon-containing layer may be about 0.02 to about 20 Torr, or about 0.02 to about 10 Torr, or about 0.03 to about 10 Torr, or about 1 to about 20 Torr, or about 0.5 to about 5 Torr. The penetration depth may also depend on the period of time that the silicon-containing layer is exposed to the oxygen-containing material. For example, the oxygen-containing material may diffuse in a downward direction, and a deeper penetration depth may be achieved when the exposure is performed with a longer exposure time. The penetration depth may also depend on the composition of the silicon-containing layer or the substrate temperature.

[0197] In some embodiments, the penetration depth of the oxygen-containing material may be on the nanometer scale. For example, the penetration depth may be a few nanometers, or more than 10 nm. The amount (or density) of the oxygen-containing material in the silicon-containing layer may be proportional to the period of time that the silicon-containing layer is exposed to the oxygen-containing material.

[0198] The penetration depth of the oxygen-containing material may be from about 1% to about 50%, or about 1% to about 40%, or about 1% to about 30%, or about 1% to about 20%, or about 1% to about 10%, or about 1% to about 5% of the depth starting from the top of the feature.

[0199] In some embodiments, the carbon element in the silicon-containing layer can be replaced by an oxygen-containing substance. For example, the carbon element in the Si-C bond in the silicon-containing layer can be replaced by an oxygen-containing substance (such as oxygen radicals in an oxygen plasma), thereby forming an Si-O bond. This oxidation reaction can form a silicon-oxide-containing portion that contains silicon oxide. The silicon-oxide-containing portion refers to the oxidized portion in the silicon-containing layer. The silicon-oxide-containing portion (i.e., the oxidized portion) can at least include a silicon component and an oxygen component that are chemically bonded to each other, forming one or more Si-O bonds, and can have the chemical formula Si x O y , where x≥1 and y≥1. Relative to the deposited silicon-containing layer, the silicon-oxide-containing portion (i.e., the oxidized portion) may be substantially carbon-deficient or have a significantly reduced carbon content. For example, after being exposed to and oxidized by oxygen radicals, the silicon-oxide-containing portion can have a carbon-deficient or substantially carbon-deficient composition. In one example, about 10% to about 40% of the carbon element in the Si-C bond in the oxidized portion can be replaced by oxygen. In some embodiments, a silicon carbon oxide layer can be deposited in a recessed feature. In some embodiments, hydrogen can be incorporated into the silicon carbon oxide during deposition. The silicon carbon oxide can include undoped and doped silicon carbon oxides, and the doped silicon carbon oxide can include hydrogenated silicon carbon oxide. After the silicon carbon oxide is exposed to and oxidized by oxygen radicals in an oxygen plasma, the silicon carbon oxide can include a silicon-oxide-containing portion that contains silicon oxide (e.g., the silicon-oxide-containing portion) or a silicon carbon oxide that has a significantly lower carbon content relative to the deposited silicon carbon oxide.

[0200] In some embodiments, an oxygen-containing substance can be provided through the top surface of the feature. For a silicon-containing layer deposited at or near the top surface of the feature, the distribution of the oxygen-containing substance may be large and may decrease as the depth drops to the penetration depth. Beyond this penetration depth, the amount of the oxygen-containing substance can drop to zero or be substantially zero. In one example, the silicon carbon oxide deposited on the recessed surfaces (e.g., the upper sidewall and the lower sidewall) in a trench can be exposed to the oxygen-containing substance. After oxidation, the silicon carbon oxide on the top surface and the upper sidewall may lose carbon and its composition can change to silicon oxide. The silicon-containing layer deposited on the lower sidewall and / or the bottom surface in the trench may not be oxidized.

[0201] In operation 140, the silicon oxide portion from operation 130 can be etched from the silicon-containing layer. In some embodiments, operation 140 can result in the formation of a partially etched silicon-containing layer. A partially etched silicon-containing layer refers to a silicon-containing layer that has undergone at least one oxidation and etching operation. A partially etched silicon-containing layer is a silicon-containing layer that does not have an oxygen-containing substance, and thus will not be removed by one or more etching chemicals such as hydrogen fluoride in subsequent etching operations. A partially etched silicon-containing layer can be a silicon-containing layer outside the penetration depth, and thus is not oxidized or does not have a silicon-oxygen bond. A partially etched silicon-containing layer can be located at the lower sidewall or bottom surface of a recessed feature, where the oxygen-containing substance is introduced from a showerhead above the substrate. On the other hand, depending on the conditions for introducing the oxygen-containing substance into the recessed feature, a partially etched silicon-containing layer can also be formed on the top surface or upper sidewall surface of the recessed feature. A partially etched silicon-containing layer can refer to a partially filled gap (e.g., a trench or a hole or a via) in one or more features. A fully filled feature or a feature with a fully filled gap can refer to a feature where the level of the silicon-containing layer in the gap (e.g., a trench or a hole or a via) is similar to or higher than the top surface level of the feature. A fully filled feature can have no voids and thus is dense. In some embodiments, depending on the deposition parameters and / or deposition manner, a fully filled feature can include one or more voids formed in the gap filling material (e.g., a silicon-containing material).

[0202] During etching, any suitable etchant can be used. In some embodiments, hydrogen fluoride (HF) or other etching reactants can be used as the etching chemical. A silicon-containing layer (e.g., SiOC) or ruthenium can be resistant to HF etching. The etching chemical can be configured to selectively etch silicon oxide without significantly reacting with other adjacent materials. For example, the etching selectivity with respect to silicon nitride can be further increased by adding an amine. After a substrate including a silicon-containing layer is exposed to an oxygen-containing substance, it can be immersed in a diluted HF solution to etch the silicon oxide portion. Other portions of the silicon-containing layer that are not exposed to the oxygen-containing substance can not be etched by hydrogen fluoride or other etching reactants. The diluted HF solution can be provided in vapor form at an elevated temperature to etch the silicon oxide portion of the silicon-containing layer in the gas phase. The diluted HF solution can be atomized to etch the silicon oxide portion of the silicon-containing layer. Vaporized or atomized HF can be diluted to a concentration suitable for etching the silicon oxide portion in the silicon-containing layer. In some embodiments, silicon tetrafluoride (SiF4) may be produced, which is a reaction byproduct of the reaction of hydrogen fluoride with silicon oxide. Other etching reactants can include nitrogen trifluoride (NF3), tetrafluoromethane (CF4), trifluoromethane (CHF3), difluoromethane (CH2F2), fluoromethane (CH3F), hexafluoride (C2F6), octafluoropropane (C3F8), octafluorocyclobutane (C4F8), hexafluorocyclobutene (C4F6), 1,2,3,3,4-pentafluorocyclobuten-4-yl radical (C4F5) or a mixture thereof.

[0203] During this operation, an oxidized silicon-containing layer (also referred to as a silicon oxide-containing portion) on the top surface and / or upper sidewalls can be etched away, while the deposited silicon-containing layer that is not exposed to or penetrated by the oxygen-containing substance can be retained on the lower sidewalls and / or bottom surface without significant compositional change, thereby forming a partially etched silicon-containing layer at the lower sidewalls and / or bottom surface of the feature. The partially etched silicon-containing layer can have the same composition as the deposited silicon-containing layer. In some embodiments, the partially etched silicon-containing layer after etching can be a conformal layer.

[0204] Operations 120-140 can be repeated one or more times to achieve the desired deposition characteristics. In some embodiments, operations 120-140 are repeated to control the deposition of the silicon-containing layer (or silicon-containing material) in the recessed features that can be filled with the silicon-containing material. By repeating the cycle that includes operations 120-140, the gap filling process can be advanced until the gap filling process of filling the feature or gap with the silicon-containing material is completed. The progress of the gap filling process can be determined by monitoring the level of the silicon-containing layer at the end of each cycle. As the cycle progresses, the level of the silicon-containing layer measured from the bottom of the feature may increase. After a predetermined number of cycles, this level can be substantially the same as or higher than the feature height, at which point the gap filling can be considered complete. Here, the "level" of the silicon-containing layer can refer to the thickness of the silicon-containing layer after etching the silicon-containing layer in the recessed feature. The thickness of the silicon-containing layer can be the distance between the bottom of the feature and the lowest point of the silicon-containing layer within the gap (or volume) of the feature.

[0205] Returning to the cycle of repeating the gap filling process, after forming the partially etched silicon-containing layer in operation 140 of the first cycle, the silicon-containing layer can be conformally deposited in the feature in operation 120 of the second cycle. For example, the silicon-containing layer can be deposited on the top surface and upper sidewalls where the silicon-containing layer was deposited and etched in the recessed feature in the first cycle. The silicon-containing layer can also be deposited above the top of the partially etched silicon-containing layer formed in operation 140 of the first cycle, thereby increasing the level of the layer filling the gap in the trench. The silicon-containing layer deposited in operation 120 of the second cycle can be conformal and can be free of seams and / or voids. In some embodiments, the silicon-containing layer in the second cycle may not be completely conformal. For example, in some embodiments, one or more seams and / or voids may remain in the silicon-containing material after the gap filling is completed. The chemical composition of the silicon-containing layer deposited in operation 120 of the second cycle can be the same as or substantially the same as the chemical composition of the partially etched silicon-containing layer formed in operation 140 of the first cycle. In operation 130, an oxygen-containing substance can be provided to the silicon-containing layer, which can replace the carbon element in the Si-C bond in the silicon-containing layer with oxygen, thereby forming a silicon oxide with Si-O bonds. In some embodiments, this oxidation reaction can be limited to the silicon-containing layer exposed to the oxygen-containing substance.

[0206] The penetration depth in operation 130 can control the process of gap filling. In some embodiments, the penetration depth in operation 130 of the second cycle can be configured to be shorter than that in the first cycle. Thus, the distance that the oxygen-containing material diffuses downward from the top surface of the feature can also be shorter than that in the first cycle. The silicon-containing layer below the penetration depth may not be oxidized and thus may not be etched in operation 140. After operation 140, the level of the remaining silicon-containing layer can be higher than that after the first cycle, thereby advancing the gap filling. The etching conditions in operation 140 of the second cycle can be substantially similar to those in the first cycle. For example, HF or other etching reactants in liquid or vapor (or atomized) form can selectively etch the silicon-containing oxide portion relative to other materials on the substrate. Other etching reactants can include nitrogen trifluoride (NF3), tetrafluoromethane (CF4), trifluoromethane (CHF3), difluoromethane (CH2F2), fluoromethane (CH3F), carbon hexafluoride (C2F6), octafluoropropane (C3F8), octafluorocyclobutane (C4F8), hexafluorocyclobutene (C4F6), 1,2,3,3,4-pentafluorocyclobuten-4-yl radical (C4F5), or a mixture thereof. Operations 120-140 can be repeated until the gap filling advances to the top surface of the feature in operation 150. In some embodiments, operations 120-140 can be repeated until the silicon-containing layer can fill the gap above the top surface of the feature. Any excess silicon-containing layer above the top surface can be removed by chemical mechanical planarization (CMP).

[0207] Figures 2A - 2D A cross-sectional schematic diagram for gap filling of a feature of an exemplary substrate according to some embodiments. The operations of gap filling can include additional, fewer, or different operations compared to Figures 2A - 2D those shown. Figure 2A An example of a feature 200 of a semiconductor substrate is shown, where a trench (or hole or volume or gap) 204 formed between adjacent structures 206 includes sidewalls 208 (including upper sidewall 224 and lower sidewall 226), a bottom surface 210, and a top surface 212. The structures 206 can be an array of metal lines. In some embodiments, the structures 206 can include ruthenium (Ru). The Ru structures can be deposited by any suitable method, such as by CVD, ALD, or physical vapor deposition (PVD), such as sputter deposition. In some embodiments, one or more additional layers can be formed on the structures 206 to form the top surface 212. The one or more layers can include a nitride hard mask 214. The nitride hard mask 214 can be formed by PECVD. In some embodiments, depending on the device application, the pitch of the feature 200 can be about 20 nm, and the gap can be about 10 nm or less. The height of the feature 200 can be about 30 to about 200 nm, or about 50 to about 200 nm.

[0208] Figure 2BShows a silicon-containing layer 220 formed in feature 200. The silicon-containing layer 220 can be formed along the top surface 212, sidewalls 208, and bottom surface 210 in trench 204 by any suitable deposition technique (such as CVD, PECVD, ALD, or PEALD). In one example, the silicon-containing layer 220 can be silicon carbide, silicon carbon oxide, hydrogenated silicon carbon oxide (SiCOH), or silicon carbon oxynitride. The silicon-containing layer 220 can be a conformal layer with high step coverage. The thickness of the silicon-containing layer 220 deposited in the recessed feature 200 can be about 0.3 to about 5 nm, or about 0.5 to about 4 nm, or about 0.7 to about 3 nm.

[0209] Figure 2C Shows that a portion of the silicon-containing layer is oxidized after being exposed to an oxygen-containing substance. The oxygen-containing substance can include oxygen, ozone, hydrogen peroxide, their plasmas, oxygen-containing radicals (which can be generated by their plasmas), or mixtures thereof. In one example, oxygen radicals can be generated by an oxygen plasma. In one example, the oxygen plasma can be formed in a remote plasma source located upstream of the processing chamber and can be provided to the semiconductor substrate in a downward direction through a showerhead. Oxygen, ozone, or hydrogen peroxide can be provided by one or more gas supply sources or atomizers fluidly connected to the processing chamber and can be adsorbed on the recessed feature surface and other surfaces on the semiconductor substrate. During exposure to the oxygen-containing substance, the oxygen-containing substance can diffuse into the silicon-containing layer 220. The oxygen-containing substance can diffuse in any direction. Some oxygen-containing substances can diffuse a certain distance in a downward direction towards the bottom 210 of feature 200, i.e., the penetration depth. The oxygen-containing substance in the silicon-containing layer 220 can react with the carbon element in the Si-C bonds in the silicon-containing layer 220. In some embodiments, the carbon element in Si-C can be replaced by the oxygen-containing substance to form a silicon-containing oxide portion 222 including Si-O bonds. Carbon can be removed from the silicon-containing layer 220 during exposure. The silicon-containing oxide portion 222 can be the portion of the silicon-containing layer that is exposed to the oxygen-containing substance. In one example, the silicon-containing oxide portion 222 can be formed on the top surface 212 and / or upper sidewalls 224, where the carbon element in the Si-C bonds is replaced by the oxygen-containing substance. The silicon-containing oxide portion 222 can include silicon oxide.

[0210] The silicon-containing layer 220 formed on the lower sidewalls 226 and / or bottom surface 210 may not be exposed to the oxygen-containing substance and may not be oxidized. The composition of the silicon-containing layer 220 can be the same as that of the freshly deposited silicon-containing layer 220. The penetration depth of the oxygen-containing substance can control the depth of the oxidized silicon-containing layer. An extended penetration depth can increase the volume of the subsequently etched oxidized silicon-containing layer and reduce the volume of the deposited silicon-containing layer. A reduced penetration depth can reduce the volume of the oxidized silicon-containing layer and increase the volume of the deposited silicon-containing layer. For example, the penetration depth can be configured to be higher than the level 216 of the silicon-containing layer in feature 200. It should be understood, Figure 2CIt is only a schematic diagram for distinguishing the silicon oxide-containing part 222 from the unoxidized (i.e., just deposited) silicon-containing layer 220, and the profile of the penetration depth (shown as the boundary line 230 between the silicon oxide-containing part 222 and the unoxidized silicon-containing layer 220) can be unrestricted. For example, the boundary line 230 may not be limited to an arc shape. The boundary line 230 may be, for example, conical.

[0211] Figure 2D Shows a partially etched silicon-containing layer in a recessed feature after an etching operation. After oxidation as Figure 2C shown, the silicon oxide-containing part 222 in the silicon-containing layer can be selectively etched relative to other adjacent materials (e.g., ruthenium 206, unoxidized silicon-containing layer (e.g., silicon carbon oxide) 220, or nitride hard mask 214). This selective etching can result in the formation of a silicon-containing layer 220 that is not exposed to oxygen-containing substances and thus is not oxidized. After the etching operation, the composition of the silicon-containing layer 220 can remain the same as that at the time of deposition. The selective etching can be performed by immersing the feature 200 in a dilute HF solution or spraying the dilute HF solution onto the substrate at atmospheric temperature or elevated temperature.

[0212] Figures 3A - 3D Is a cross-sectional schematic diagram of a feature of an exemplary substrate according to some embodiments after a second or any gap filling after a first gap filling. For example, Figures 3A - 3D Shows gap filling of a feature in which at least one silicon-containing layer has been formed. Compared with Figures 3A - 3D shown, the operation of gap filling can include additional, fewer, or different operations.

[0213] Figure 3A Shows that the feature 300 includes a first partially etched silicon-containing layer 320 formed before depositing the silicon-containing layer 340. It should be understood that the depth and profile of the silicon-containing layer 320 can be non-limiting. The first partially etched silicon-containing layer 320 can be formed on the lower surface 310 and the lower surface 326 having a level 330. The silicon-containing layer 340 can be deposited in the recessed feature 300. For example, the silicon-containing layer 340 can be deposited on the upper sidewall 324, the top surface 512, and the first partially etched silicon-containing layer 320, thus filling the gap and increasing the level of the silicon-containing layer in the gap relative to the existing gap filling. The composition of the silicon-containing layer 320 can be the same as that of the silicon-containing layer 340. The silicon-containing layer 340 can be conformally deposited in the recessed feature 300 without forming seams and / or voids.

[0214] The silicon-containing layer 340 can be deposited in the recessed feature using any suitable deposition technique (such as CVD, PECVD, ALD, PEALD, or other techniques). The first partially etched silicon-containing layer 320 can be or include silicon carbon oxide, silicon carbon oxide with hydrogen (SiCOH), silicon nitride oxide, or silicon carbon nitride oxide. In some embodiments, the composition of the silicon-containing layer 340 can be the same as that of the partially etched silicon-containing layer 320.

[0215] In Figure 3B , Figure 3A the silicon-containing layer 340 in can be exposed to an oxygen-containing substance to at least partially oxidize the silicon-containing layer 340. In some embodiments, the oxygen-containing substance can be oxygen, ozone, hydrogen peroxide, oxygen-containing free radicals, their plasmas, or a mixture thereof. In some embodiments, the penetration depth of the oxygen-containing substance from the top surface of the feature 300 can be adjusted to be shorter than the penetration depth of the first partially etched silicon-containing layer 320. For example, the penetration depth can be configured such that Figure 3B the oxygen-containing substance in does not diffuse below the level 350. In this example, the oxidation reaction can be limited to the portion near or above the level 350, resulting in the silicon-containing oxide portion 360. The silicon-containing oxide portion 360 can include the silicon-containing layer formed on the upper sidewall 324 and the top surface 512. The silicon-containing layer 340 outside the penetration depth is not exposed to the oxygen-containing substance and thus is not oxidized. The composition of the silicon-containing layer 340 can remain unchanged and can be the same as the composition when it was just deposited.

[0216] Figure 3C The second partially etched silicon-containing layer 370 after etching the silicon-containing oxide portion 360 is shown. The second partially etched silicon-containing layer 370 can include the first partially etched silicon-containing layer 320 and the non-oxidized silicon-containing layer 340. In some embodiments, after the etching operation, the level 350 of the second partially etched silicon-containing layer 370 is higher than the level 330 of the first partially etched silicon-containing layer 320, thereby advancing the gap filling. The etching conditions for the silicon-containing oxide portion 360 can be substantially similar to the etching conditions used to form the first partially etched silicon-containing layer 320.

[0217] In some embodiments, the gap filling cycle including deposition, oxidation, and etching (such as Figures 2B - 2D shown in and / or 3A - 3C) can be repeated until the gap filling is completed. In some embodiments, when the level of the silicon-containing layer is substantially approximate to or higher than the level of the nitride hard mask 514, the gap filling of the recessed feature can be completed. Figure 3D A cross-sectional schematic diagram of the feature with the gap filling completed after repeating the gap filling cycle multiple times according to some embodiments is shown. In each cycle, the conformal deposition of the silicon-containing layer can result in gap filling without forming seams and / or voids. The silicon-containing layer formed in each gap filling cycle can have the same composition.

[0218] The number of gap fill cycles can depend on deposition parameters, including deposition precursors, reactant ions and / or radicals, by-products, and / or parameters that control the depth of penetration. For example, an extended depth of penetration of an oxygen-containing species can increase the volume of the silicon-containing oxide portion that is subsequently etched. This condition will etch the silicon-containing layer to a deep depth and may involve increasing the number of gap fill cycles including deposition, oxidation, and etching before the gap fill is complete. Reducing the depth of penetration can also reduce the volume of the silicon-containing layer exposed to the oxygen-containing species. This will etch the silicon-containing layer to a shallower depth.

[0219] After repeating the gap fill cycles, an excess silicon-containing layer may form above the top surface 512 of the feature 300. In some embodiments, the silicon-containing layer 370 can fill the gap and cover the top surface 512 of the feature 300, as Figure 3D shown. This excess silicon-containing layer may constitute a capping layer. The excess silicon-containing layer above the top surface of the feature 300 can be removed by CMP processing to control the height of the silicon-containing layer relative to the silicon nitride hard mask 114. The number of cycles to completely fill the feature can depend on the pitch of the trenches, the gap width and / or depth, the silicon-containing layer composition, the chamber pressure, or the like. For example, the gap fill cycles including silicon-containing layer deposition, oxidation, and etching can be repeated about 3 to about 15 times, or about 4 to about 12 times, or about 5 to about 10 times to conformally fill a feature having a gap of about 10 nm and a depth of about 100 nm.

[0220] Figures 4A - 4D A cross-sectional schematic diagram of gap filling for a feature of an exemplary substrate according to some embodiments. Figures 4A - 4D Shows a gap fill process based on at least one or more non-conformal depositions of a silicon-containing layer in a recessed feature. Figures 4A - 4D The gap fill process shown in can begin with receiving a substrate including a feature, where at least one silicon-containing layer is conformally deposited, oxidized, and etched to have a partially etched silicon-containing layer 410 having a level 420 according to some embodiments. It should be understood that the depth and profile of the silicon-containing layer 410 can be non-limiting.

[0221] Figure 4A Shows the formation of a non-conformal silicon-containing layer in a recessed feature. In some embodiments, the silicon-containing layer 430 can be deposited on the top surface 412 and sidewalls 408 (including upper sidewall 424 and lower sidewall 426) in the feature 400. The silicon-containing layer 430 can also be deposited on the first partially etched silicon-containing layer 410 having a level 420 in the feature 400, as Figure 4AAs shown. During the deposition of the silicon-containing layer 430, mass transport limitations may result in "bread-loafing" (or "pinched off") deposition, which presents a thicker deposition at the top surface 412 and a thinner deposition at the recessed surfaces such as the sidewalls 408. This may cause the top of the feature opening to close before the feature is completely filled.

[0222] In another embodiment, the silicon-containing layer 430 may be deposited without closing the top of the feature opening. Instead, a thicker deposition at the top surface 412 and a thinner deposition at the recessed surfaces may be obtained.

[0223] The deposition may be carried out by ALD. Different from CVD processing, ALD processing utilizes surface-mediated deposition reactions to deposit films in a layer-by-layer manner, and such films can generally be conformal. On the other hand, although ALD can deposit highly conformal films, it may be difficult to deposit films in high aspect ratio features. The step coverage and uniformity of the film along the sidewalls depend on, for example, the transport of deposition precursors, reactant ions, and / or radicals, as well as by-products. As the lateral dimensions of the feature narrow, the transport and diffusion of deposition precursors and any reactant species in the feature gradually become more difficult. Therefore, due to diffusion limitations, the top of the feature is exposed to more precursor and reactant species, while the bottom of the feature is exposed to fewer precursor and reactant species. This may result in the formation of seams and / or voids in high aspect ratio features. In some embodiments, the silicon-containing layer 430 may be deposited to intentionally form voids 440 within the gap filling material in the recessed feature, as Figure 4A shown.

[0224] Figure 4B shows the silicon-containing layer in the feature 400 being exposed to an oxygen-containing species. The oxygen-containing species may adsorb on the silicon-containing layer 430 and diffuse through the silicon-containing layer 430. When the oxygen-containing species are provided from above the feature 400, the silicon-containing layer formed on the top surface 412 and floating above and filling the gap inlet may be oxidized, thus forming a silicon-containing oxide portion 450. In some embodiments, the penetration depth of the oxygen-containing species may be controlled such that the oxygen-containing species can diffuse to a position between the top 460 and the bottom 470 of the void 440. Figure 4B shows that the penetration depth (which is shown by the boundary line 474 between the silicon-containing oxide portion 450 and the silicon-containing layer 430) is closer to the top 460 than to the bottom 470 of the void 440. Figure 4B shows that the silicon-containing layer 430 is not exposed to the oxygen-containing species and thus is not oxidized. The composition of the silicon-containing layer 430 may not be changed by the oxidation reaction.

[0225] Figure 4C shows a second partially etched silicon-containing layer 480 after etching the silicon-containing oxide portion 450. The silicon-containing oxide portion 450 ( Figure 4B(China) by etching with a diluted HF solution as described herein. After etching, the resulting feature 400 may have a silicon-containing layer 480, which includes a first partially etched silicon-containing layer 410 and a silicon-containing layer 430 that is not oxidized by an oxygen-containing substance. In some embodiments, the composition of the silicon-containing layer 430 is the same as or substantially the same as that of the first partially etched silicon-containing layer 410. In some embodiments, the composition of the silicon-containing layer 430 can be configured to be different from that of the first partially etched silicon-containing layer 410 to change the dielectric properties of the gap-fill material. In some embodiments, the silicon-containing layer 480 may be non-conformal. In some embodiments, the upper sidewalls may have a thicker silicon-containing layer, while the lower sidewalls may have a thinner layer.

[0226] A gap-fill cycle including deposition, exposure, and etching operations (e.g., operations as Figures 4A - 4C shown) can be repeated one or more times. The number of gap-fill cycles can depend on deposition parameters, including deposition precursors, reactant ions and / or radicals, by-products, and / or parameters controlling the penetration depth. For example, an extended penetration depth of the oxygen-containing substance can increase the volume of the silicon-containing oxide portion subsequently etched. This condition will etch the silicon-containing layer to a deep depth and may result in an increased number of gap-fill cycles including deposition, oxidation, and etching before gap filling is completed. Reducing the penetration depth can also reduce the volume of the silicon-containing layer exposed to the oxygen-containing substance and can etch the silicon-containing layer to a shallower depth.

[0227] Figure 4D Shows a cross-sectional view of a feature after repeating a cycle of performing deposition, exposure, and etching operations (e.g., operations as Figures 4A - 4C shown). For example, the silicon-containing layer can be formed non-conformally. The feature opening can have a thicker layer, while the sidewalls of the feature can have a thinner layer. After the feature opening is closed, the silicon-containing layer 480 (i.e., the gap-fill material having the same composition as the silicon-containing layer) can include voids 444. In some embodiments where voids 444 are formed after depositing the silicon-containing layer 430 (as Figure 4A shown), the voids 444 can be formed to be smaller than the voids 400. In some embodiments, processing parameters can be controlled to form seams and / or voids below the top level of adjacent structures 406. Any excess silicon-containing layer formed above the nitride mask 414 can be removed by CMP to make the silicon-containing layer flat relative to the top of the nitride mask 414. Figures 4A - 4D The embodiments shown can have the advantage of generally reducing the number of gap-fill cycles or controlling (e.g., reducing) the dielectric constant of the silicon-containing layer 480 in the gaps formed between adjacent structures 406. Device

[0228] Figure 5Schematic illustrations of embodiments of an atomic layer deposition (ALD) processing station 500 are presented, which has a processing chamber 502 for maintaining a low-pressure environment. A plurality of ALD processing stations 500 may be included in a common low-pressure processing tool environment. For example, Figure 5 Embodiments of a multi-station processing tool 500 are presented. In some embodiments, one or more hardware parameters of the ALD processing station 500 (including those discussed in detail below) may be programmatically adjusted by one or more computer controllers 550.

[0229] The ALD processing station 500 is in fluid communication with a reactant delivery system 501 to deliver processing gases to a showerhead 506. The reactant delivery system 501 includes a mixing vessel 504 for mixing and / or conditioning the processing gases, such as a silicon-containing precursor gas, a nitrogen-containing species, an oxygen-containing species, a carbon-containing species, or a hydrogen-containing species, for delivery to the showerhead 506. The oxygen-containing species may include oxygen (O2), ozone (O3), hydrogen peroxide, carbon monoxide (CO), carbon dioxide (CO2), nitrogen dioxide (NO2), nitrous oxide (N2O), or a mixture thereof. The carbon-containing species may include acetylene (C2H2), ethylene (C2H4), propylene (C3H6), or a mixture thereof. The hydrogen-containing species may include hydrogen (H2), methane (CH4), ethane (C2H6), or a mixture thereof. The nitrogen-containing species may include nitrogen (N2), ammonia (NH3), diazene (N2H2), or hydrazine (N2H4), or a mixture thereof. One or more mixing vessel inlet valves 520 may control the introduction of the processing gases into the mixing vessel 504. One or more valves 505 may control the introduction of the gases into the showerhead 506.

[0230] As an example, Figure 5 embodiments include a vaporization point 503 for vaporizing liquid reactants to be supplied to the mixing vessel 504. In some embodiments, the vaporization point 503 may be a heated vaporizer. The saturated reactant vapor generated by the vaporizer may condense in downstream delivery pipes. Exposure of incompatible gases to the condensed reactants may generate small particles. These small particles may clog the pipes, impede valve operation, contaminate the substrate, etc. Some methods for addressing these issues include purging and / or evacuating the delivery pipes to remove residual reactants. However, purging the delivery pipes may increase the cycle time of the processing station, thereby reducing the throughput of the processing station. Thus, in some embodiments, the delivery pipes downstream of the vaporization point 503 may be heat traced. In some examples, the mixing vessel 504 may also be heat traced. In one non-limiting example, the pipes downstream of the vaporization point 503 to the mixing vessel 304 have a temperature profile that extends from about 40°C to about -55°C or from about 60°C to about 65°C.

[0231] In some embodiments, a liquid precursor or liquid reactant may be vaporized in a liquid injector. For example, the liquid injector may inject pulses of the liquid reactant into a carrier gas stream upstream of a mixing vessel. In one embodiment, the liquid ejector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, the liquid injector may atomize the liquid into dispersed microdroplets, which are then vaporized in a heated delivery tube. Smaller droplets may vaporize faster than larger droplets, thereby reducing the delay between liquid injection and complete vaporization. Faster vaporization may reduce the length of the tube downstream of the vaporization point 503. In one case, the liquid injector may be mounted directly to the mixing vessel 504. In another case, the liquid injector may be mounted directly to the showerhead 506.

[0232] In some embodiments, a liquid flow controller (LFC) may be provided upstream of the vaporization point 503 to control the mass flow rate of the liquid for vaporization and delivery to the ALD processing station 500. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. Next, the piston valve of the LFC may be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize the liquid flow using feedback control, which may extend the time for liquid reactant dosing. Thus, in some embodiments, the LFC may dynamically switch between a feedback control mode and a direct control mode. In some embodiments, this may be performed by deactivating the sensing tube of the LFC and the PID controller.

[0233] The showerhead 506 distributes a processing gas to the substrate 512. In Figure 5 the embodiment shown, the substrate 512 is located below the showerhead 506 and is shown resting on a pedestal 508. The showerhead 506 may have any suitable shape and may have any suitable number and configuration of ports for distributing the processing gas to the substrate 512.

[0234] In some embodiments, a microvolume 507 is located below the showerhead X106. Performing ALD and / or CVD processing in the microvolume rather than the entire volume of the processing station may reduce reactant exposure and purge times, may reduce the time to change processing conditions (such as pressure, temperature, etc.), and may limit exposure of the processing station robot to the processing gas. Exemplary microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. The microvolume also affects productivity. When the deposition rate per cycle decreases, the cycle time is also shortened. In some cases, for a given target film thickness, the latter effect is significant enough to improve the overall throughput of the module.

[0235] In some embodiments, the susceptor 508 can be raised or lowered to expose the substrate 512 to the volume between the substrate 512 and the showerhead 506. It should be understood that in some embodiments, the susceptor height can be adjusted programmatically by a suitable computer controller 550.

[0236] In another case, in embodiments where the plasma is ignited, adjusting the height of the susceptor 508 can allow the plasma density to change during plasma activation in the process. At the end of the processing stage, the susceptor 508 can be lowered during another substrate transfer stage to allow the substrate 512 to be removed from the susceptor 508.

[0237] In some embodiments, the susceptor 508 can be temperature controlled by a heater 510. In some embodiments, the susceptor 508 can be heated to a temperature of about 25°C to about 800°C, or about 200°C to about 700°C during the deposition of the silicon nitride film described in the disclosed embodiments. In some embodiments, the susceptor is set at a temperature of about 25°C to about 800°C, or about 200°C to about 300°C.

[0238] In addition, in some embodiments, the pressure control of the ALD processing station 500 can be provided by a butterfly valve 518. As Figure 5 shown in the embodiments, the butterfly valve 518 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the ALD processing station 500 can also be adjusted by changing the flow rate of one or more gases introduced into the ALD processing station 500.

[0239] In some embodiments, the position of the showerhead 506 can be adjusted relative to the susceptor 508 to change the volume between the substrate 512 and the showerhead 506. In addition, it should be understood that the vertical positions of the susceptor 508 and / or the showerhead 506 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the susceptor 508 can include a rotating shaft for rotating the direction of the substrate 512. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more suitable computer controllers 550.

[0240] In some embodiments where plasma can be used as discussed above, the showerhead 506 and the pedestal 508 are in electrical communication with a radio frequency (RF) power supply 514 and a matching network 516 to power the plasma. For example, the plasma can be used to treat a silicon oxide surface before depositing silicon nitride. In some embodiments, the plasma energy can be controlled by controlling one or more of the process chamber pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 514 and the matching network 516 can operate at any suitable power to form a plasma with a desired radical species composition. For a single-station chamber, an example of a suitable power is from about 150 W to about 6000 W. For a 4-station chamber, the plasma power can include four generators, each with a power up to about 6000 W, for a total of about 24000 W. To treat a silicon-containing layer, the substrate can be exposed to one or more oxygen-containing species (e.g., oxygen radicals) or a mixture of oxygen-containing species and an optional inert gas, and a plasma is ignited using the RF power supply source 514 and the matching network 516.

[0241] In some embodiments, the substrate can be exposed to a nitrogen-containing species, an oxygen-containing species, a carbon-containing species, or a hydrogen-containing species, and a plasma is ignited to treat the substrate using the plasma power (e.g., about 500 to about 6000 W per 300 mm wafer surface area). For example, when a plasma with a plasma power between about 500 and about 6000 W is ignited, the substrate surface can be oxidized by exposing the substrate to an oxygen-containing species. The plasma can be generated remotely (e.g., in a remote plasma generator) or directly in the chamber that houses the substrate (i.e., in-situ). The RF power supply 514 can provide RF power at any suitable frequency. In some embodiments, the RF power supply 514 can be configured to control the high-frequency and low-frequency RF power supplies independently of each other. Exemplary low-frequency RF frequencies can include, but are not limited to, frequencies between 0 kHz and 500 kHz or up to about 2 MHz. Exemplary high-frequency RF frequencies can include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 30 MHz, or greater than 60 MHz. It should be understood that any suitable parameter can be adjusted discretely or continuously to provide the plasma energy for surface reactions.

[0242] In some embodiments, a remote plasma generator may be fluidly connected to a reactant delivery system 501. The remote plasma generator may receive one or more nitrogen-containing materials, oxygen-containing materials, carbon-containing materials, or hydrogen-containing materials from the reactant delivery system 501. For example, when an oxygen-containing material is supplied to the remote plasma generator, an oxygen-containing plasma may be generated when the plasma is ignited. The remote plasma generator may also be fluidly connected to a processing chamber 502. In some embodiments, the remote plasma generator may be fluidly connected to a showerhead 506 such that the oxygen-containing plasma may be provided to a substrate in the processing chamber 502 via the showerhead 506.

[0243] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one case, the plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another case, the plasma density and / or the processing gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be adjusted programmatically based on measurements from the in-situ plasma monitors. For example, the OES sensor may be used in a feedback loop to provide programmed control of the plasma power. It should be understood that in some embodiments, other monitors may be used to monitor the plasma and other processing properties. The monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0244] In some embodiments, instructions for a controller 350 may be provided via input / output control (IOC) sequencing instructions. In one example, instructions for setting conditions during a processing stage may be included in a corresponding recipe stage of a processing recipe. In some cases, the processing recipe stages may be arranged in sequence such that all instructions for a processing stage are executed simultaneously with that processing stage. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe stage. For example, a first recipe stage may include instructions for transporting a substrate into a processing chamber. A second recipe stage may include instructions for setting the flow rate of a silicon-containing precursor gas, instructions for setting the flow rate of hydrogen, instructions for setting the flow rate of a carrier gas (e.g., argon, helium, neon, krypton, and xenon), instructions for setting the chamber pressure and the substrate temperature, and a time delay instruction for the second recipe stage. A third recipe stage may include instructions for setting the flow rate of an inert and / or silicon-containing precursor gas, instructions for setting the flow rate of an oxygen-containing material, instructions for setting the frequency and power of an RF source, and a time delay instruction for the second recipe stage. It should be understood that these recipe stages may be further subdivided and / or repeated in any suitable manner within the scope of the disclosed embodiments. In some embodiments, the controller 550 may include the following regarding Figure 6any feature of the system controller 650 described above.

[0245] As described above, one or more processing stations may be included in a multi-station processing tool. Figure 6 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 600 includes a first processing chamber 602 and a second processing chamber 604. The first processing chamber 602 includes a plurality of processing stations, namely four stations 680A-D, each of which may process wafers. The first processing chamber 602 is configured to perform plasma processing operations on wafers. The second processing chamber 404 is configured to perform depositions on wafers and may be considered a deposition chamber. The second processing chamber 604 also includes a plurality of processing stations, namely four stations 682A-D, each of which may process wafers. The first and second processing chambers 602 and 604 may be considered multi-station processing chambers.

[0246] Tool 600 also includes a wafer transfer unit configured to transfer one or more wafers within tool 600. Additional features of tool 600 will be discussed in more detail below, and various features are discussed herein as part of the technology. In the depicted illustration, the wafer transfer unit includes a first robotic arm unit 608 in a first wafer transfer module 610 and a second robotic arm unit 612 in a second wafer transfer module 614, which may be considered a equipment front end module (EFEM), configured to receive a container of wafers (e.g., a front opening unified pod (FOUP) 616). The first robotic arm unit 608 is configured to transfer wafers between the first processing chamber 602 and the second processing chamber 604 and between the second robotic arm unit 612. The second robotic arm unit 612 is configured to transfer wafers between the FOUP and the first robotic arm unit 608. After processing a wafer in the first processing chamber 602, the wafer transfer unit is capable of transferring the wafer from the first processing chamber 602 to the second processing chamber 604, where one or more layers of encapsulation material may be deposited on one or more wafers.

[0247] Similar to the above, the first wafer transfer module 610 can be a Vacuum Transfer Module (VTM). The air lock 620, also known as a load lock, as shown, can be individually optimized to perform various manufacturing processes. The tool 600 also includes a FOUP 618, which is configured to reduce the pressure of the tool 600 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and maintain the tool 600 at that pressure. This includes maintaining the first and second processing chambers 602 and 604, as well as the first wafer transfer module 610, at a vacuum or low pressure. The second wafer transfer module 614 can be at a different pressure, e.g., atmospheric pressure. When the wafer is transferred throughout the tool 600, it is thus maintained at a vacuum or low pressure. For example, when the wafer is transferred from the first processing chamber 602 to the first wafer transfer module 610 and the second processing chamber 604, the wafer is maintained at a vacuum or low pressure and not exposed to atmospheric pressure.

[0248] In other examples, the substrate is placed in one of the plurality of FOUPs 618 and the second robotic arm unit 612 or the front-end robot transports the substrate from the FOUP 618 to an aligner, which allows the substrate to be properly centered before being etched or deposited or otherwise processed thereon. After alignment, the substrate is moved by the second robotic arm unit 612 into the air lock 620. Since the air lock module has the ability to match the environments between the ATM and the VTM, the substrate can move between the two pressure environments without being damaged. From the air lock 620, the substrate is moved by the first robotic arm unit 608 through the first wafer transfer module 610 or VTM 610 and into the first processing chamber 602. To effect this substrate movement, the first robotic arm unit 608 uses end effectors on each of its arms.

[0249] Figure 6 An implementation of a system controller 629 for controlling the processing conditions and hardware states of the tool 600 is also depicted. The system controller 629 can include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). The processor may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0250] In some embodiments, system controller 629 controls all activities of tool 600. System controller 629 executes system control software that is stored in a mass storage device, loaded into a memory device, and executed on a processor. Alternatively, control logic may be hard-coded in system controller 629. Application specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays or FPGAs), etc. may be used for these purposes. Wherever "software" or "code" is used in the following discussion, functionally equivalent hard-coded logic may be used. System control software may include instructions for controlling parameters such as timing, gas mixture, gas flow rate, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power level, RF power level, substrate pedestal, chuck, and / or susceptor position, and specific processes performed by tool 600. System control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of process tool components for performing various process tool processes. System control software may be coded in any suitable computer-readable programming language.

[0251] In some embodiments, system control software may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and / or programs stored on a mass storage device and / or memory device associated with system controller 629 may be employed in some embodiments. Examples of programs or program segments for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0252] The substrate positioning program may include program code for a process tool component that loads a substrate onto a pedestal and controls the spacing between the substrate and other parts of tool 600.

[0253] The process gas control program may include code for controlling gas composition (e.g., silicon-containing precursor gases, nitrogen-containing species, carrier gases, inert gases, and / or purge gases as described herein) and flow rate, and optionally for flowing gas into one or more process stations prior to deposition to stabilize the pressure in the process station. The pressure control program may include code for controlling the pressure in a process station by adjusting, for example, a throttle valve in the exhaust system of the process station, the gas flow into the process station, etc.

[0254] The heater control program may include code for controlling the current flowing to a heating unit for heating a substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (e.g., helium or nitrogen) to the substrate.

[0255] According to an embodiment of the present disclosure, a plasma control program may include code for setting an RF power level applied to a processing electrode in one or more processing stations.

[0256] According to an embodiment of the present disclosure, a pressure control program may include code for maintaining a pressure in a processing chamber.

[0257] In some embodiments, there may be a user interface associated with the system controller 429. The user interface may include a display screen, a graphical software display of the equipment and / or processing conditions, and user input devices such as a pointing device, a keyboard, a touch screen, a microphone, etc.

[0258] In some embodiments, the parameters adjusted by the system controller 429 may relate to processing conditions. Non-limiting examples include processing gas composition and flow rate, temperature, pressure, plasma conditions (such as RF bias power level), etc. These parameters may be provided to the user in the form of a recipe, which may be input using the user interface.

[0259] Analog and / or digital input connections from various processing tool sensors to the system controller 629 may provide signals for monitoring the processing. Signals for controlling the processing may be output on the analog and digital output connections of the tool 600. Non-limiting examples of processing tool sensors that may be monitored include: mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain processing conditions.

[0260] The system controller 629 may provide program instructions for implementing the deposition process described above. The program instructions may control various processing parameters, such as DC power level, RF bias power level, pressure, temperature, etc. According to various embodiments described herein, the instructions may control the parameters to operate the in-situ deposition of the film stack.

[0261] The system controller 629 will generally include one or more memory devices and one or more processors configured to execute the instructions such that the device will perform the methods according to the disclosed embodiments. A machine-readable medium containing instructions for controlling processing operations according to the disclosed embodiments may be coupled to the system controller 629.

[0262] In some implementations, the system controller 629 is part of a system that can be part of the above examples. Such systems can include semiconductor processing equipment that includes one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer chucks, gas flow systems, etc.). These systems can be integrated with electronics for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. The electronics can be referred to as a "controller" that can control various components or sub-components of one or more systems. Depending on the processing conditions and / or the type of system, the system controller 629 can be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out of tools and other transfer tools, and / or load locks that connect or dock with a particular system.

[0263] Broadly speaking, the system controller 629 can be defined as electronics that has various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, enabling cleaning operations, enabling endpoint measurements, etc. The integrated circuits can include chips in the form of firmware that stores 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). The program instructions can be instructions sent to the system controller 629 in the form of various individual settings (or program files) that define operation parameters for performing a specific process on or for a semiconductor wafer or system. In some embodiments, the operation parameters can be part of a recipe defined by a process engineer to complete one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0264] In some implementations, system controller 629 can be part of or coupled to a computer that is integrated with, coupled to, otherwise networked to the system, or a combination thereof. For example, system controller 629 can be in the "cloud" or be all or part of a fab host system, which can allow remote access to wafer processing. The computer can enable remote access to the system to monitor the current progress of manufacturing operations, examine the history of past manufacturing operations, examine trends or performance criteria for multiple manufacturing operations, change parameters of the current process, set processing steps to follow the current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system via a network, which can include a local network or the Internet. The remote computer can include a user interface that enables input or programming of parameters and / or settings, which are then sent from the remote computer to the system. In some examples, system controller 629 receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters can be specific to the type of process to be performed and the type of tool, and system controller 629 is configured to interface with or control the tool. Thus, as described above, system controller 629 can be distributed, for example, by including one or more discrete controllers that are networked together and work towards a common purpose, such as the processing and control described herein. An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber that communicate with one or more integrated circuits remotely (e.g., at the platform level or as part of a remote computer), which are combined to control the processing on the chamber.

[0265] Example systems can include, but are 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 cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing system that can be associated with or used for the manufacture and / or preparation of semiconductor wafers.

[0266] As described above, depending on one or more processing steps to be performed by the tool, system controller 629 can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in the material transport that shuttles wafer containers to and from tool locations and / or load ports in a semiconductor manufacturing facility.

[0267] Figure 7ADepicts a cross-sectional side view of an exemplary apparatus in accordance with some embodiments. As described below, the apparatus 200 is capable of rapidly and precisely controlling the temperature of a substrate, including performing thermal atomic layer etching (ALE) operations, one example being the Prevos manufactured by Lam Research Corporation (Fremont, California). TM Selective etching tool.

[0268] The apparatus 700 includes a processing chamber 702, a pedestal 704 having a plurality of substrate supports 708 configured to support a substrate 718, and a gas distribution unit 710. The processing chamber 702 includes sidewalls 712A, a top 712B, and a bottom 712C that at least partially define an interior chamber volume 714, which can be considered an inflated chamber volume. As described herein, in some embodiments, it may be desirable to actively control the temperature of the processing chamber walls 712A, top 712B, and bottom 712C to prevent unwanted condensation on their surfaces. Some emerging semiconductor processing operations direct vapors (such as water and / or alcohol vapors) onto the substrate, where they adsorb to the substrate but may also undesirably adsorb to the inner surfaces of the chamber. This can lead to unwanted deposition and etching on the inner surfaces of the chamber, which can damage the chamber surfaces and cause particles to flake onto the substrate, resulting in substrate defects. To reduce and prevent unwanted condensation on the inner surfaces of the chamber, the temperature of the chamber walls, top, and bottom can be maintained at a temperature at which the chemicals used in the processing operations do not condense.

[0269] Active temperature control of the chamber surface can be achieved by using heaters to heat the chamber walls 712A, top 712B, and bottom 712C. As Figure 7A shown, chamber heater 716A is located on chamber wall 712A and configured to heat it, chamber heater 716B is located on top 712B and configured to heat it, and chamber heater 716C is located on bottom 712C and configured to heat it. Chamber heaters 716A - 716C can be resistive heaters configured to generate heat when an electric current flows through a resistive element. Chamber heaters 716A - 716C can also be fluid conduits through which a heat transfer fluid can flow, such as a heating fluid, which can include heated water. In some instances, chamber heaters 716A - 716C can be a combination of a heating fluid and a resistive heater. Chamber heaters 716A - 716C are configured to generate heat to bring the inner surfaces of each chamber wall 712A, top 712B, and bottom 712C to a desired temperature, which can range from about 40°C to about 400°C, or about 40°C to about 250°C, or about 40°C to about 150°C, or about 80°C to about 130°C, or about 90°C to about 120°C. It has been found that, under some conditions, water and alcohol vapors do not condense on surfaces maintained at about 90°C or higher. Although Figure 7AAlthough not shown, the chamber heaters 716A - 716C may include one or more temperature sensors operably coupled to the chamber heaters 716A - 716C to monitor the chamber temperature.

[0270] The chamber walls 712A, top 712B, and bottom 712C may also be made of various materials capable of withstanding the chemicals used in the processing technology. These chamber materials may include, for example, aluminum, anodized aluminum, aluminum with a polymer (such as plastic), metal or metal alloy with a yttrium oxide coating, metal or metal alloy with a zirconia coating, and metal or metal alloy with an alumina coating; in some instances, the material of the coating may be a mixture or layers of different material combinations, such as alternating layers of alumina and yttrium oxide, or alternating layers of alumina and zirconia. These materials are configured to withstand the chemicals used in the processing technology, such as any anhydrous HF, water vapor, methanol, isopropyl alcohol, chlorine, fluorine gas, nitrogen, hydrogen, helium, and mixtures thereof.

[0271] The apparatus 700 may also be configured to perform processing operations under vacuum or near - vacuum, such as at a pressure of about 0.1 Torr to about 100 Torr, or about 20 Torr to about 200 Torr, or about 0.1 Torr to about 10 Torr, or about 1 Torr to about 20 Torr, or about 0.5 Torr to about 5 Torr. The apparatus 700 may include a vacuum pump 784 configured to evacuate the interior 714 of the chamber to a low pressure, such as a vacuum having a pressure of about 0.1 Torr to about 100 Torr (including about 0.1 Torr to about 10 Torr, and about 20 Torr to about 200 Torr, or about 0.1 Torr to about 10 Torr, or about 1 Torr to about 20 Torr, or about 0.5 Torr to about 5 Torr).

[0272] Various features of the susceptor 704 will now be discussed. The susceptor 704 includes a heater 722 (in Figure 7A(enclosed by a dashed rectangle), which has a plurality of LEDs 724 configured to emit visible light (whose wavelength ranges from 400 nm to 800 nm, including 450 nm). The heater LEDs emit this visible light to the backside of the substrate, thereby heating the substrate. Visible light with a wavelength of about 400 nm to 800 nm can quickly and efficiently heat a silicon substrate from ambient temperature (e.g., about 20 °C) to a temperature as high as about 600 °C because silicon absorbs visible light in this range. In contrast, radiative heating (including infrared light radiation) may not be able to efficiently heat silicon to a temperature as high as about 400 °C because silicon tends to be transparent to infrared light at temperatures below about 400 °C. Additionally, radiative heaters that directly heat the top side of the substrate, as in many conventional semiconductor processes, can cause damage or other adverse effects to the top side film. Many "hot plate" heaters that rely on solid-to-solid heat transfer between the substrate and a heating plate (e.g., a pedestal with heating coils) have relatively slow heating and cooling rates and provide non-uniform heating, which may be caused by substrate warping and inconsistent contact with the heating plate. For example, heating some pedestals to a desired temperature, heating from a first higher temperature to a second higher temperature, and cooling the pedestal to a lower temperature may take several minutes.

[0273] The plurality of LEDs of the heater can be arranged, electrically connected, and electrically controlled in various ways. Each LED can be configured to emit visible blue light and / or visible white light. In certain embodiments, white light (produced using a wavelength range in the visible light portion of the EM spectrum) is used. In some semiconductor processing operations, white light can reduce or prevent unwanted thin film interference. For example, some substrates have backside films that reflect different amounts of different light wavelengths, thus causing non-uniform and potentially inefficient heating. Using white light can reduce this unwanted reflection variation by averaging the thin film interference over the broad visible spectral range provided by the white light. In some instances, depending on the material on the backside of the substrate, using visible non-white light (e.g., blue light with a wavelength of 450 nm) may be advantageous, for example, to provide a single or narrow band wavelength that can provide more efficient, more powerful, and more direct heating to some substrates that have better absorption for the narrow band wavelength than for white light.

[0274] Multiple types of LEDs can be employed. Examples include chip-on-board (COB) LEDs or surface-mounted diode (SMD) LEDs. For SMD LEDs, the LED chips can be soldered to a printed circuit board (PCB), which can have multiple electrical contacts enabling control of the individual diodes on the chip. For example, a single SMD chip can have three diodes (e.g., red, blue, or green) that can be individually controlled to produce different colors. The size range of SMD LED chips can be, for example, 2.8×2.5 mm, 3.0×3.0 mm, 3.5×2.8 mm, 5.0×5.0 mm, and 5.6×3.0 mm. For COB LEDs, each chip can have more than three diodes (e.g., nine, twelve, dozens, hundreds, or more) printed on the same PCB. Regardless of the number of diodes, COB LED chips typically have one circuit and two contacts, thus providing a simple design and effective monochromatic applications. The ability and performance of an LED to heat a substrate can be measured by the number of watts of heat emitted by each LED; this heat in watts can directly contribute to heating the substrate.

[0275] Figure 7B A top view of a substrate heater with multiple LEDs is depicted. The substrate heater 722 includes a printed circuit board 726 and multiple LEDs 724, some of which are labeled; the depicted multiple includes approximately 1,300 LEDs. External connectors 728 are connected via traces to provide power to the multiple LEDs 724. As Figure 7B shown, the LEDs can be arranged along a number of arcs that radially deviate from the center 730 of the substrate heater 722 at different radii; within each arc, the LEDs can be equally spaced from each other. For example, an arc 732 is circled with a partially shaded dot pattern and includes 16 LEDs 724 and is part of a circle of radius R that extends around the center 730. The 16 LEDs 724 can be considered equally spaced from each other along the arc 732.

[0276] In some embodiments, the LEDs can also be arranged along a circle around the center of the substrate heater. In some instances, some LEDs can be arranged along a circle while others can be arranged along an arc. Figure 7C A top view of another example of a substrate heater with multiple LEDs is depicted. Figure 7C The substrate heater 722 includes a printed circuit board 726 and multiple LEDs 724, some of which are labeled. Here, the LEDs 724 are arranged along a number of circles that radially deviate from the center 730 of the substrate heater 722 at different radii; within each circle, the LEDs can be equally spaced from each other. For example, a circle 734 is circled with a partially shaded ring and includes 78 LEDs 724 and has a radius R that extends around the center 730. The 78 LEDs 724 can be considered equally spaced from each other along the circle 734. As compared withFigure 7B Compared with the arrangement in Figure 7C the arrangement of the LEDs in Figure 7B can provide a more uniform light and heat distribution pattern across the backside of the substrate because the substrate heater 722 in the region containing the external connection in may provide cold spots on the substrate that are not heated, especially since the substrate and the heater remain stationary relative to each other during processing; the substrate and the substrate heater do not rotate.

[0277] In some embodiments, the plurality of LEDs may include at least about 1,000 LEDs, such as about 1,200, 1,500, 2,000, 3,000, 4,000, 5,000, or more than 6,000. In some instances, each LED may be configured to use about 4 watts or less at 100% power, including using about 3 watts at 100% power and using about 1 watt at 100% power. These LEDs may be arranged and electrically connected to individually controllable zones to achieve temperature adjustment and fine-tuning across the substrate. In some instances, the LEDs may be grouped into at least 20, such as individually controllable zones, such as including at least about 25, 50, 75, 80, 85, 90, 95, or 100 zones. These zones may enable temperature adjustment in the radial and azimuthal (i.e., angular) directions. These zones may be arranged in a defined pattern, such as in a rectangular grid, a hexagonal grid, or other suitable pattern for generating a desired temperature profile. The zones may also have different shapes, such as square, trapezoidal, rectangular, triangular, oblong, oval, circular, annular (e.g., ring), partial annular (e.g., ring sector), arcuate, segmented, and sectors centered at the center of the heater and having a radius less than or equal to the total PCB radius of the substrate heater. For example, in FIG. 7, the LEDs have 88 zones that are organized into at least 20 (e.g., 20 or 21) concentric rings. These zones are capable of adjusting the temperature at many locations across the substrate to produce a more uniform temperature distribution and a desired temperature profile, such as a temperature around the edge of the substrate that is higher than the temperature at the center of the substrate. The independent control of these zones may also include the ability to control the power output of each zone. For example, each zone may have at least 15, 20, or 25 adjustable power outputs. In some instances, each zone may have one LED, thus enabling each LED to be individually controlled and adjusted, which may result in a more uniform heating profile on the substrate. Thus, in some embodiments, each LED in the plurality of LEDs in the substrate heater may be individually controllable.

[0278] In certain embodiments, the substrate heater 722 is configured to heat the substrate to multiple temperatures and maintain each such temperature for various durations. The substrate heater can be configured to heat the substrate to a temperature between about 50°C and 700°C, including any temperature or range between these temperatures. Additionally, in some embodiments, the substrate heater 722 is configured to heat the substrate to any temperature within these ranges in, for example, less than about 60 seconds, less than about 45 seconds, less than about 30 seconds, or less than about 15 seconds. In certain embodiments, the substrate heater 722 is configured to heat the substrate at one or more heating rates, such as between at least about 0.1°C / second and at least about 20°C / second.

[0279] The substrate heater can increase the temperature of the substrate by causing the LED to emit visible light at one or more power levels, including at least about 80%, at least about 90%, at least about 95%, or at least about 100% power. In some embodiments, the substrate heater is configured to emit light at 10W to 4000W, including at least about 10W, at least about 30W, at least about 0.3 kilowatts (kW), at least about 0.5kW, at least about 2kW, at least about 3kW, or at least about 4kW. The device is configured to provide from about 0.1kW to about 9kW of power to the pedestal; the power supply is connected to the substrate heater through the pedestal but is not shown in the figure. During the temperature rise, the substrate heater can operate at high power and can operate at a lower power level (e.g., including from about 5W to about 0.5kW) to maintain the temperature of the heated substrate.

[0280] The pedestal can include a reflective material on its inner surface that reflects and directs the light emitted by the LED onto the back side of the substrate supported by the pedestal during operation. In some such embodiments, the substrate heater can include such a reflective material located on the top surface 740 of the PCB 726, as Figure 7A shown, and a plurality of LEDs 724 are located on the top surface 740. The reflective material can include aluminum, such as polished aluminum, stainless steel, aluminum alloy, nickel alloy, and other protective layers that can prevent metal oxidation and / or enhance the reflectivity of a specific wavelength (e.g., achieving a reflectivity greater than 99% for a specific wavelength), as well as other durable reflective coatings. Additionally or alternatively, the pedestal 704 can have a bowl 746, and the substrate heater 722 is at least partially located in the bowl 746. The bowl 746 can have an exposed inner surface 748 of the pedestal sidewall 749, and the reflective material can be located thereon. The reflective material improves the heating efficiency of the substrate heater and reduces the unwanted heating of the PCB 726 and the pedestal 704 by advantageously redirecting the light back onto the substrate, which otherwise would be absorbed by the PCB 726 and the pedestal 704.

[0281] In some embodiments, the substrate heater may further include a base cooler that is thermally connected to the LEDs such that heat generated by the plurality of LEDs can be transferred from the LEDs to the base cooler. This thermal connection allows heat to conduct from the plurality of LEDs along one or more heat flow paths between these components to the base cooler. In some instances, the base cooler is in direct contact with one or more elements of the substrate heater, while in other instances, other conductive elements, such as a heat conducting plate (e.g., including metal), are interposed between the substrate heater and the base cooler. Return reference Figure 7A , the substrate heater includes a base cooler 736 that is in direct contact with the bottom of the PCB 726. Heat is configured to flow from the LEDs to the PCB 726 and to the base cooler 736. The base cooler 736 also includes a plurality of fluid conduits 738 through which a heat transfer fluid (e.g., water) is configured to flow to receive the heat and thus cool the LEDs in the substrate heater 722. The fluid conduits 738 may be connected to a container and pump (not shown) located outside the chamber. In some instances, the base cooler may be configured to have cooled water (e.g., about 5°C to 20°C) flowing through it.

[0282] As provided herein, it may be advantageous to actively heat the outer surface of the processing chamber 702. In some instances, it may also be advantageous to heat the outer surface of the heating pedestal 704 to prevent unwanted condensation and deposition on its outer surface. As Figure 7A shown, the pedestal 704 may further include a pedestal heater 744 inside the pedestal 704 that is configured to heat the outer surface of the pedestal 704, including its sides 742A and bottom 742B. The pedestal heater 744 may include one or more heating elements, such as one or more resistive heating elements and fluid conduits through which a heating fluid is configured to flow. In some instances, both the base cooler and the pedestal heater may have fluid conduits that are fluidly connected to each other such that the same heat transfer fluid can flow through both the base cooler and the pedestal heater. In these embodiments, the fluid may be heated to between 50°C and 130°C, including about 90°C and 120°C.

[0283] The pedestal may also include a window to protect the substrate heater, which includes a plurality of LEDs, from damage caused by exposure to the processing chemicals and pressures used during the processing operation. As Figure 7AAs shown, the window 750 can be located above the substrate heater 722 and sealed to the sidewall 749 of the base 704 to create an inflated chamber volume within the base that is fluidically isolated from the interior of the chamber. This inflated chamber volume can also be considered the interior of the bowl 746. The window can be composed of one or more materials that are transparent to visible light emitted by the LEDs, including light having wavelengths in the range of 400 nm to 800 nm. In some embodiments, the material can be quartz, sapphire, quartz with a sapphire coating, or calcium fluoride (CaF). There may also be no holes or openings within the window. In some embodiments, the heater can have a thickness of about 15 to 30 mm, including about 20 mm and about 25 mm.

[0284] Figure 7D depicts a base with additional features according to various embodiments Figure 7A As Figure 7D shown, the window 750 includes a top surface 752 facing the substrate 718 supported by the base 704 and a bottom surface 754 facing the substrate heater 722. In some embodiments, the top surface 752 and the bottom surface 754 can be flat planar surfaces (or substantially flat, e.g., within ±10% or 5% of flat). In some other instances, the top 752, the bottom 754, or both the top 752 and the bottom 754 can be non-planar surfaces. The non-planarity of these surfaces can be configured to refract and / or direct the light emitted by the LEDs 724 of the substrate heater 722 to heat the substrate more efficiently and / or effectively. The non-planarity can also be along part or all of the surface. For example, the entire bottom surface can have a convex or concave curvature, and in another example, the outer annular region of the bottom surface can have a convex or concave curvature while the remainder of the surface is planar. In a further example, these surfaces can have multiple but different non-planar portions, such as having a conical portion at the center of the surface, the conical portion adjacent to a planar annular portion, and the planar annular portion adjacent to a frustum of a cone surface at the same or different angles. In some embodiments, the window 750 can have the feature of being a lens array that is oriented to focus the light emitted by one or more LEDs (e.g., each LED).

[0285] Since the window 750 is located above the substrate heater 722, the window 750 is heated by the substrate heater 722, which can affect the thermal environment around the substrate. Depending on one or more materials used for the window 750, such as quartz, the window can retain heat and gradually retain more heat during the processing of one or more substrates. This heat can be transferred to the substrate by radiation, thus directly heating the substrate. In some instances, the window can cause the temperature to increase between 50 °C and 80 °C compared to the heater temperature. This heat can also create a temperature gradient across the entire thickness or vertical dimension of the window. In some instances, the top surface 752 is 30 °C hotter than the bottom surface 754. Therefore, it may be advantageous to adjust and configure the chamber to address and reduce the thermal effects of the window. This can include detecting the temperature of the substrate and adjusting the substrate heater to account for the heat retained by the window.

[0286] This can also include various configurations of the susceptor, such as actively cooling the window. In some embodiments, as Figure 7A and 7D shown, the window 750 can be offset from the substrate heater 722 by a first distance 756. In some embodiments, the first distance can be from about 2 mm to about 50 mm, including from about 5 mm to about 40 mm. A cooling fluid (such as an inert gas) can flow between the window 750 and the substrate heater 722 to cool both the window 750 and the substrate heater 722. The susceptor can have one or more inlets and one or more outlets for allowing this gas to flow within the plenum volume or bowl 746 of the susceptor 704. The one or more inlets are fluidly connected to an inert gas source external to the processing chamber 702, which can include a through-fluid conduit that can be at least partially routed inside the susceptor 704. The one or more outlets are fluidly connected to an exhaust device or other environment external to the processing chamber 702, which can also be a through-fluid conduit extending within the susceptor. In Figure 7E which depicts a susceptor with additional features according to various embodiments, one or more inlets 751 are located in the sidewall 749 and extend through the inner surface 748; the one or more inlets are also fluidly connected to an inert gas source 772 (such as an inert gas source) through a path that partially passes through a fluid conduit 755 of the susceptor 704. A single outlet 753 is located in the central region of the substrate heater 722, that is, not exactly at the center but adjacent to the center. In some embodiments, the one or more gas inlets and the one or more outlets can be switched such that the one or more outlets extend through the sidewall 749 (i.e., the item 751 in Figure 7D ), and the one or more inlets can be the central region of the substrate heater 722 (i.e., the item in Figure 7E ), and the one or more inlets can be the central region of the substrate heater 722 (i.e., the item in Figure 7Ethe object in (753). In some embodiments, there may be more than one outlet; in some embodiments, there may be only a single gas inlet. In some embodiments, one or more gas inlets extend through the inner surface 748 of the base sidewall 749 below the LED heater 722, and one or more gas outlets extend through another part of the base sidewall 749, such as the mounting bracket between the LED heater 722 and the base sidewall 749.

[0287] In some embodiments, the window may be arranged to be in direct thermal contact with the substrate heater, and the base cooler may be configured to cool both the PCB and the window. In some embodiments, also as Figure 7A and Figure 7D shown, the window 750 may be thermally connected to the sidewall 749 of the base 704 to transfer some of the heat retained in the window 750 to the base 704. The transferred heat may be further transferred out of the base using, for example, the base heater 744, which may pass a fluid heated to, for example, about 20°C to about 100°C through the base 704. The heated fluid will be cooler compared to the temperature of the base 704 thermally connected to the window 750. In some embodiments, the window 750 may have one or more fluid conduits located within the window 750, and a transparent cooling fluid may be configured to flow through the fluid conduits. The fluid may be routed from a fluid source or container outside the chamber through the base to the window.

[0288] As Figure 7A and 7D shown, the substrate support 708 of the base 704 is configured to support the substrate 718 above and offset from the window 750 and the substrate heater 722. In certain embodiments, the temperature of the substrate can be quickly and precisely controlled by thermally floating or thermally isolating the substrate within the chamber. It is desirable to configure the substrate to have a minimum thermal mass for heating and cooling. The thermal float is configured to position the substrate such that it has a minimum thermal contact (including direct and radiative) with other objects in the chamber.

[0289] Thus, the base 704 is configured in some embodiments to support the substrate 718 by thermally floating or thermally isolating the substrate within the interior 714 of the chamber. The plurality of substrate supports 708 of the base 704 are configured to support the substrate 718 such that the thermal mass of the substrate 718 is reduced as much as possible to only the thermal mass of the substrate 718. Each substrate support 708 may have a substrate support surface 720 that provides a minimum contact with the substrate 718. The number of substrate supports 708 may range from at least 3 to, for example, at least 6 or more. The surface area of the support surface 720 may also be the minimum area required to adequately support the substrate during processing operations (e.g., to support the weight of the substrate and prevent inelastic deformation of the substrate).

[0290] The substrate support is also configured to prevent the substrate from contacting other elements of the base, including the surface of the base and features below the substrate. As Figure 7A and 7D seen in, the substrate support 108 holds the substrate 718 above and offset from the next adjacent surface of the base 704 below the substrate 718, which adjacent surface is the top surface 752 of the window 750 (identified in Figure 7D ). As can be seen from Figure 7A , there is a volume or gap below the substrate in addition to contact with the substrate support. As Figure 7D shown, the substrate 718 is offset from the top surface 752 of the window 750 by a distance 758. This distance 758 affects the thermal effect on the substrate 718 caused by the window 750. The greater the distance 758, the smaller the effect. It has been found that a distance 758 of 2 mm or less results in significant thermal coupling between the window and the substrate; thus, a distance 758 greater than 2 mm is desired, such as at least about 5 mm, about 10 mm, about 15 mm, about 20 mm, about 30 mm, about 50 mm, or about 100 mm.

[0291] The substrate 718 is also offset from the substrate heater 722 by a distance 760 (in some instances, measured from the top surface of the substrate heater 722, which top surface can be the top surface of the LED 724). This distance 760 affects many aspects of heating the substrate 718. In some embodiments, a distance 760 of about 10 mm to about 90 mm, or about 5 mm to about 100 mm, or about 10 mm to about 30 mm provides a substantially uniform heating pattern and acceptable heating efficiency.

[0292] As described above, the substrate support 708 is configured to support the substrate 718 above the window. In some embodiments, these substrate supports are stationary and fixed in place; they are not lift pins or support rings. In some embodiments, at least a portion of each substrate support 708 including the support surface 720 can be made of a material that is transparent to the light emitted by at least the pair of LEDs 724. This material can be quartz or sapphire in some instances. The light transmissivity of these substrate supports 708 enables the visible light emitted by the LEDs 724 of the substrate heater 722 to pass through the substrate supports 708 and reach the substrate 718, such that the substrate supports 708 do not block the light and the substrate 718 can be heated in the area where it is supported. This can provide more uniform heating of the substrate 718 compared to substrate supports made of a material that is transparent to the visible light portion. In some other embodiments, the substrate supports 708 can be made of an opaque material (such as zirconia (ZrO2)).

[0293] In some embodiments, the susceptor may be configured to directly support a substrate (not shown). The susceptor may be configured with lift pins or other movable support members to position the substrate within a deposition zone in the environment of the substrate. The substrate may be movable vertically within the chamber. In some embodiments, the susceptor includes an electrostatic chuck. The electrostatic chuck may be the uppermost part of the susceptor and may include one or more electrostatic clamping electrodes embedded within the body of the electrostatic chuck. The substrate may be supported on the top surface of the electrostatic chuck. In some embodiments, one or more of the electrostatic clamping electrodes may be coplanar or substantially coplanar. The electrostatic clamping electrodes may be powered by a DC power source or a DC clamping voltage (e.g., from about 200V to about 2000V) such that the substrate can be held on the electrostatic chuck by electrostatic attraction. The power to the electrostatic clamping electrodes may be provided through a first wire connected to the electrostatic clamping electrodes. The electrostatic chuck may also include one or more heating elements embedded within the body of the electrostatic chuck. The one or more heating elements may include resistive heaters. In some embodiments, the one or more heating elements are located below the one or more electrostatic clamping electrodes. The one or more heating elements may be configured to heat the substrate to a temperature greater than about 200°C, greater than about 450°C, greater than about 500°C, greater than about 550°C, greater than about 600°C, greater than about 650°C, or greater than about 700°C. The one or more heating elements provide selective temperature control of the substrate. The power to the one or more heating elements may be provided through a second wire connecting the one or more heating elements and a power source.

[0294] In some embodiments, such as Figure 7D those shown in, the substrate support 708 may be disposed closer to the central axis 762 of the window 750 than the outer diameter 764 of the window. In some instances, a portion of these substrate supports may extend above and over the window 750.

[0295] Return reference Figure 7A , in some embodiments, the susceptor is also configured to move vertically. This may include moving the susceptor such that the gap 786 between the panel 776 of the gas distribution unit 710 and the substrate 718 can be in the range of about 2 mm to about 70 mm. Vertically moving the susceptor enables active cooling of the substrate as well as fast cycle times for processing operations, including flowing and purging gases, as it creates a small volume between the gas distribution unit 710 and the substrate 718. This movement may also create a small processing volume between the substrate and the gas distribution unit, which can result in smaller purge and processing volumes, thus reducing purge and gas movement times and increasing throughput.

[0296] The gas distribution unit 710 is configured to flow a process gas (which may include liquids and / or gases, such as reactants, modifying molecules, transforming molecules, or removal molecules) onto the substrate 718 in the chamber interior 714. The gas distribution unit 710 may be configured to atomize a liquid into fine droplets in the chamber interior 714 at atmospheric temperature. In some embodiments, the process gas may include (diluted) hydrogen fluoride (HF), oxygen, ozone, hydrogen peroxide, or combinations thereof. As Figure 7A shown, the gas distribution unit 710 includes one or more fluid inlets 770 that are fluidly connected to one or more gas sources 772 and / or one or more vapor sources 774. The gas distribution unit 110 and other units or components that may be in fluid contact with the process gas may be designed and fabricated to be chemically resistant or inert to the process gas. In some embodiments, the gas lines and mixing chambers may be heated to prevent unwanted condensation of the vapors and gases flowing therein. These lines may be heated to at least about 40°C, at least about 80°C, at least about 90°C, at least about 120°C, at least about 130°C, or at least about 150°C. The one or more vapor sources may include one or more gas and / or liquid sources that are vaporized. The vaporization may be a direct injection vaporizer, a flow-through vaporizer, or both. In some embodiments, one or more vapor sources and one or more process gases may be configured to operate sequentially or simultaneously. The gas distribution unit 710 also includes a panel 776 that contains a plurality of through-holes 778 that fluidly connect the gas distribution unit 710 to the chamber interior 714. These through-holes 778 are fluidly connected to the one or more fluid inlets 770 and also extend through the front surface 777 of the panel 776, which is configured to face the substrate 718. In some embodiments, the gas distribution unit 710 may be regarded as a top plate, while in some other embodiments, it may be regarded as a showerhead.

[0297] The through-holes 778 may be configured in various ways to deliver a uniform gas flow onto the substrate. In some embodiments, these through-holes may all have the same outer diameter, such as between about 0.03 inches and about 0.05 inches, including about 0.04 inches (1.016 mm). These panel through-holes may also be arranged across the entire panel to produce a uniform flow out of the panel.

[0298] Return reference Figure 7A, the gas distribution unit 710 may further include a unit heater 780 that is thermally connected to the panel 776 such that heat can be transferred between the panel 776 and the unit heater 780. The unit heater 780 may include a fluid conduit through which a heat transfer fluid can flow. Similar to the above, the heat transfer fluid can be heated to a temperature range of, for example, about 20°C to 120°C. In some instances, the unit heater 780 can be used to heat the gas distribution unit 710 to prevent undesirable condensation of vapors and gases; in some such instances, the temperature can be at least about 90°C or 120°C.

[0299] In some embodiments, the gas distribution unit 710 may include a second unit heater 782 configured to heat the panel 776. The second unit heater 782 may include one or more resistive heating elements, fluid conduits for heating fluid flow, or both. The use of two heaters 780 and 782 in the gas distribution unit 710 can achieve various heat transfers within the gas distribution unit 710. This can include using the first and / or second unit heaters 780 and 782 to heat the panel 776 to provide a temperature-controlled chamber, as described above, to reduce or prevent undesirable condensation on the components of the gas distribution unit 710.

[0300] The apparatus 700 may also be configured to cool the substrate. The cooling may include flowing a cooling gas over the substrate, moving the substrate near the panel to allow heat transfer between the substrate and the panel, or both. Actively cooling the substrate can achieve more precise temperature control and faster temperature transitions, which reduces processing time and increases throughput. In some embodiments, the first unit heater 780 through which the heat transfer fluid flows can be used to cool the substrate 718 by transferring the heat transferred from the substrate 718 out of the panel 776. Thus, the substrate 718 can be cooled by positioning it adjacent to the panel 776 with a gap 786 of, for example, less than or equal to 5 mm or 2 mm such that the heat in the substrate 718 is radiated to the panel 776 and transferred out of the panel 776 by the heat transfer fluid in the first unit heater 780. The panel 776 can thus be regarded as a heat sink for the substrate 718 to cool the substrate 718.

[0301] In some embodiments, for example, the apparatus 700 may further include a cooling fluid source 773, which may contain a cooling fluid (gas or liquid) and a cooler (not shown) configured to cool the cooling fluid to a desired temperature, such as less than or equal to about 90 °C, less than or equal to about 70 °C, less than or equal to about 50 °C, less than or equal to about 20 °C, less than or equal to about 10 °C, less than or equal to about 0 °C, less than or equal to about -50 °C, less than or equal to about -100 °C, less than or equal to about -150 °C, less than or equal to about -190 °C, about -200 °C, or less than or equal to about -250 °C. The apparatus 700 includes a conduit for delivering the cooling fluid to the one or more fluid inlets 770, and a gas distribution unit 710 configured to direct the cooling fluid onto the substrate. In some embodiments, the fluid may be in a liquid state as it flows into the processing chamber 702 and may turn into a vapor state when it reaches the interior 714 of the chamber, for example if the interior 714 of the chamber is at a low pressure, such as described above, for example about 0.1 Torr to about 10 Torr, or 0.1 Torr to about 100 Torr, or about 20 Torr to about 200 Torr. The cooling fluid may be an inert element, such as nitrogen, argon, or helium. In some instances, the cooling fluid may include or may consist only of non-inert elements or mixtures, such as hydrogen. In certain embodiments, the apparatus may be configured to cool the substrate at one or more cooling rates, such as at least about 5 °C / second, at least about 10 °C / second, at least about 15 °C / second, at least about 20 °C / second, at least about 30 °C / second, or at least about 40 °C / second.

[0302] In some embodiments, the apparatus 700 may actively cool the substrate by moving the substrate closer to the panel and directing a cooling gas onto the substrate. In some instances, active cooling is more effective by flowing the cooling gas when the substrate is adjacent to the panel. The effectiveness of the cooling gas may also depend on the type of gas used.

[0303] In some embodiments, the apparatus 700 may include a mixing plenum for mixing and / or conditioning the process gas for delivery before it reaches the fluid inlet 770. One or more mixing plenum inlet valves may control the introduction of the process gas into the mixing plenum. In some other embodiments, the gas distribution unit 710 may include one or more mixing plenums within the gas distribution unit 710. The gas distribution unit 710 may also include an annular flow path fluidly connected to the through holes 778, which may evenly distribute the received fluid to the through holes 778 to provide a uniform flow onto the substrate.

[0304] The apparatus 700 may also include one or more additional non-contact sensors for detecting the temperature of the substrate. For example, such sensors may include an improved pyrometer. Although traditional pyrometers cannot detect certain substrates within a specific temperature range, the pyrometers described herein overcome these problems. For example, the pyrometer is configured to detect multiple emission ranges to detect various types of substrates at various temperature ranges, such as doped, lightly doped, or undoped. This includes configurations for detecting emission ranges of from about 0.95 microns to about 1.1 microns, about 1 micron, from about 1 to about 4 microns, and / or from about 8 to 15 microns. The pyrometer is also configured to detect the temperature of the substrate at shorter wavelengths to distinguish the signal from the thermal noise of the chamber.

[0305] The pyrometer may include a transmitter configured to emit an infrared light signal and a detector configured to receive the emission. Referring Figure 7A , the apparatus includes a pyrometer 788 and a detector 790, the pyrometer 788 having a transmitter within the pyrometer 788. The pyrometer may be configured to emit a signal on one side (top or bottom) of the substrate and to receive the signal on the other side of the substrate. For example, the transmitter may emit a signal on the top of the substrate while the detector is below the substrate and receives the signal that has passed through and beneath the substrate. Thus, the apparatus may have at least one first port 792A on the top of the processing chamber 702, such as port 792A that passes through the center of the gas distribution unit 710, and a second port 792B that passes through the susceptor 704 and the substrate heater 722. The transmitter in the pyrometer 788 may be connected to one of the ports 792A or 792B by an optical fiber connection, such as Figure 7A the first port 792A shown in Figure 7A , while the detector is optically connected to the other port, such as Figure 7A the second port 792B in

[0306] The apparatus 700 may also include one or more optical sensors 798 to detect one or more metrics of the visible light emitted by the LED. In some embodiments, these optical sensors may be one or more photodetectors configured to detect the light and / or light intensity emitted by the LED of the substrate heater. In Figure 7AIn [the figure], a single optical sensor 798 is shown as being connected to the interior 714 of the chamber via an optical fiber connection such that the optical sensor 798 can detect the light emitted by the substrate heater 722. The optical sensor 798 and additional optical sensors can be disposed at different locations, such as the top and sides, of the processing chamber 702 to detect the emitted light at different locations within the processing chamber 702. As described below, this enables the measurement and adjustment of the substrate heater, such as adjusting one or more independently controllable LED regions. In some embodiments, there may be multiple optical sensors 798 arranged along a circle or multiple concentric circles to measure multiple LED regions throughout the processing chamber 702. In some embodiments, the optical sensors can be disposed within the interior 714 of the chamber.

[0307] In some embodiments, the apparatus described herein can include a controller configured to control multiple aspects of the apparatus to perform the techniques described herein. For example, returning to reference Figure 7A , apparatus 700 includes a controller 731 (which can include one or more physical or logical controllers) that is communicatively coupled to and controls some or all of the operations of the processing chamber. The system controller 731 can include one or more memory devices 733 and one or more processors 735. In some embodiments, when the disclosed embodiments are executed, the apparatus includes, for example, a switching system operatively coupled to the system controller 731 for controlling flow rate and duration, a substrate heating unit, a substrate cooling unit, loading and unloading of the substrate in the chamber, thermal floating of the substrate, and a process gas unit. For example, the switching system can control the flow rate and duration of water vapor in the chamber such that one or more monolayers of water are controllably adsorbed onto the substrate or the silicon nitride surface. In some embodiments, the apparatus can have a switching time of up to about 500 milliseconds (ms) or up to about 750 ms. The switching time can depend on the flow chemistry, the selected recipe, the reactor architecture, and other factors.

[0308] In some embodiments, the switching system of the apparatus can be coupled to one or more contact or non-contact sensors to monitor the substrate temperature, one or more temperature sensors can be operatively coupled to the chamber heater to monitor the chamber temperature, or coupled to the gas distribution unit to monitor and control the flow rate and duration of one or more gaseous reactants and vapors.

[0309] In some implementations, the controller is part of a system, which can be part of the above examples. Such systems can include semiconductor processing equipment, which includes one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronics for controlling their operations before, during, and after the processing of semiconductor wafers or substrates. The electronics can be referred to as a "controller", which can control various components or sub-components of one or more systems. Depending on the processing requirements and / or the type of system, the controller can be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out of tools connected or docked to a particular system and other transfer tools and / or load locks.

[0310] Broadly speaking, a controller can be defined as electronics that has various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, enabling cleaning operations, enabling endpoint measurements, etc. The integrated circuits can include chips in the form of firmware that stores 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). The program instructions can be instructions sent to the controller in the form of various individual settings (or program files), which define the operating parameters for performing a specific process on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer to complete one or more processing steps during the fabrication of one or more (types of) layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or die of a wafer.

[0311] In some implementations, the controller can be part of or coupled to a computer that is integrated with, coupled to, networked to the system in other ways, or a combination thereof. For example, the controller can be in the "cloud" or be all or part of a fab host system, which can allow remote access to wafer processing. The computer can implement remote access to the system to monitor the current progress of a manufacturing operation, review the history of past manufacturing operations, review trends or performance criteria for multiple manufacturing operations, to change parameters of the current process, set processing steps to follow the current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system via a network, which can include a local network or the Internet. The remote computer can include a user interface that enables the input or programming of parameters and / or settings, which are then sent from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify the parameters for each processing step to be performed during one or more operations. It should be understood that the parameters can be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, the controller can be distributed, for example, by including one or more discrete controllers that are networked together and work towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes is one or more integrated circuits on a chamber that communicate with one or more integrated circuits remote (e.g., at the platform level or as part of a remote computer), which combine to control the processing on the chamber.

[0312] The apparatus / processes described herein can be used for, but are not limited to, performing in a CVD or PECVD chamber or module, an ALD or PEALD chamber or module, an atomic layer etch (ALE) chamber or module, a plasma etch chamber or module, and any other semiconductor processing system that may be associated with or used in the manufacture and / or production of semiconductor wafers, displays, LEDs, photovoltaic panels, and the like. In some embodiments, an exemplary system can include a combination of an ALD (thermal ALD) or PEALD chamber or module and an ALE chamber or module such that one or more depositions and oxidations are performed on a substrate, followed by one or more etches without breaking the vacuum in the chamber or exposing the substrate to the ambient atmosphere.

[0313] As described above, the controller can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in the material transport that shuttles a wafer container between a tool location and / or load port in a semiconductor manufacturing facility, depending on one or more processing steps to be performed by the tool.

[0314] In some embodiments, the apparatus may also be configured to generate a plasma and use the plasma for some of the processes in a variety of embodiments. This may include having a plasma source configured to generate a plasma inside a chamber, such as capacitively coupled plasma (CCP), inductively coupled plasma (ICP), upper remote plasma, and lower remote plasma.

[0315] The apparatus described herein can be used in a variety of etching techniques, including but not limited to continuous etching methods and cyclic methods, such as atomic layer etching.

[0316] According to the embodiments herein, a method of filling the interstitial gaps of features with a silicon-containing material is disclosed. A silicon-containing material having a low dielectric constant (k~3) can be gap-filled in high aspect ratio features without forming voids in the gap-fill material. The processes disclosed herein can be used as interconnect processes as well as gate metal processes. Conclusion

[0317] Although the above embodiments have been described in some detail for purposes of clear understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and devices of the embodiments of the present invention. Accordingly, the embodiments of the present invention should be considered illustrative rather than restrictive, and these embodiments are not limited to the details given herein.

Claims

1. A method, comprising: Depositing a silicon-containing layer in one or more recessed features of a substrate; Exposing at least a portion of the silicon-containing layer to an oxygen-containing species, thereby forming a silicon-containing oxide portion in the silicon-containing layer; and At least partially etching the silicon-containing oxide portion.

2. The method according to claim 1, wherein depositing the silicon-containing layer comprises: Introducing a silicon precursor to adsorb on the surface of the substrate and thermally decompose to form the silicon-containing layer.

3. The method according to claim 1, wherein the silicon-containing layer comprises silicon carbide, silicon carbon oxide, silicon carbon oxynitride (SiCOH), or silicon carbon oxynitride.

4. The method according to claim 1, wherein the silicon-containing layer comprises a conformal layer.

5. The method according to claim 1, wherein the silicon-containing layer comprises an intercalation layer.

6. The method according to claim 1, wherein the oxygen-containing species diffuses into the silicon-containing layer to a penetration depth.

7. The method according to any one of claims 1-6, wherein the oxygen-containing species comprises oxygen, ozone, hydrogen peroxide, oxygen-containing free radicals, a plasma thereof, or a mixture thereof.

8. The method according to any one of claims 1-6, wherein exposing the at least a portion of the silicon-containing layer comprises: Converting the portion of the silicon-containing layer into the silicon-containing oxide portion.

9. The method according to any one of claims 1-6, wherein at least a portion of the silicon-containing layer is exposed to the oxygen-containing species at a pressure of about 0.5 Torr to about 5 Torr.

10. The method according to any one of claims 1-6, wherein at least a portion of the silicon-containing layer is exposed to the oxygen-containing species at a pressure of about 1 Torr to about 20 Torr.

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