Implementing selective deposition of tantalum nitride barrier layers in back-end process vias

Abstract

A pretreatment method of facilitating deposition of a metal-containing film includes exposing a semiconductor substrate to a reducing agent and an inhibitor. Silicon-containing inhibitor and reducing agent pre-treatments may be used in conjunction with deposition of metal-containing barrier films, and optionally with post-treatments to remove the inhibitor. Selective deposition may be accomplished by utilizing a silicon-containing inhibitor having at least one Si-H group and an organic moiety.

Description

[0001] By incorporating references The PCT application form is filed together with this specification as part of this application. Each application listed in the concurrently filed PCT application form that claims a benefit or priority under this application is incorporated herein by reference in its entirety for all purposes. Background Technology

[0002] Semiconductor manufacturing processes involve metallization during back-end logic (BEOL) processing. Contacts are formed by depositing conductive interconnect material in openings on the surface of an insulating material positioned between two spaced conductive layers. The interconnect material can be made of aluminum or copper. Copper offers a lower resistivity than aluminum. However, copper diffuses, leading to the formation of undesirable intermetallic alloys, thus requiring the use of a barrier layer material.

[0003] Tantalum nitride is a suitable barrier layer material for use with copper. However, conventional tantalum nitride barrier layer deposition processes are non-selective and can lead to increased resistance. Therefore, a selective and efficient tantalum nitride deposition process would be advantageous.

[0004] The background description provided herein is for the purpose of presenting the general context of this disclosure. The work of the currently designated inventor, within the scope described in this background section and in aspects of the specification that could not be identified as prior art at the time of filing, neither expressly nor impliedly acknowledges that it is prior art to this disclosure. Summary of the Invention

[0005] A pretreatment method for promoting the deposition of metal-containing films and an apparatus for performing the method are provided. The pretreatment method includes exposing a semiconductor substrate to a reducing agent and an inhibitor. The silicon-containing inhibitor and reducing agent pretreatment can be used in conjunction with the deposition of a metal-containing barrier film, and with an optional post-treatment to remove the inhibitor. Selective deposition can be achieved by utilizing a silicon-containing inhibitor having at least one Si-H group and an organic moiety. For example, the properties of through-hole resistance can be improved using the methods described herein.

[0006] Therefore, in a first aspect, this disclosure includes a method for preparing a substrate for metal-containing film deposition. In some embodiments, the method includes providing a substrate in a processing chamber; exposing the substrate to a reducing agent to obtain a reduced substrate; and exposing the reduced substrate to an inhibitor to obtain a pretreated substrate.

[0007] In some implementations, the inhibitor is a silicon-containing inhibitor or an oxygen-containing inhibitor.

[0008] In some embodiments, the silicon-containing inhibitor has a head group containing at least one Si-H group and a tail group containing an organic moiety.

[0009] In some implementations, the head group is -SiH3.

[0010] In some implementations, the silicon-containing inhibitor is RSiHX. 1 X 2 R is the organic part; X 1 and X 2 Each of them is independently hydrogen, halogen, optionally substituted aliphatic group, optionally substituted cycloaliphatic group, or optionally substituted aromatic group.

[0011] In some embodiments, the organic part is or includes an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted cycloaliphatic group, an optionally substituted cyclohexaphatic group, an optionally substituted aromatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroalkyl group, an optionally substituted heteroalkenyl group, an optionally substituted heteroalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted cyclohexaalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

[0012] In some embodiments, the organic part is or includes an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted cycloaliphatic group, an optionally substituted cyclohexaphatic group, an optionally substituted aromatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroalkyl group, an optionally substituted heteroalkenyl group, an optionally substituted heteroalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted cyclohexaalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

[0013] In some embodiments, the organic portion is or includes a branched hydrocarbon group, or the organic portion includes one or more halogen substituents, or the organic portion is or includes a branched hydrocarbon group and includes one or more halogen substituents; or the organic portion has 6 to 20 carbon atoms in a straight-chain, branched, or cyclic group.

[0014] In some embodiments, the organic part is or includes -XLZ, and X is a covalent bond, optionally substituted alkylene, optionally substituted alkenyl, optionally substituted ynylene, optionally substituted alkoxy, optionally substituted heteroalkylene, optionally substituted heteroalkenyl, optionally substituted heteroynylene, optionally substituted aryl, optionally substituted aryloxy, or optionally substituted heterocyclic diester; L is a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1-、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S-, or -O-; Z is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted ynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroynyl, optionally substituted aryl, or optionally substituted heterocyclic; and R 1 and R 2 Each of them is independently hydrogen or optionally a substituted alkyl group.

[0015] In some implementations, the oxygen-containing inhibitor is acetylacetone.

[0016] In some embodiments, the exposure of the substrate to a reducing agent or to a reduced substrate occurs in a plasma, and the plasma is a remote plasma or a direct plasma.

[0017] In some implementations, the reducing agent is a nitrogen-containing reagent or a hydrogen-containing reagent.

[0018] In some embodiments, the nitrogen-containing reagent is nitrogen, ammonia, hydrazine, azide, or a combination thereof.

[0019] In some implementations, the hydrogen-containing reagent is hydrogen, methane, acetylene, or water.

[0020] In some implementations, the metal is tantalum, titanium, molybdenum, cobalt, indium, or ruthenium.

[0021] In some embodiments, the metal-containing film is tantalum nitride, indium oxide, tungsten nitride, or titanium nitride.

[0022] In a second aspect, this disclosure includes a method for processing a substrate. In some embodiments, the method includes providing a substrate in a processing chamber; exposing the substrate to a reducing agent to obtain a reduced substrate; exposing the reduced substrate to an inhibitor to obtain a pretreated substrate; supplying a metal-containing precursor to the processing chamber to obtain a metal-containing film on the pretreated substrate; and selectively post-treating the metal-containing film with plasma to remove the inhibitor.

[0023] In some implementations, the inhibitor is a silicon-containing inhibitor or an oxygen-containing inhibitor.

[0024] In some embodiments, the silicon-containing inhibitor includes a head group containing at least one Si-H group and a tail group containing an organic moiety.

[0025] In some implementations, the head group is -SiH3.

[0026] In some implementations, the silicon-containing inhibitor is RSiHX. 1 X2 R is the organic part; X 1 and X 2 Each of them is independently hydrogen, halogen, optionally substituted aliphatic group, optionally substituted cycloaliphatic group, or optionally substituted aromatic group.

[0027] In some implementation schemes, X 1 and X 2 Each of them is independently a optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, or optionally substituted aryl.

[0028] In some embodiments, the organic part is or includes an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted cycloaliphatic group, an optionally substituted cyclohexaphatic group, an optionally substituted aromatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroalkyl group, an optionally substituted heteroalkenyl group, an optionally substituted heteroalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted cyclohexaalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

[0029] In some embodiments, the organic portion is or includes a branched hydrocarbon group, or the organic portion includes one or more halogen substituents, or the organic portion is or includes a branched hydrocarbon group and includes one or more halogen substituents; or the organic portion has 6 to 20 carbon atoms in a straight-chain, branched, or cyclic group.

[0030] In some embodiments, the organic part is or includes -XLZ, and X is a covalent bond, optionally substituted alkylene, optionally substituted alkenyl, optionally substituted ynylene, optionally substituted alkoxy, optionally substituted heteroalkylene, optionally substituted heteroalkenyl, optionally substituted heteroynylene, optionally substituted aryl, optionally substituted aryloxy, or optionally substituted heterocyclic diester; L is a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1 -、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S-, or -O-; Z is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted ynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroynyl, optionally substituted aryl, or optionally substituted heterocyclic; and R 1 and R 2 Each of them is independently hydrogen or optionally a substituted alkyl group.

[0031] In some implementations, the oxygen-containing inhibitor is acetylacetone.

[0032] In some implementations, the exposure of the substrate to a reducing agent or to a reduced substrate occurs in a plasma, which is either a remote plasma or a direct plasma.

[0033] In some implementations, the reducing agent is a nitrogen-containing reducing agent or a hydrogen-containing reducing agent.

[0034] In some embodiments, the nitrogen-containing reducing agent is nitrogen, ammonia, hydrazine, azide, or a combination thereof.

[0035] In some implementations, the hydrogen-containing reducing agent is hydrogen, methane, acetylene, or water.

[0036] In some implementations, the metal is tantalum, titanium, molybdenum, cobalt, indium, or ruthenium.

[0037] In some embodiments, the metal-containing film is tantalum nitride, indium oxide, tungsten nitride, or titanium nitride.

[0038] In a third aspect, this disclosure includes a method for selectively depositing a tantalum nitride barrier layer. In some embodiments, the method includes providing a substrate having a metal surface and a dielectric surface in a processing chamber; exposing the substrate to a reducing agent to obtain a reduced substrate; exposing the reduced substrate to an inhibitor to obtain a pretreated substrate; supplying a tantalum-containing precursor and a nitrogen-containing reactant to the processing chamber to selectively form a tantalum nitride barrier layer on the metal surface above the pretreated substrate; and post-treating the tantalum nitride barrier layer with plasma to remove the inhibitor.

[0039] In a fourth invention, this disclosure includes an apparatus for selective deposition. In some embodiments, the apparatus includes a processing chamber; a substrate holder within the processing chamber; one or more gas inlets for allowing gas to flow into the processing chamber; a vacuum source for removing gas from the processing chamber; a plasma generator for generating plasma within the processing chamber; and one or more controllers including machine-readable instructions for operating the one or more gas inlets, the vacuum source, and the plasma generator to perform deposition on a semiconductor substrate, wherein the machine-readable instructions of the one or more controllers include instructions for performing the methods described herein.

[0040] These and other aspects are further described below with reference to the accompanying drawings. Attached Figure Description

[0041] Figure 1A process flow diagram is presented for a non-limiting method for preparing a substrate for metal film deposition, according to some disclosed embodiments.

[0042] Figure 2 A process flow diagram of a non-limiting method for processing a substrate, based on some publicly disclosed embodiments, is presented.

[0043] Figure 3 A schematic diagram is provided illustrating a non-limiting method for selectively depositing tantalum nitride barrier layers according to some disclosed embodiments.

[0044] Figure 4 A schematic diagram of an atomic layer deposition (ALD) chamber suitable for implementing various schemes is shown.

[0045] Figure 5 Another schematic diagram of another ALD room suitable for implementing multiple implementation schemes is shown. Detailed Implementation

[0046] The following description provides numerous specific details to offer a thorough understanding of the presented embodiments. The disclosed embodiments can be implemented without some or all of these specific details. In other respects, well-known process operations have not been described in detail to avoid unnecessarily confusing the disclosed embodiments. Although the disclosed embodiments are described in conjunction with specific implementations, it should be understood that this is not intended to limit the scope of the disclosed embodiments.

[0047] Figure 1 A process flow diagram is presented for a non-limiting method 100 for preparing a substrate for metal film deposition, according to some publicly disclosed embodiments.

[0048] In operation 102, a substrate is provided in a processing chamber. The substrate is placed on a heated base with a temperature range of about 150°C to about 350°C and a pressure range of about 0.5 Torr to about 18 Torr. The substrate may be a silicon wafer, such as a 200 mm, 300 mm, or 450 mm wafer, including wafers having one or more layers of material (e.g., dielectric, conductive, or semiconductive materials) deposited thereon. In many embodiments, the substrate is patterned. The patterned substrate may have “features” such as pillars, rods, grooves, through-holes, or contact holes, which may be characterized as one or more narrow and / or recessed openings, contractions within the feature, and high aspect ratios. Features may be formed in one or more of the aforementioned layers. One example of a feature is a pillar or rod in a semiconductor substrate or a layer on the substrate. Another example is a groove in a substrate or layer.

[0049] In some embodiments, features such as pillars may have aspect ratios of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or higher. Features may also have dimensions close to the opening size, such as an opening diameter or linewidth between about 10 nm and 500 nm, for example, between about 25 nm and about 300 nm. The disclosed methods can be performed on substrates with features having openings less than about 150 nm. Vias, recesses, or other recessed features may be referred to as unfilled features or features. According to various embodiments, the feature profile may gradually narrow and / or include overhangs at the feature opening. A concave profile is a profile that narrows from the bottom, closed end, or interior of the feature to the feature opening. A concave profile can be generated by asymmetric etch kinetics during patterning and / or by overhangs resulting from non-conformal film steps in previous film deposition (e.g., deposition of a diffusion barrier layer). In various examples, the width of the opening at the top of the feature may be smaller than the width at the bottom of the feature.

[0050] In operation 104, the substrate is exposed to a reducing agent to form a reduced substrate. In some embodiments, the reducing agent exposure may be thermal exposure or in plasma. The surface of the reduced substrate is cleaned to prepare it for deposition. The reducing agent may be a nitrogen-containing reagent, such as nitrogen, ammonia, hydrazine, azides, or combinations thereof. In some embodiments, the reducing agent may be a hydrogen-containing reagent, such as hydrogen, methane, acetylene, or water. The reducing agent may be a reducing gaseous substance. In some embodiments, the reducing agent may include additional gases, such as carbon monoxide (CO), diborane (B₂H₆), sulfite compounds, carbon and / or hydrocarbons, or phosphites.

[0051] Suitable plasmas can be generated remotely or directly. Direct plasma (or directly generated plasma) is plasma in which the plasma (appropriate concentrations of electrons, neutral matter, radicals, and positive ions) is located close to the substrate surface during deposition, sometimes separated from the substrate surface only by a plasma sheath. Ions play an important role in direct plasma processes. In some embodiments, the plasma is generated remotely. Remote plasma (or remotely generated plasma) is plasma generated at a distance from the substrate. The main reactants may be remotely generated plasma radicals.

[0052] In some embodiments, operation 104 can be performed at a temperature of about 100°C to about 400°C. The reducing agent may optionally be co-flowed with an inert gas. In some embodiments, the reducing agent may be co-flowed with an inert gas, such as argon at a flow rate of about 500 to about 11,500 sccm.

[0053] In some implementations, the reducing agent can be treated with plasma in the plasma dose to decompose it into its radical form. The plasma can be generated or present within the treatment chamber itself. Alternatively, the plasma can typically be located at a location removed from the treatment chamber, such as in a remote plasma system.

[0054] For example, a reducing agent can be introduced into a direct plasma reactor, where it generates plasma to produce precursors for plasma treatment. The reducing agent can be introduced and held in the treatment chamber prior to plasma treatment.

[0055] Alternatively, plasma treatment can be performed simultaneously with the introduction of a reducing agent. In-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma generated between the nozzle and the substrate holder. Depending on whether positive ion collisions occur, the substrate or nozzle can be a charged electrode. Common applied power for in-situ plasma generators ranges from approximately 100 W to approximately 1000 W.

[0056] Plasma can also be generated remotely, with precursors for plasma processing being generated outside the processing chamber.

[0057] Operation 104 can be performed at pressures of approximately 0.5 to approximately 20 Torr, or approximately 3 to approximately 9 Torr; with a four-station module (QSM) power of approximately 0.5 to approximately 6.5 kW and an RF time of approximately 0.05 to approximately 60 seconds. The reactive plasma carrier gas includes, but is not limited to, Ar, He, N2, O2, N2O, and CO2.

[0058] Operation 106 is optionally to purge the processing chamber with an inert gas. The purge chamber may involve a flowing purge gas or purging gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve venting the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, purging may include one or more venting sub-stages for venting the processing chamber. Purging may have any suitable duration, for example, from about 0 seconds to about 60 seconds, such as about 0.01 seconds. The purge flow rate may be from about 500 to about 5000 sccm; in some embodiments, the temperature during purging may be from about 120°C to about 350°C, and the pressure may be from about 1 Torr to about 20 Torr, or from about 3 Torr to about 18 Torr.

[0059] In operation 108, the reduced substrate is exposed to an inhibitor to obtain a pretreated substrate under thermal or plasma conditions. The inhibitor may be an oxygen-containing inhibitor or a silicon-containing inhibitor. This "dry" treatment may be preferred over conventional "wet" treatments using inhibitors because it can provide ease of use and higher yields under certain conditions. In some embodiments, an inhibitor-enhancing agent may be co-treated with the inhibitor. The inhibitor-enhancing agent may comprise alkyl substituents with a chain length of 2 to 20 carbons and may be oxygen-containing or silicon-containing. In some embodiments, combinations of inhibitors may be used, such as two or more oxygen-containing inhibitors, two or more silicon-containing inhibitors, or a combination of at least one oxygen-containing inhibitor and at least one silicon-containing inhibitor.

[0060] Silicon-containing inhibitors may include any inhibitor comprising at least one Si atom and at least one organic moiety. As used herein, the term "organic moiety" refers to a portion of a compound containing at least one carbon atom. In one embodiment, the silicon-containing inhibitor comprises at least one Si-H bond or group. In another embodiment, the silicon-containing inhibitor comprises at least three Si-H bonds and an organic moiety, namely RSiH3, where R is the organic moiety.

[0061] In one embodiment, the silicon-containing inhibitor comprises a head group containing one Si atom and a tail group containing an organic moiety. In another embodiment, the head group is or includes -SiH3 or -SiH2X. 1 or -SiHX 1 X 2 , where X 1 and X 2 Each of these is independently selected from the group consisting of: hydrogen (H), halogens, optionally substituted aliphatic groups, optionally substituted cyclic aliphatic groups, or optionally substituted aromatic groups. In a particular embodiment, X 1 and X 2 Each of these is independently hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). In other embodiments, X 1 and X 2 Each of them is independently H, halogen, or optionally substituted C. 1-6 alkyl.

[0062] In other embodiments, the silicon inhibitor is or includes RSiHX. 1 X 2 Where R is the organic part, and X 1 and X 2 Each of these is any of the groups described herein. In a particular embodiment, X 1 and X 2 Each of these is independently H, F, Cl, Br, or I. In another embodiment, X1 and X 2 Each of them is independently a H halogen or an optional substituted C. 1-6 alkyl.

[0063] The non-limiting organic moiety (or R) may be or include optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted cycloaliphatic, optionally substituted cyclohexaaliphatic, or optionally substituted aromatic. In other embodiments, the organic moiety may be or include optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted cycloalkyl, optionally substituted cyclohexaalkyl, optionally substituted aryl, or optionally substituted heterocyclic. Examples of substituents in the organic moiety may include any alkyl or aryl group described herein. In certain embodiments, the organic moiety includes a branched hydrocarbon. In other embodiments, the organic moiety includes optionally substituted alkyl groups having one or more halogen substituents (e.g., one or more fluorine substituents).

[0064] In other embodiments, the organic portion is or includes -XLZ, wherein: X is a covalent bond, optionally substituted alkylene, optionally substituted alkenyl, optionally substituted ynylene, optionally substituted alkoxy, optionally substituted heteroalkylene, optionally substituted heteroalkenyl, optionally substituted heteroynylene, optionally substituted aryl, optionally substituted aryloxy, or optionally substituted heterocyclic diester; L is a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1 -、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S-, or -O-; Z is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted ynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroynyl, optionally substituted aryl, or optionally substituted heterocyclic; and R 1 and R 2 Each of them is independently H or an optional substituted alkyl group.

[0065] In some embodiments, X is an optionally substituted alkylene group; L is a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1-、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S-, or -O-; Z is H or an optionally substituted alkyl group; R 1 and R 2 Each of them is independently H or an optional substituted C. 1-6 alkyl.

[0066] In a particular embodiment, the organic moiety comprises 6 to 26 carbon atoms (e.g., 6 to 24, 6 to 20, 6 to 18, 8 to 26, 8 to 24, 8 to 20, 8 to 18, 10 to 26, 10 to 24, 10 to 20, or 10 to 18 carbon atoms) in a straight-chain, branched, or cyclic group. Optionally, the organic moiety may be or include optionally substituted C atoms. 6-26 Alkyl, optionally substituted C 6-26 alkenyl, optionally substituted C 6-26 alkynyl group, optionally substituted C 6-26 Heteroalkyl, optionally substituted C 6-26 Heterene group, optionally substituted C 6-26 Heterene group, optionally substituted C 6-26 cycloalkyl, optionally substituted C 6-26 Cyclohexane, optionally substituted C 6-26 aryl, or optionally substituted C 6-26 Heterocyclic group.

[0067] Non-restrictive silicon-containing inhibitors include n-octadecylsilane (C 18 H 40 Si), tridecylsilane (C 13 H 30 Si), dodecylsilane (C) 12 H 28 Si), undecylsilane (C 11 H 26 Si), decylsilane (C) 10 H 24 Si), dec-4-ylsilane (C 10 H 24 Si), nonylsilane (C9H) 22 Si), nonyl-4-ylsilane (C9H) 22 Si, nonan-4-ylsilane), octyl-2-ylsilane (C8H) 20 Si, octan-2-ylsilane, octylsilane (C8H) 20 Si), heptylsilane (C7H) 18 Si), heptylsilane (C7H) 18Si, heptan-4-ylsilane, (tetrazolium-1,1,2,2-tetrahydrooctyl)silane (C8H7F) 13 Si), 10-undecenylsilane (C 11 H 24 Si), etc.

[0068] Oxygen-containing inhibitors may include any inhibitor comprising at least one oxygen atom and at least one organic moiety. In one embodiment, the oxygen-containing inhibitor comprises at least one OH bond or group. Non-limiting oxygen-containing inhibitors include acetylacetone and hydroxamic acid.

[0069] Other inhibitors, such as nitrogen-containing compounds including propargylamine, may also be useful in some cases.

[0070] Appropriate plasma can be generated remotely or directly. Method 100 involves pretreating the metal surface of the substrate to reduce it while depositing inhibitors, which facilitates the production of substrates including vias with low resistivity.

[0071] Furthermore, the introduction of both the reducing agent and the inhibitor can be thermal, or the introduction of both the reducing agent and the inhibitor can be plasma-based, or the introduction of one of the reducing agent and the inhibitor can be thermal while the other is plasma-based.

[0072] Figure 2 A process flow diagram of a non-limiting method 200 for processing a substrate according to some disclosed embodiments is presented, which includes a reducing agent / inhibitor pretreatment, metal deposition, and optional post-treatment to remove the inhibitor.

[0073] In operation 202, a substrate is provided in the processing chamber, as described above regarding... Figure 1 As described in operation 102.

[0074] In operation 204, the substrate is exposed to a reducing agent to form a reduced substrate, as described above. Figure 1 Operation 104 is described.

[0075] Operation 206 can optionally purge the treatment chamber with inert gas, as described above. Figure 1 The operation described in 106.

[0076] In operation 208, the reduced substrate is exposed to an inhibitor to obtain a pretreated substrate, as described above. Figure 1 The operation described in 108.

[0077] In operation 210, a metal-containing precursor is supplied to a processing chamber to form a metal-containing film. Non-limiting metals include cobalt (Co), copper (Cu), tungsten (W), ruthenium (Ru), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), and / or molybdenum (Mo), combinations thereof, and their doped forms. The metal-containing precursor may be transported in a carrier gas, including but not limited to Ar, He, N2, O2, N2O, and CO2.

[0078] In operation 212, the metal-containing film can be selectively treated with plasma to remove inhibitors. Furthermore, purging can be selectively performed between operations 210 and 212 under the conditions described above.

[0079] The advantages of method 200 include that, due to the metal surface reduction preparation, the inhibitor adheres better to the metal in some cases.

[0080] Figure 3 Process 300 is schematically shown, depicting a non-limiting method for selectively depositing tantalum nitride (TaN) barrier layers. As used herein, TaN refers to any useful stoichiometry in the composition, including TaN, Ta2N, Ta3N5, Ta4N5, Ta4N, Ta5N6, and Ta6N. 2.5 , and its mixtures.

[0081] As can be seen, the substrate 310 includes a first region 311 and a second region 312, wherein the second region 312 is different from and adjacent to the first region 311. In one embodiment, the first region 311 includes a conductive material (e.g., a metal), and the second region 312 includes a semi-conductive or non-conductive material (e.g., a semiconductor or a dielectric). In another embodiment, the first region 311 includes a semi-conductive material, and the second region 312 includes a non-conductive material.

[0082] Non-limiting conductive materials may include metals, such as transition metals including cobalt (Co), copper (Cu), tungsten (W), ruthenium (Ru), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), and / or molybdenum (Mo), combinations thereof, and their doped forms. Non-limiting semiconducting materials include silicon (Si), germanium (Ge), silicon-germanium (SiGe), germanium-silicon (GeSi), doped Si, doped Ge, and (in some cases) silicon carbide. Non-limiting nonconducting materials may include nonmetals or dielectrics, such as low-κ dielectrics. Examples of low-κ dielectrics include dielectrics with a relative permittivity (κ) less than about 4.0 or less than about 3.0, and dielectrics from about 2.0 to 4.0, 2.0 to 2.0, 2.5 to 4.0, or 2.5 to 3.0. Low-κ dielectrics include silicon dioxide (SiO2) (including doped SiO2 (e.g., carbon-doped oxide (CDO) or carbon-doped SiO2), porous SiO2, porous doped SiO2 (e.g., porous CDO)), silicon nitrides, silicon carbides (in some cases), silicon carbide, silicon nitride, silicon carbide, etc.

[0083] Back to Figure 3 Process 300 may include 301 exposing the substrate to a reducing agent, 302 introducing a silicon-containing inhibitor, 303 introducing a tantalum-containing precursor and a nitrogen-containing precursor to deposit a tantalum nitride barrier layer, and 304 optionally removing the inhibitor layer. Each operation is discussed sequentially. Operations 301 and 302 are pretreatment steps performed before deposition step 303, while operation 304 is a post-treatment. In some embodiments, the inhibitor may be an oxygen-containing inhibitor or a silicon-containing inhibitor, such as... Figure 3 As shown.

[0084] In operation 301, the substrate is exposed to a reducing agent to form a reduced substrate, as described above. Figure 1 Operation 104 is described.

[0085] In operation 302, the reduced substrate is exposed to an inhibitor to obtain a pretreated substrate, as described above regarding... Figure 1 The operation described in 108.

[0086] In operation 302, the inhibitor is shown as a silicon-containing inhibitor introduced onto the surface of substrate 310. Due to the affinity of the inhibitor molecules for first region 311, an inhibitor layer 320 is selectively provided on first region 311. The second region 312 is largely free of silicon-containing inhibitor, thus providing a non-inhibited surface.

[0087] The inhibitor layer 320 can be characterized by its location, for example, being positioned closer to the first region than the second region. The inhibitor layer is also characterized by the orientation of the silicon-containing inhibitor. Figure 3As shown, the silicon-containing inhibitor is characterized by a head group (represented by a circle) at one end and a tail group (represented by a line) at the other end, wherein the head group is close to the surface of the first region 311. Not every inhibitor molecule needs to be oriented in this manner, and the inhibitor layer may include an ordered layer or a disordered layer, wherein the ordered layer has head groups precisely oriented to the surface of the first region, and the disordered layer has some, but not all, of the head groups oriented in the same direction.

[0088] Furthermore, the inhibitor layer can be a monolayer (a single molecular layer, including ordered or disordered monolayers) or a multilayer (more than one molecular layer, including ordered or disordered bilayers or other multilayers). In a multilayer, each layer is oriented in any useful manner, for example, the head groups of the first layer are predominantly oriented towards the surface of the first region, and the second layer is disposed on the first layer with its tail groups oriented towards the tail groups of the first layer. Such a multilayer can have any useful configuration of layers and silicon-containing inhibitors, which can be envisioned to minimize energy interactions during self-assembly.

[0089] The properties of the inhibitor layer can be represented by the following: its mass variation, which may represent the number of intact or cleaved inhibitor molecules; its water contact angle (WCA), which may represent the density or packing of one or more layers; and / or its CH bending or stretching pattern using FTIR, which may represent the density or packing of one or more layers. In one embodiment, the inhibitor layer is characterized by a WCA (water contact angle) greater than about 90°C or about 100°C to 120°C.

[0090] Silicon-containing inhibitors (e.g., any of those described herein) can be introduced onto the surface using suitable process conditions. In one embodiment, the silicon-containing inhibitor is provided to the chamber at a dispensing time of about 5 to 600 seconds, and / or at a temperature of about 50°C to 400°C or 50°C to 100°C, and / or at a pressure of 5 Torr to 10 Torr. In a particular embodiment, the silicon-containing inhibitor is provided with an inert carrier gas. In some embodiments, the silicon-containing inhibitor may be heated in an N2 carrier gas to a temperature between about 50°C and about 100°C. The delivery of the inhibitor to the chamber can be continuous or pulsed. Additional process conditions are described herein.

[0091] like Figure 3 As shown, operation 303 includes depositing material 330 on the second region 312 by introducing a tantalum-containing precursor (also referred to herein as a Ta-based precursor) and a nitrogen-containing reactant under thermal atomic layer deposition conditions. In one embodiment, material 330 is provided as a layer. As used herein, selective deposition can mean selectively depositing a silicon-containing inhibitor on the first region and / or selectively depositing material on the second region. Because the inhibitor layer 320 blocks deposition, material 330 is selectively deposited on the second region 312.

[0092] In certain embodiments, the Ta-based precursor is an organometallic compound comprising at least one Ta center and at least one ligand capable of reacting with a reducing gas or alkyne. In some non-limiting embodiments, the Ta-based precursor further includes an organic moiety that may be reactive in the presence of patterned radiation, for example, by removal or elimination from the metal center, or by reaction or polymerization with other portions within the membrane.

[0093] In some implementations, the Ta-based precursor comprises a structure having formula (I): T a R b L c (I), in: Each R is independently an EUV-unstable group, a halogen, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted amino group, an optionally substituted imino group, or an optionally substituted alkylene group; each L is independently a ligand or other part that reacts with a reducing gas or alkyne. b≥0; and c≥0.

[0094] In other embodiments, b is 1 and c is 3. In other embodiments, c ≥ 1. In still other embodiments, b ≥ 1. In a particular embodiment, L is an optionally substituted amino group (e.g., -NR). N1 R N1 , where R N1 and R N2 Each of these is independently H or an optionally substituted alkyl group, such as methyl, ethyl, butyl, isopropyl, tert-butyl, n-butyl, etc. In some embodiments, R is an EUV-unstable group comprising a double-bonded ligand (e.g., =NR). i or = CR i R ii , where R i and R ii Each of them is independently H, an optionally substituted straight-chain alkyl group, an optionally substituted branched-chain alkyl group, or an optionally substituted cycloalkyl group, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, etc.

[0095] In other embodiments, the Ta-based precursor comprises a structure having formula (IA): R=T a (L) b (IA), in: R is = NR i or =CR i R ii ; Each of L is independently a halogen, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted amino group, an optionally substituted bis(trialkylsilyl)amino group, an optionally substituted trialkylsilyl group, or a divalent ligand bonded to Ta, wherein the divalent ligand is -NR. i -Ak-NR ii -; R i and R ii Each of them is independently H, an optionally substituted straight-chain alkyl group, an optionally substituted branched alkyl group, or an optionally substituted cycloalkyl group; Ak is an optionally substituted alkylene group or an optionally substituted alkenylene group; and b≥1.

[0096] In some embodiments, the optionally substituted amino group is -NR. 1 R 2 , where R 1 and R 2 Each of them is independently H or an alkyl group; or R is wherein 1 and R 2 Together with the nitrogen atom attached to each of them, they form a heterocyclic group as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino group is -N(SiR) 1 R 2 R 3 )2, where R 1 R 2 and R 3 Each of these is independently an optionally substituted alkyl group. In yet other embodiments, the optionally substituted trialkylsilyl group is -SiR. 1 R 2 R 3 , where R 1 R 2 and R 3 Each of them is independently an optional substituted alkyl group.

[0097] In some implementations, the Ta-based precursor is R=Ta(NR) N1 R N2 )3, where R N1 and R N2 Each of the alkyl groups is independently an optionally substituted alkyl group (e.g., methyl, ethyl, butyl, isopropyl, tert-butyl, n-butyl, etc.), and R is a double bond ligand (e.g., =NR). i or =CHR i , where R i(These are optionally substituted alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, etc.). In such a precursor, the double-bonded ligand acts as both a nitrogen source and an EUV-indestabilizing group, while the three amino ligands act as reaction sites to attach to existing functional groups on the surface of the deposition substrate.

[0098] Non-restricted Ta-based precursors include pentapenta(dimethylamino)tantalum(V) (Ta[NMe2]5), tert-pentylimine tris(dimethylamino)tantalum(V) (Ta(=N-CHMe2Et)(NMe2)3, and (tert-butylimine)tris(diethylamino)tantalum(V) (Ta(=N- t- Bu)(NEt2)3), (tert-butylimino)tris(dimethylamino)tantalum(V) (Ta(=N- t- Bu)(NEt2)3), and (tert-butylimino)tris(ethylmethylamino)tantalum(V) (Ta(=N- t- Bu)(NMeEt)3). In some embodiments, suitable tantalum-containing precursors include tert-butyliminotris(dimethylamino)tantalum and tantalum pentachloride. Other tantalum precursors include (Et2N)5Ta, (Me2N)5Ta, (EtMeN)5Ta, (Me5C5)TaCl4, (acac)(EtO)4Ta, Br5Ta, I5Ta, F5Ta, (NO3)5Ta, (t-BuO)5Ta, (i-PrO)5Ta, (EtO)5Ta, and (MeO)5Ta.

[0099] Nitrogen-containing reactants are reactants or mixtures of reactants that include at least one nitrogen atom, such as ammonia, hydrazine, amines (amines containing carbon), such as methylamine, dimethylamine, ethylamine, isopropylamine, tert-butylamine, di-tert-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isopentylamine, 2-methylbut-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-tert-butylhydrazine, and aromatic groups containing amines, such as aniline, pyridine, and benzoylamine. The amine can be a primary amine, secondary amine, tertiary amine, or quaternary amine (e.g., tetraalkylammonium compounds). Nitrogen-containing reactants may contain heteroatoms other than nitrogen; for example, hydroxylamine, tert-butoxycarbonylamine, and N-tert-butylhydroxylamine are nitrogen-containing reactants. Exemplary nitrogen-containing reactants include nitrogen gas, ammonia, and amines.

[0100] Materials can be deposited using vapor-phase deposition processes such as ALD, CVD, and their plasma-enhanced forms. Non-limiting materials include non-conductive materials, such as insulators, as well as oxides, metal oxides, nitrides, metal nitrides, carbides, metal carbides, or oxynitrides. Examples of materials include alumina, zinc oxide, zirconium oxide, hafnium oxide, silicon oxide, silicon oxynitride, silicon nitride, or titanium oxide. Multiple cycles (e.g., 10, 100, 200, or more cycles) can be used to deposit material layers. Other conditions may include deposition times of approximately 5 to 600 seconds and / or temperatures of approximately 25°C to 500°C and / or pressures of approximately 10 mTorr to 10 Torr.

[0101] Back to Figure 3 Operation 304 is optional and may include removing the inhibitor layer from the first region 311. In this way, the substrate may be further processed to provide a connection that is physically or electrically connected to the first region. For example, if the first region 311 is a metal line, removing the inhibitor layer 320 may allow the deposition of a metal via that is electrically connected to the metal line and electrically isolated from other metal lines in the substrate through the presence of a selectively deposited material 330.

[0102] Conventional TaN barrier deposition techniques involve non-selectively depositing TaN followed by etching. This layer is then shielded and etched again to allow openings to be formed in vias, where direct metal-to-metal contacts can be created. This approach involves too many steps, which can reduce yield and increase the likelihood of misalignment. Selective deposition, as described in method 300 above, is more efficient and also produces substrates with approximately 5% to 30% lower resistivity than conventional processes.

[0103] Device Figure 4 An embodiment of a processing workstation 400 is schematically shown, which can be used to deposit materials using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which can be plasma-enhanced. For simplicity, the processing station 400 is depicted as a standalone processing station having a processing chamber 402 for maintaining a low-pressure environment. However, it should be understood that multiple processing stations 400 may be contained within a common processing facility environment. It should also be understood that in some embodiments, one or more computer controllers may programmatically adjust one or more hardware parameters of the processing station 400 (including the parameters discussed in detail herein).

[0104] Processing station 400 is in fluid communication with reactant delivery system 401, which delivers process gas to distribution nozzle 406. Reactant delivery system 401 includes a mixing container 404 for mixing and / or adjusting the process gas to be delivered to nozzle 406. One or more mixing container inlet valves 420 control the introduction of process gas into mixing container 404. Similarly, nozzle inlet valve 405 controls the introduction of process gas into nozzle 406.

[0105] Some reactants, like BTBAS, can be stored in liquid form, then vaporized and subsequently transported to a processing station. For example, Figure 4 The implementation includes an evaporation point 403 for evaporating liquid reactants to be supplied to mixing vessel 404. In some implementations, evaporation point 403 may be a heated evaporator. Reactant vapors generated from such an evaporator may condense in a downstream delivery line. Exposure of incompatible gases to the condensed reactants may generate small particles. These particles can clog lines, impede valve operation, contaminate substrates, etc. Some methods for addressing these problems involve sweeping and / or purging the delivery line to remove residual reactants. However, sweeping the delivery line increases processing station cycle time and reduces processing station throughput. Therefore, in some implementations, the delivery line downstream of evaporation point 403 may be thermally tracked. In some examples, mixing vessel 404 may also be thermally tracked. In a non-limiting example, the line downstream of evaporation point 403 has a high temperature distribution extending from about 100°C to about 150°C at mixing vessel 404.

[0106] In some embodiments, the reactant liquid can evaporate at a liquid injector. For example, the liquid injector can pulse-inject liquid reactants into a carrier gas flow upstream of the mixing vessel. In one case, the liquid injector evaporates the reactants by instantaneously changing the liquid pressure from higher to lower. In another case, the liquid injector can atomize the liquid into dispersed droplets, which then evaporate in a heated delivery line. It should be understood that smaller droplets evaporate faster than larger droplets, thus reducing the delay between liquid injection and completion of evaporation. Faster evaporation reduces the length of the line downstream of evaporation point 403. In one case, the liquid injector can be directly mounted to the mixing vessel 404. In another case, the liquid injector can be directly mounted to the nozzle 406.

[0107] In some embodiments, a flow controller may be provided upstream of the evaporation point 403 to control the evaporation and the mass flow rate of the liquid delivered to the treatment station 400. For example, the flow controller (LFC) may include a thermal mass flow meter (MFM) located downstream of the LFC. The LFC's plunger valve can then be adjusted in response to feedback control signals provided by a proportional-integral-derivative (PID) controller electrically communicating with the MFM. However, using feedback control may take a second or longer to stabilize the flow. This could prolong the dispensing time of the liquid reactants. Therefore, in some embodiments, the LFC may dynamically switch between a feedback control mode and a direct control mode. In some embodiments, the LFC may dynamically switch from a feedback control mode to a direct control mode by disabling the sensing tubes of both the LFC and the PID controller.

[0108] Nozzle 406 dispenses process gas to substrate 412. Figure 4 In the illustrated embodiment, the substrate 412 is located below the nozzle 406 and is shown resting on the base 408. It should be understood that the nozzle 406 can have any suitable shape and can have any suitable number and arrangement of ports for distributing process gases to the substrate 412.

[0109] In some implementations, the microvolume (not shown) is located below nozzle 406. Performing ALD and / or CVD processes in a microvolume within the processing station reduces reactant exposure and sweep time, decreases the time required to change process conditions (such as pressure, temperature, etc.), and limits the exposure of the processing station robot to process gases compared to performing ALD and / or CVD processes throughout the entire volume. Examples of microvolume sizes may include, but are not limited to, volumes between 0.1 liters and 2 liters. This microvolume also affects production yield. While the deposition rate per cycle is reduced, the cycle time is also reduced. In some cases, the latter effect is significant enough to improve the overall yield of modules targeting a specific film thickness.

[0110] In some embodiments, the base 408 may be raised or lowered to expose the substrate 412 to the microvolume and / or to change the volume of the microvolume. For example, during a substrate transfer phase, the base 408 may be lowered to allow the substrate 412 to be loaded onto the base 408. During a deposition process phase, the base 408 may be raised to place the substrate 412 within the microvolume. In some embodiments, the microvolume may completely surround the substrate 412 and a portion of the base 408 to create a region of high flow resistance during the deposition process.

[0111] Optionally, the base 408 may be lowered and / or raised during part of the deposition process to adjust the process pressure, reactant concentration, etc., within the microvolume. Lowering the base 408 allows the microvolume to be emptied while the treatment chamber 402 is maintained at a base pressure during deposition. Exemplary ratios of the microvolume's volume to the treatment chamber's volume may include, but are not limited to, ratios between 1:500 and 1:10. It should be understood that in some embodiments, the base height may be programmatically adjusted via a suitable computer controller.

[0112] In another scenario, adjusting the height of the pedestal 408 can alter the plasma density during plasma activation and / or process cycles included in the deposition process. Upon completion of a deposition process stage, the pedestal 408 can be lowered during another substrate transfer stage to allow removal of the substrate 412 from the pedestal 408.

[0113] While the exemplary microvolume changes described herein refer to a height-adjustable base, it should be understood that in some embodiments, the position of the nozzle 406 relative to the base 408 can be adjusted to change the volume of the microvolume. Furthermore, it should be understood that the vertical position of the base 408 and / or the nozzle 406 can be changed by any suitable mechanism within the scope of the invention. In some embodiments, the base 408 may include a rotation axis for rotating the orientation of the substrate 412. 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.

[0114] Back Figure 4 In the illustrated embodiment, nozzle 406 and base 408 are electrically connected to an RF power supply 414 and a matching network 416 for supplying energy to the plasma. In some embodiments, plasma energy can be controlled by controlling one or more of the following: processing station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, RF power supply 414 and matching network 416 can be operated at any suitable power to generate a plasma with a desired free radical composition. Examples of suitable power have been included in the paragraphs above. Similarly, RF power supply 414 can provide RF power at any suitable frequency. In some embodiments, RF power supply 414 can be used to independently control high-frequency and low-frequency RF power supplies. Examples of low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 500 kHz. Examples of high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It should be understood that any suitable parameters can be adjusted discretely or continuously to provide plasma energy for surface reactions. In a non-limiting example, the plasma power can be pulsed intermittently relative to a continuously powered plasma to reduce ion bombardment of the substrate surface.

[0115] In some implementations, the plasma can be monitored in situ using one or more plasma monitors. In one case, plasma power can be monitored using one or more voltage and current sensors (such as VI probes). In another case, plasma density and / or the concentration of process gases can be measured using one or more optical emission spectroscopy (OES) sensors. In some implementations, one or more plasma parameters can be programmed to adjust based on measurements from such in-situ monitors. For example, OES sensors can be used in the feedback loop of programmed control providing plasma power. It should be understood that in some implementations, other monitors can be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0116] In some embodiments, the plasma can be controlled via input / output control (IOC) sequence instructions. In one example, instructions for setting plasma conditions for a plasma process stage may be included in the corresponding plasma activation formulation stage of the deposition process formulation. In some cases, process formulation stages may be configured sequentially such that all instructions for the deposition process stage are executed synchronously with that process stage. In some embodiments, instructions for setting one or more plasma parameters may be included in a formulation stage preceding the plasma process stage. For example, a first formulation stage may include instructions for setting the flow rates of the inert gas and / or reactant gas, instructions for setting the plasma generator to a power setpoint, and time delay instructions for the first formulation stage. A subsequent second formulation stage may include instructions for activating the plasma generator and time delay instructions for the second formulation stage. A third formulation stage may include instructions for deactivating the plasma generator and time delay instructions for the third formulation stage. It should be understood that these formulation stages may be further subdivided and / or repeated in any suitable manner within the scope of the invention.

[0117] In some deposition processes, plasma ignition lasts on the order of several seconds or longer. In some implementations, even shorter plasma ignitions can be used. These can be on the order of 10 ms to 1 second, typically around 20 to 80 ms, with one specific example being 50 ms. This very short RF plasma ignition requires extremely fast plasma stabilization. To achieve this, the plasma generator can be configured such that impedance matching is pre-set to a specific voltage while allowing frequency fluctuation. Typically, high-frequency plasma is generated at an RF frequency of approximately 13.56 MHz. In the various embodiments disclosed herein, frequency fluctuations are allowed to values ​​different from this standard value. By allowing frequency fluctuation while fixing the impedance matching to a predetermined voltage, the plasma can stabilize more quickly, a result that can be important when using very short plasma ignitions associated with certain types of deposition cycles.

[0118] In some embodiments, the temperature of the base 408 can be controlled by the heater 410. Additionally, in some embodiments, pressure control of the deposition processing station 400 can be provided via a butterfly valve 418. Figure 4 As shown in the implementation, butterfly valve 418 can regulate the vacuum provided by a downstream vacuum pump (not shown). However, in some implementations, the pressure control of processing station 400 can be adjusted by changing the flow rate of one or more gases introduced into processing station 400.

[0119] In some implementations, instructions for the controller 450 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process stage may be included in the corresponding formulation stage of the process formulation. In some cases, process formulation stages may be configured sequentially such that all instructions for a process stage are executed synchronously with that process stage. In some implementations, instructions for setting one or more reactor parameters may be included in the formulation stage. For example, a first formulation stage may include instructions for setting the flow rate of a silicon-containing precursor gas, instructions for setting the flow rate of a carrier gas (e.g., argon), and time delay instructions for the first formulation stage. A second formulation stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gases, instructions for optionally heating, instructions for setting the flow rate of a carrier gas (e.g., argon), and time delay instructions for the second formulation stage.

[0120] The subsequent third formulation stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gases, instructions for adjusting the flow rate of the second silicon-containing precursor, and time delay instructions for the third formulation stage. The fourth formulation stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gases, instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fourth formulation stage. The subsequent fifth formulation stage may include instructions for setting the flow rate of nitrogen-containing gas, instructions for igniting the plasma, instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fifth formulation stage.

[0121] The sixth formulation stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gases, instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the sixth formulation stage. It should be understood that these formulation stages may be further divided and / or repeated in any suitable manner within the scope of this disclosure. In some embodiments, the controller 450 may include the following regarding... Figure 5 Any of the features described in the system controller 550.

[0122] Figure 5 A schematic view of an embodiment of a multi-station processing tool 500 is shown, having an inbound loading lock 502 and an outbound loading lock 504, one or both of which may contain a remote plasma source. An atmospheric pressure manipulator 506 is configured to move a wafer from a cassette loaded via a carrier 508 through an atmospheric port 510 into the inbound loading lock 502. The wafer is placed on a base 512 within the inbound loading lock 502 by the manipulator 506, the atmospheric port 510 is closed, and the loading lock is evacuated. When the inbound loading lock 502 contains a remote plasma source, the wafer can be exposed to remote plasma processing within the loading lock before being introduced into the processing chamber 514. Additionally, the wafer can also be heated within the inbound loading lock 502, for example, to remove moisture and adsorbed gases. Next, the chamber transfer port 516 leading to the processing chamber 514 is opened, and another robotic arm (not shown) places the wafer into the reactor on the base of the first station shown in the reactor for processing. Although in Figure 5 The implementation shown in the figure includes a loading lock, but it should be understood that in some implementations, the substrate can be allowed to go directly into the processing station.

[0123] The drawn processing room 514 contains 4 processing stations. Figure 5The embodiments shown are numbered 1 to 4. Each station has a heated base (shown as 518 for station 1) and a gas line inlet. It should be understood that in some embodiments, each processing station may have different or multiple uses. Although the drawn processing chamber 514 contains four stations, it is to be understood that a processing chamber according to this disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments, a processing chamber may have three or fewer stations.

[0124] Figure 5 Some embodiments of a wafer handling system 590 for transferring wafers within processing chamber 514 are also depicted. In some embodiments, the wafer handling system 590 can transfer wafers between various processing stations and / or between a processing station and a loading lock. It should be understood that any suitable wafer handling system can be employed. Non-limiting examples include wafer turntables and robotic arms for handling wafers. Figure 5 An implementation scheme for a system controller 550 used to control the process conditions and hardware status of the processing tool 500 is also illustrated. The system controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 may include a computer or CPU, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0125] In some implementations, system controller 550 controls all activities of processing tool 500. System controller 550 executes system control software 558 stored in mass storage device 554, load memory device 556, and executed by processor 552. System control software 558 may contain instructions for controlling timing, gas mixing, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power level, RF frequency, substrate, pedestal, chuck and / or pedestal position, and other parameters for specific processes performed by processing tool 500. System control software 558 may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be written to control the operation of processing tool components necessary to perform various processing tool processes according to the disclosed methods. System control software 558 may be coded in any suitable computer-readable programming language.

[0126] In some embodiments, system control software 558 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of the plasma-enhanced ALD (PEALD) process may include one or more instructions executed by system controller 550. Instructions for setting the process conditions for a PEALD process stage may be included in the corresponding PEALD formulation stage. In some embodiments, the PEALD formulation stages may be scheduled sequentially so that all instructions for a PEALD process stage are executed simultaneously with that process stage.

[0127] In some implementations, other computer software and / or programs associated with system controller 550 and stored in mass storage device 554 and / or memory device 556 may be employed. Examples of programs or program segments used for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0128] The substrate positioning procedure may include program code for a processing tool assembly that loads the substrate onto the base 518 and controls the spacing between the substrate and other parts of the processing tool 500.

[0129] The process gas control program may include code for controlling the gas composition and flow rate, and optionally code for stabilizing the pressure in one or more processing stations before deposition. The process gas control program may include code for controlling the gas composition and flow rate within any publicly disclosed range. The pressure control program may include code for controlling the pressure within the processing station by adjusting, for example, throttling valves in the processing station's exhaust system, the gas flow into the processing station, etc. The pressure control program may include code for maintaining the pressure in the processing station within any publicly disclosed pressure range.

[0130] The heater control program may contain code for controlling the current flowing to the heating element used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) toward the substrate. The heater control program may include instructions to maintain the temperature of the substrate within any publicly disclosed range.

[0131] The plasma control program may include code for setting the RF power level and frequency applied to the processing electrodes in one or more processing stations, such as code for using any RF power level disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0132] In some implementations, a user interface may be associated with the system controller 550. The user interface may include a display screen, a graphical software display of the device and / or process conditions, and user input devices such as clicking devices, keyboards, touch screens, microphones, etc.

[0133] In some implementations, the parameters regulated by the system controller 550 relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF power level, frequency, and exposure time), etc. These parameters can be provided to the user in the form of a recipe, which can be input using the user interface.

[0134] Signals used for monitoring the process can be provided from various processing tool sensors via analog and / or digital input connections of system controller 550. Signals used for controlling the process can be output via analog and digital output connections of processing tool 500. Non-limiting examples of processing tool sensors that can be monitored include mass flow controllers, pressure sensors (e.g., pressure gauges), thermocouples, and the like. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0135] The disclosed implementation scheme can be implemented using any suitable chamber. Exemplary deposition apparatuses include, but are not limited to, devices from the ALTUS®, VECTOR®, and / or SPEED® product families (each available from Lam Research Corp. (Fremont, California)) or any other various commercially available processing systems. Two or more stations can perform the same function. Similarly, two or more stations can perform different functions. Each station can be designed / configured to perform specific functions / methods as needed.

[0136] In some implementations, the controller is part of a system, which may be part of the examples described above. Such a system may 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 may be integrated with electronics for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. The electronics may 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 system type, the controller may be programmed to control any process 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 in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer tools and other transfer tools, and / or loading locks that are connected to or docked with a specific system.

[0137] In a broad sense, a controller can be defined as an electronic device having various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, enabling cleaning operations, enabling endpoint measurements, etc. Integrated circuits can include chips in the form of firmware storing program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions can be instructions sent to the controller in the form of various individual settings (or program files), which define operating parameters for performing a specific process on or for a semiconductor wafer or system. In some embodiments, 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 layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0138] In some implementations, the controller may be part of or coupled to a computer integrated with, coupled to, or otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or be all or part of a fab host system, allowing remote access to wafer processing. The computer may 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 of multiple manufacturing operations, change parameters of the current process, set processing steps to follow the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system via a network (which may include a local network or the Internet). The remote computer may 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, the controller receives instructions in the form of data specifying parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool, to which the controller is configured to interface with or control the tool. Therefore, as described above, a controller can be distributed, for example, by comprising one or more discrete controllers networked together and operating toward a common purpose (such as the process and control described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on-site communicating with one or more integrated circuits remotely (e.g., at the platform level or as part of a remote computer), which together control the process on-site.

[0139] Exemplary systems may include, but are not limited to, plasma etching chambers or modules, deposition chambers or modules, rotary rinsing chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfering edge etching chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etching (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing systems that may be associated with or used for the manufacture and / or preparation of semiconductor wafers.

[0140] As described above, depending on one or more processing steps to be performed by the tool, the controller may 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 plant, a host computer, another controller, or tools used in the transport of materials to and from the tool location and / or loading port in the semiconductor manufacturing plant.

[0141] The apparatus / process described herein can be used in conjunction with photolithography patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, although not necessarily, these tools / processes will be used together or operated in a common manufacturing facility. Photolithography patterning of films typically involves some or all of the following operations, each of which enables multiple feasible tools: (1) applying a photoresist to a workpiece, i.e., a substrate, using a spin coater or spray coater; (2) curing the photoresist using a hot plate or oven or a UV curing tool; (3) exposing the photoresist to visible light or UV or X-rays using a tool such as a wafer stepper; (4) developing the photoresist to selectively remove the photoresist and thereby pattern it using a tool such as a wet cleaning station; (5) transferring the photoresist pattern to the underlying film or workpiece using a dry or plasma-assisted etching tool; and (6) removing the photoresist using a tool such as an RF or microwave plasma stripper.

[0142] definition "Aliphatic" refers to a group of organisms with at least one carbon atom to 50 carbon atoms (C). 1-50 Hydrocarbon groups, such as those with 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 Aliphatic hydrocarbons, comprising alkanes (or alkyl groups), alkenes (or alkenyl groups), alkynes (or alkynyl groups), including their cyclic forms, and further comprising straight-chain and branched arrangements, as well as all stereo and positional isomers. Such aliphatic hydrocarbons may be unsubstituted or substituted with one or more groups, such as the groups described herein for alkyl groups.

[0143] "Alkenyl" refers to a group having at least two to 50 carbon atoms (C20-C50). 2-50 (For example, two to 25 carbon atoms (C) 2-25 ), or two to ten carbon atoms (C 2-10 The alkenyl group comprises an unsaturated monovalent hydrocarbon with at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon is derived from a carbon atom of a parent alkene by removing a hydrogen atom. The alkenyl group can be branched, linear, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyl groups comprise optionally substituted C atoms having one or more double bonds. 2-24 Alkyl groups. Alkenyl groups can be monovalent or polyvalent (e.g., divalent), formed by the removal of one or more hydrogens to create a suitable connection with a parent molecule group or between a parent molecule group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0144] "Alkenylene" refers to the polyvalent (e.g., divalent) form of an alkenyl group (as defined herein). Alkenylene can be substituted or unsubstituted. For example, alkenylene can be substituted with one or more substituents (as described herein with respect to alkyl groups).

[0145] "alkyl" refers to a compound having at least one carbon atom to 50 carbon atoms (C60). 1-50 (e.g., 1 to 25 carbon atoms (C) 1-25 ), or 1 to 10 carbon atoms (C 1-10 The alkyl group is a saturated monovalent hydrocarbon, wherein the saturated monovalent hydrocarbon is derived from a parent compound (e.g., an alkane) by removing a hydrogen atom from a carbon atom. The alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). Exemplary alkyl groups comprise branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogen atoms to form a suitable link with a parent molecule group or a suitable link between a parent molecule group and another substituent. For example, an alkyl group may be substituted with one, two, three, or (in the case of an alkyl group having two or more carbons) four substituents, the substituents being independently selected from the group consisting of: (1) C 1-6 Alkoxy groups (e.g., -OR, where R is C) 1-6 (2)C alkyl); 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C) 1-6 Alkyl); (3)C 1-6 Alkyl sulfonyl (e.g., -SO2-R, where R is C) 1-6 (4) Alkyl); (e.g., -C(O)NR 1 R 2 or -NHCOR 1 , where R 1 With R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof, or R, as defined herein. 1 With R 2(5) aryl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryl acyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 (12) Cycloalkyl; (13) Halogen; (14) Heterocyclic group (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein); (15) Heterocyclic oxy group (e.g., -OR, where R is a heterocyclic group as defined herein); (16) Heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (17) Hydroxyl group (e.g., -OH); N - Protected amino group; (18) Nitro group (e.g., -NO2); (19) Oxyl group (e.g., =O); (20) C 1-6 (21) Thioalkoxy (e.g., -SR, where R is an alkyl group); (22) Thiol group (e.g., -SH); (23) -CO2R 1 , where R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (23)-C(O)NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (24)-SO2R 1 , where R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b)C 4-18 Aryl and (c)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18(Aryl); (25)-SO2NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); and (26)-SiR 1 R 2 R 3 , where R 1 and R 2 and R 3 Each is independently selected from the group consisting of: (a) hydrogen, (b) halogens (e.g., F, Cl, Br, or I), (c) C 1-6 Alkyl, (d)C 2-6 alkenyl, (e) C 2-6 alkynyl group, or (f) C 1-6 Alkoxy groups (e.g., -OR, where R is C) 1-6 alkyl); and (27)-NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) N -Protective group, (c)C 1-6 Alkyl, (d)C 2-6 alkenyl, (e)C 2-6 alkynyl group, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl group, where R is C 4-18 Aryl), (h)C 3-8 cycloalkyl groups, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 3-8 The alkyl group is a cycloalkyl group, wherein in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C10. 1-3 C1-6 C 1-12 C 1-16 C 1-18 C 1-20 Or C 1-24 alkyl.

[0146] "alkylene" refers to the polyvalent (e.g., divalent) form of an alkyl group (as described herein). Exemplary alkylenes include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene is C10. 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 216 C 2-18 C 2-20 or C 2-24 Alkylenes. Alkylenes can be branched or straight-chain. Alkylenes can also be substituted or unsubstituted. For example, an alkylene can be substituted with one or more substituents (as described herein with respect to alkyl groups).

[0147] “alkyleneoxy” refers to an alkylene group (as defined herein) that is attached to a parent molecule group via an oxygen atom.

[0148] "Alkynyl" refers to a group having at least two to 50 carbon atoms (C20-C50). 2-50 (For example, two to 25 carbon atoms (C) 2-25 ), or two to ten carbon atoms (C 2-10 And an unsaturated monovalent hydrocarbon with at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from a parent alkyne by removing a hydrogen atom from a carbon atom. The alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). An exemplary alkynyl group comprises an optionally substituted C with one or more triple bonds. 2-24 Alkyl groups. Alkynyl groups can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or polyvalent (e.g., divalent), formed by the removal of one or more hydrogens to create a suitable link with a parent molecule group or a suitable link between a parent molecule group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, an alkynyl group can be substituted with one or more substituents, as described herein with respect to alkyl groups.

[0149] "alkynylene" refers to the polyvalent (e.g., divalent) form of an alkynyl group (as defined herein). Alkynyne groups can be substituted or unsubstituted. For example, an alkynylene group can be substituted with one or more substituents (as described herein with respect to alkyl groups).

[0150] "Aromatic" means a cyclic conjugated group or portion having 5 to 15 (unless otherwise specified) ring atoms of a monocyclic (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized π-electron system. Typically, the number of out-of-plane π electrons corresponds to Huckel's rule (4n+2). The connection point with the parent structure is typically through the aromatic portion of the fused ring system. Such aromatic groups can be unsubstituted or substituted with one or more groups, such as the groups described herein for alkyl or aryl groups. Other substituents may include aliphatic, haloaliphatic, halogen, nitrate, cyano, sulfonate, sulfonyl, or others.

[0151] "Aryl" refers to a compound containing at least five to 15 carbon atoms (C64- ... 5-15 (For example, five to ten carbon atoms (C) 5-10 The aryl group is an aromatic carbocyclic group having a monocyclic or multiple fused rings, the fused rings being or not aromatic, provided that the connection point with the remaining positions of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen (e.g., aliphatic, heteroaliphatic, aromatic, other functional groups or any combination thereof). Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur and phosphorus. Similarly, the term non-heteroaryl, also included in the term aryl, is defined as a group containing an aromatic group and not containing a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four or five substituents, the substituents being independently selected from the group consisting of: (1) C 1-6 Alkyl groups (e.g., -C(O)-R, where R is C) 1-6 (2)C alkyl); 1-6 Alkyl; (3)C 1-6 Alkoxy groups (e.g., -OR, where R is C) 1-6 Alkyl); (4)C 1-6 Alkoxy-C 1-6 Alkyl groups (e.g., -LOR, where L and R are each independently C).1-6 Alkyl); (5)C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C) 1-6 Alkyl); (6)C 1-6 alkylsulfinyl-C 1-6 Alkyl groups (e.g., -LS(O)-R, where L and R are each independently C). 1-6 Alkyl); (7)C 1-6 Alkyl sulfonyl (e.g., -SO2-R, where R is C) 1-6 Alkyl); (8)C 1-6 alkylsulfonyl-C 1-6 Alkyl groups (e.g., -L-SO2-R, where L and R are each independently C). 1-6 (9) alkyl; (10) aryl; (e.g., -NR) 1 R 2 , where R 1 With R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 Together with the nitrogen atoms to which they are attached, they form heterocyclic groups 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 L 1 C 1-6 Alkyl; L 2 For covalent bonds or C 1-6 Alkyl; R 1 With R 2 Each is independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 Together with the nitrogen atoms to which they are attached, they form heterocyclic groups as defined herein; R 3 With R 4 Each independently is H or C 1-6 (12) Alkyl group; (13) Heteroaryl group; (14) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18(14) Aryl (e.g., -C(O)-R, where R is aryl); (15) Azide (e.g., -N3); (16) Cyano (e.g., -CN); (17) C 1-6 Azide alkyl groups (e.g., -L-N3, where L is C) 1-6 (18) Alkyl); (e.g., C(O)H); (19) Alkyl-C 1-6 Alkyl groups (e.g., -LC(O)H, where L is C) 1-6 Alkyl); (20)C 3-8 cycloalkyl; (21)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 3-8 (22) cycloalkyl; (23) halogen; (24) C 1-6 Haloalkyl (e.g., -L) 1 -X or -L 2 -C(X)(R 1 )-R 2 L 1 C 1-6 Alkyl; L 2 For covalent bonds or C 1-6 Alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 With R 2 Each independently is H or C 1-6 (24) Alkyl group; (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein); (25) Heterocyclic group (e.g., -OR, where R is a heterocyclic group as defined herein); (26) Heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (27) Hydroxyl group (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L) 1 -OH or -L 2 -C(OH)(R 1 )-R 2 L 1 C 1-6 Alkyl; L 2 It is covalent or alkyl; and R 1 With R 2 Each independently represents H or C as defined in this article. 1-6 (29) alkyl; (30) nitro; 1-6 Nitroalkyl (e.g., -L) 1 -NO or -L 2 -C(NO)(R 1 )-R, where L 1C 1-6 Alkyl; L 2 It is covalent or alkyl; and R 1 With R 2 Each independently represents H or C as defined in this article. 1-6 Alkyl); (31) N - Protected amino groups; (32) N -Protective amino-C 1-6 Alkyl group; (33) oxo group (e.g., =O); (34) C 1-6 Thioalkoxy groups (e.g., -SR, where R is C) 1-6 Alkyl); (35) Thio-C 1-6 Alkoxy-C 1-6 Alkyl groups (e.g., -LSR, where L and R are each independently C). 1-6 Alkyl); (36)-(CH2) r CO2R 1 Where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (37)-(CH2) r CONR 1 R 2 , where r is an integer from 0 to 4, and R 1 With R 2 Each of the following groups can be selected independently: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (38)-(CH2) r SO2R 1 , where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b)C 4-18 Aryl and (c)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18(Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4 and R 1 With R 2 Each of the following groups can be selected independently: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4 and R 1 With R 2 Each of the following groups is independently selected: (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 alkenyl, (e)C 2-6 alkynyl group, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 cycloalkyl groups, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 3-8 (41) a thiol (e.g., -SH); (42) a perfluoroalkyl group (e.g., -(CF2)nCF3, where n is an integer from 0 to 10); (43) a perfluoroalkoxy group (e.g., -O-(CF2)nCF3, where n is an integer from 0 to 10); (44) an aryloxy group (e.g., -OR, where R is aryl); (45) a cycloalkoxy group (e.g., -OR, where R is cycloalkyl); (46) a cycloalkylalkoxy group (e.g., -OLR, where L is alkyl and R is cycloalkyl); (47) an arylalkoxy group (e.g., -OLR, where L is alkyl and R is aryl); and (48) a -SiR group. 1 R 2 R 3 , where R 1 and R 2 and R 3Each is independently selected from the group consisting of: (a) hydrogen, (b) halogens, such as F, Cl, Br, or I, and (c) C. 1-6 Alkyl, (d)C 2-6 alkenyl, (e) C 2-6 alkynyl group, or (f)C 1-6 Alkoxy groups (e.g., -OR, where R is C) 1-6 Alkyl group). In a particular embodiment, the unsubstituted aryl group is C10. 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 or C 6-10 Aryl.

[0152] "Arylene" refers to the polyvalent (e.g., divalent) form of an aromatic group (as described herein). Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthraceneyl, or phenanthrene. In some embodiments, the arylene group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 Or C6-10 arylene groups. Aromatic groups can be branched or straight-chain. Aromatic groups can also be substituted or unsubstituted. For example, an arylene group can be substituted by one or more substituents (as described herein with respect to aryl groups).

[0153] “Aryleneoxy” refers to an arylene group attached to a parent molecule group via an oxygen atom (as defined herein).

[0154] A "covalent bond" refers to the covalent interaction between two components. Non-restrictive covalent bonds include single bonds, double bonds, triple bonds, or spirocyclic bonds, in which at least two molecular groups are bonded to the same carbon atom.

[0155] "Cycloaliphatic" means an aliphatic group as defined herein, which is cyclic. The cycloaliphatic group may be saturated or unsaturated.

[0156] “Cycloalkyl” means a monovalent, saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbon atoms (unless otherwise specified), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclic [2.2.1. heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group can be substituted with one or more groups, including those described herein as alkyl.

[0157] "Cycloheteroaliphatic" refers to cyclic heteroaliphatic groups (as defined herein). Such cyclic heteroaliphatic groups can be saturated or unsaturated.

[0158] “Cycloheteroalkyl” refers to a monovalent, saturated or unsaturated, non-aromatic cyclic hydrocarbon group consisting of three to eight carbon atoms, and containing at least one heteroatom, which may be selected from (but is not limited to) oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms. Cycloheteroalkyl groups may also be substituted or unsubstituted. For example, a cycloheteroalkyl group may be substituted with one or more groups (including those described herein with respect to alkyl groups).

[0159] "Halogenated" refers to F, Cl, Br, or I.

[0160] "Heteroaliphatic" means an aliphatic group as defined herein that contains from at least one heteroatom to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 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.

[0161] “Heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” respectively mean an alkyl, alkenyl, or alkynyl group as defined herein (which may be branched, linear, or cyclic) containing from at least one to 20 heteroatoms (e.g., 1 to 15 heteroatoms or 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. Heteroalkyl, alkenyl, and / or alkynyl groups may also be substituted or unsubstituted. For example, a heteroalkyl, alkenyl, and / or alkynyl group may be substituted with one or more groups (including those described herein with respect to alkyl).

[0162] “Heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” refer to an alkylene, alkenylene, or alkynylene group (as defined herein) comprising at least one to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which may be branched, linear, or cyclic, and the heteroatoms may be selected from (but are not limited to) oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms. Heteroalkylene, heteroalkenylene, and / or heteroalkynylene may also be substituted or unsubstituted. For example, a heteroalkylene, heteroalkenylene, and / or heteroalkynylene may be substituted with one or more groups (including those described herein with respect to alkyl).

[0163] "Heterocyclic group" means a 3, 4, 5, 6, or 7-membered ring (e.g., a 5, 6, or 7-membered ring) that, unless otherwise specified, contains one, two, three, or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, selenium, or halogen). A 3-membered ring has zero to one double bond, 4- and 5-membered rings have zero to two double bonds, and 6- and 7-membered rings have zero to three double bonds. The term "heterocyclic group" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of the aforementioned heterocycles is fused to one, two, or three rings independently selected from aromatic rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and another monocyclic heterocycle (e.g., indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothiophene, etc.). Heterocyclic compounds include acridinyl, adenyl, alloxazinyl, azaadamantanyl, and azabenzimidazolyl. Azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azapanyl, azapinyl, azatidinyl, azatyl, aziridinyl, azirinyl, azocanyl, azoocinyl, azaonanyl, benzimidazole Benzidazolyl, benzozisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinylbenzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazepinyl zolyl), benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazepinyl benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl l), benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsulfonyl, benzylsulfonylimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl),Chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazabicyclobutadieneyl, diaziridinethionyl, diazabicyclooctyl Diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl) Dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolyl nyl), dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxxiranyl, dioxenyl, dioxxinylDioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, mepirazinyl homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazole), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatyl inyl), indigoyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolilyl, isoquinolinyl, isoquinoli nyl), isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, diazanaphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolylNaphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl ), oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, p-phenanthrinyl henanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, pipeidinyl Piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinylPyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrryl), pyrylium, quinazolinyl zolinyl), quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl ydrofuranyl), tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetraazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H) -1,5,2-Dithiadiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienylThiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyranone ronyl), thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, etc. ， And its modified forms (e.g., including one or more oxo groups and / or amino groups) and their salts. Heterocyclic groups can be substituted or unsubstituted. For example, a heterocyclic group can be substituted by one or more substituents (such as those described herein with respect to aryl groups).

[0164] "Heterocyclyldiyl" refers to the divalent form of a heterocyclic group (as described herein). In one example, a heterocyclyldiyl is formed by removing a hydrogen atom from the heterocyclic group. Exemplary heterocyclyldiyl groups include piperdylidene, quinolinediyl, etc. Heterocyclyldiyl groups can also be substituted or unsubstituted. For example, a heterocyclyldiyl group can be substituted with one or more substituents (as described herein with respect to heterocyclic groups).

[0165] The term "independent selection" (when referring to the selection of R substituents in a molecule containing multiple R groups) means that the selection of R substituents at different atoms of the molecule is independent, and the selection of R substituents at a single atom with multiple R substituents is also independent.

[0166] "Substituted" means having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents include, but are not limited to, alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonate, cyano, halogen, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylic acid, dithiocarboxylic acid, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclic, ether, ester, silicon-containing moiety, thioester, or combinations thereof. The substituent itself can be substituted. For example, the amino substituent itself may be monosubstituted or independently disubstituted by other substituents as defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic rings).

[0167] Those skilled in the art will understand that the definitions provided above are not intended to include unacceptable substitution patterns (e.g., a methyl group substituted with five different groups). Such unacceptable substitution patterns are readily identifiable by those skilled in the art. Any functional groups disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise stated herein.

[0168] As used herein, the term “about” should be understood to take into account minor increases and / or decreases beyond the value, changes that do not significantly affect the desired function of the parameter beyond the value. In some cases, “about” covers a difference of + / - 10% from any of the stated values. As used herein, this term modifies any stated value, a range of values, or the endpoints of one or more ranges.

[0169] The term "atomic layer deposition" (ALD) generally refers to a process in which a film is formed on a substrate in the form of one or more individual layers by sequentially adsorbing precursors onto the substrate and then chemically converting the adsorbed precursors to form a film layer. Examples of ALD processes include plasma-enhanced ALD (PEALD) and thermal ALD (TALD). PEALD and TALD utilize plasma and heat of reactive gases, respectively, to promote the chemical conversion of precursors adsorbed onto the substrate into a film on the substrate. The terms "growth," "deposition," and variations thereof can also be used to refer to film formation.

[0170] The terms “atomic layer deposition cycle” and “ALD cycle” generally refer to a single cycle in which a chemical precursor is adsorbed onto a substrate surface and then chemically converted to form a film on the substrate.

[0171] The term "dielectric film" generally refers to a layer of insulating material that can be polarized by applying an electric field. Exemplary dielectric films include silicon oxide (SiO2), silicon nitride (Si3N4), and silicon oxynitride (Si3N2). 4(1-x) O 6x ), silicon carbide (SiC), silicon oxycarbide (SiO) 2(1-x) C x Aluminum nitride (AlN), aluminum oxide (Al2O3), tin oxide (e.g., SnO, SnO2), gallium nitride (GaN), boron nitride (BN), and gallium arsenide (GaAs) films.

[0172] The term "doping" and its variations generally refer to the introduction of impurities into a material to modify one or more physical properties. The term "dopant" generally refers to a chemical substance introduced as an impurity into another material during a doping process.

[0173] The term "flow control hardware" broadly refers to components configured to fluidly communicate one or more chemical sources with a processing chamber. Flow control hardware may include, for example, one or more mass flow controllers and / or valves. Exemplary chemical sources include dielectric film precursor sources, halogen-containing precursor sources, reactant gas sources, and inert gas sources.

[0174] The term "forming a gas mixture" generally refers to mixing multiple gases before introducing them into the processing chamber, or mixing any one or both of multiple gases in the processing chamber.

[0175] The term "inert gas" generally refers to a gaseous material that does not react with other chemicals in the processing chamber during substrate processing. Exemplary inert gases include helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe), as well as nitrogen (N2) in some processes.

[0176] The term "plasma" generally refers to a gas containing cations, free radicals, and free electrons. The term "in-situ plasma" generally refers to plasma formed at a processing station within a processing chamber. The term "remote plasma" generally refers to plasma formed at a location far from a processing station within a processing chamber.

[0177] The term "plasma generator" generally refers to a combination of components that can be used to form a plasma. Exemplary components include a radio frequency power source, an impedance matching network, and one or more electrodes.

[0178] The term "precursor" generally refers to a chemical substance adsorbed onto the substrate surface during the ALD process. The precursor reacts with reactants to convert the adsorbed precursor into a film.

[0179] The term "process chamber" or "process room" generally refers to an enclosure in which chemical and / or physical processes are performed on a substrate. The pressure, substrate temperature, and atmospheric composition within the process chamber can be controlled to perform chemical and / or physical processes.

[0180] The term "processing equipment" can generally refer to a machine that includes a processing chamber and other hardware configured to enable processing to be performed in the processing chamber.

[0181] The term "processing station" generally refers to the location of the substrate within a processing chamber during processing.

[0182] The term "reactant" generally refers to a chemical substance that reacts with a precursor adsorbed onto the substrate surface in an ALD process to form a film. In various processes, the reaction between the reactant and the precursor can be facilitated by thermal energy and / or plasma.

[0183] As used herein, the term "semiconductor substrate" or "substrate" refers to a substrate at any stage of semiconductor device fabrication containing semiconductor material located anywhere within its structure. It is understood that the semiconductor material in the semiconductor substrate does not need to be exposed. An example of a semiconductor substrate is a semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material. The detailed description below assumes that the disclosed implementations are carried out on a semiconductor wafer (e.g., on a 200mm, 300mm, or 450mm semiconductor wafer). However, these disclosed implementations are not limited thereto. Workpieces can be of various shapes, sizes, and materials. Besides semiconductor wafers, other types of workpieces that can utilize these disclosed implementations include various articles of manufacture, such as printed circuit boards.

[0184] The term "through-substrate via" generally refers to a conductive path in an integrated circuit that extends through a semiconductor substrate.

[0185] The terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” used in this article are used to provide relative relationships between structures. Using these terms does not indicate or require that a particular structure must be located in a specific position within the apparatus.

[0186] in conclusion This document refers in detail to specific embodiments of this disclosure. Examples of specific embodiments are depicted in the accompanying drawings. While this disclosure will be described in conjunction with these specific embodiments, it should be understood that this disclosure should not be limited to these specific embodiments. Rather, it should include substitutions, modifications, and equivalents that fall within the spirit and scope of this disclosure. In the following description, certain specific details are set forth to provide a thorough understanding of this disclosure. This disclosure may be practiced without some or all of these specific details. In other instances, routine processing procedures have not been described in detail so as not to unnecessarily obscure this disclosure.

[0187] While the foregoing embodiments have been described in detail for clarity of purpose, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. The embodiments disclosed herein may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to avoid unnecessarily obscuring the disclosed embodiments. Furthermore, although the disclosed embodiments have been described in conjunction with specific embodiments, it should be understood that the specific embodiments are not intended to limit the disclosed embodiments. It should be noted that there are many alternative processes, systems, and apparatuses for implementing these embodiments. Therefore, these embodiments should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method for preparing a substrate, the substrate being used for metal film deposition, the method comprising: Substrate is provided in the processing chamber; The substrate is exposed to a reducing agent to obtain a reduced substrate; as well as The reduced substrate is exposed to an inhibitor to obtain a pretreated substrate.

2. The method according to claim 1, wherein the inhibitor comprises a silicon-containing inhibitor or an oxygen-containing inhibitor.

3. The method according to claim 2, wherein the silicon-containing inhibitor comprises a head group containing at least one Si-H group and a tail group containing an organic portion.

4. The method according to claim 3, wherein the head group comprises -SiH3.

5. The method of claim 3, wherein the silicon-containing inhibitor comprises RSiHX. 1 X 2 R is the organic part; and X 1 and X 2 Each of them is independently hydrogen, halogen, optionally substituted aliphatic group, optionally substituted cycloaliphatic group, or optionally substituted aromatic group.

6. The method of claim 5, wherein X 1 and X 2 Each of them is independently a optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, or optionally substituted aryl.

7. The method of claim 3, wherein the organic portion is or comprises an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted cycloaliphatic group, an optionally substituted cyclohexaphatic group, an optionally substituted aromatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroalkyl group, an optionally substituted heteroalkenyl group, an optionally substituted heteroalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted cyclohexaalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

8. The method of claim 3, wherein the organic portion is or comprises a branched hydrocarbon group, or the organic portion comprises one or more halogen substituents, or the organic portion is or comprises a branched hydrocarbon group and comprises one or more halogen substituents; or wherein the organic portion comprises 6 to 20 carbon atoms in a straight-chain, branched, or cyclic group.

9. The method of claim 3, wherein the organic portion is or includes -XLZ, and wherein: X is a covalent bond, optionally substituted alkylene, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted heteroalkylene, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted aryl, optionally substituted aryloxy, or optionally substituted heterocyclic diester. L represents a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1 -、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S- or -O-; Z is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted ynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroynyl, optionally substituted aryl, or optionally substituted heterocyclic; and R 1 and R 2 Each of them is independently hydrogen or optionally a substituted alkyl group.

10. The method of claim 2, wherein the oxygen-containing inhibitor comprises acetylacetone.

11. The method of claim 1, wherein exposing the substrate to a reducing agent or exposing the reduced substrate occurs in a plasma, and the plasma is a remote plasma or a direct plasma.

12. The method according to claim 1, wherein the reducing agent comprises a nitrogen-containing reagent or a hydrogen-containing reagent.

13. The method of claim 12, wherein the nitrogen-containing reagent comprises nitrogen, ammonia, hydrazine, azide, or a combination thereof.

14. The method of claim 12, wherein the hydrogen-containing reagent comprises hydrogen, methane, acetylene, or water.

15. The method of claim 1, wherein the metal comprises tantalum, titanium, molybdenum, cobalt, indium, or ruthenium.

16. The method according to claim 1, wherein the metal-containing film comprises tantalum nitride, indium oxide, tungsten nitride, or titanium nitride.

17. A method for processing a substrate, comprising: Substrate is provided in the processing chamber; The substrate is exposed to a reducing agent to obtain a reduced substrate; The reduced substrate is exposed to an inhibitor to obtain a pretreated substrate; A metal-containing precursor is supplied to the processing chamber to obtain a metal-containing film on the pretreated substrate; as well as Optionally, the metal-containing film is post-treated with plasma to remove the inhibitor.

18. The method of claim 17, wherein the inhibitor comprises a silicon-containing inhibitor or an oxygen-containing inhibitor.

19. The method of claim 18, wherein the silicon-containing inhibitor comprises a head group containing at least one Si-H group and a tail group containing an organic moiety.

20. The method of claim 19, wherein the head group comprises -SiH3.

21. The method of claim 18, wherein the silicon-containing inhibitor comprises RSiHX. 1 X 2 R is the organic part; and X 1 and X 2 Each of them is independently hydrogen, halogen, optionally substituted aliphatic group, optionally substituted cycloaliphatic group, or optionally substituted aromatic group.

22. The method of claim 21, wherein X 1 and X 2 Each of them is independently a optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, or optionally substituted aryl.

23. The method of claim 19, wherein the organic portion is or comprises an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted cycloaliphatic group, an optionally substituted cyclohexaphatic group, an optionally substituted aromatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted heteroalkyl group, an optionally substituted heteroalkenyl group, an optionally substituted heteroalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted cyclohexaalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

24. The method of claim 19, wherein the organic portion is or comprises a branched hydrocarbon group, or the organic portion comprises one or more halogen substituents, or the organic portion is or comprises a branched hydrocarbon group and comprises one or more halogen substituents; or wherein the organic portion comprises 6 to 20 carbon atoms in a straight-chain, branched, or cyclic group.

25. The method of claim 19, wherein the organic portion is or includes -XLZ, and wherein: X is a covalent bond, optionally substituted alkylene, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted heteroalkylene, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted aryl, optionally substituted aryloxy, or optionally substituted heterocyclic diester. L represents a covalent bond, -CR 1 R 2 -、-CR 1 =CR 2 -、-NR 1 -、-C(O)-、-C(O)NR 1 -、-NR 1 C(O)-, -C(O)O-, -OC(O)-, -S- or -O-; Z is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted ynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroynyl, optionally substituted aryl, or optionally substituted heterocyclic; and R 1 and R 2 Each of them is independently hydrogen or optionally a substituted alkyl group.

26. The method of claim 18, wherein the oxygen-containing inhibitor comprises acetylacetone.

27. The method of claim 17, wherein exposing the substrate to a reducing agent or exposing the reduced substrate occurs in a plasma, and the plasma is a remote plasma or a direct plasma.

28. The method of claim 17, wherein the reducing agent comprises a nitrogen-containing reducing agent or a hydrogen-containing reducing agent.

29. The method of claim 28, wherein the nitrogen-containing reducing agent comprises nitrogen, ammonia, hydrazine, azide, or a combination thereof.

30. The method of claim 28, wherein the hydrogen-containing reducing agent comprises hydrogen, methane, acetylene, or water.

31. The method of claim 17, wherein the metal comprises tantalum, titanium, molybdenum, cobalt, indium, or ruthenium.

32. The method of claim 17, wherein the metal-containing film comprises tantalum nitride, indium oxide, tungsten nitride, or titanium nitride.

33. A method for selectively depositing a tantalum nitride barrier layer, comprising: A substrate with a metallic surface and a dielectric surface is provided in the processing chamber; The substrate is exposed to a reducing agent to obtain a reduced substrate; The reduced substrate is exposed to an inhibitor to obtain a pretreated substrate; A tantalum-containing precursor and a nitrogen-containing reactant are supplied to the processing chamber to selectively form a tantalum nitride barrier layer on the metal surface above the pretreated substrate; as well as The tantalum nitride barrier layer is post-treated with plasma to remove the inhibitor.

34. An apparatus for selective deposition, the apparatus comprising: Processing room; A substrate holder, which is located in the processing chamber; One or more gas inlets for allowing gas to flow into the processing chamber; A vacuum source, used to remove gas from the processing chamber; A plasma generator for generating plasma within the processing chamber; as well as One or more controllers include machine-readable instructions for operating the one or more gas inlets, the vacuum source, and the plasma generator to perform deposition on a semiconductor substrate, the machine-readable instructions of the one or more controllers including instructions for performing the method according to claim 1.

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