Selective deposition of silicon oxide on metal surfaces

Abstract

The provided method is for selectively depositing a silicon oxide film on a metal or metal-containing surface relative to a dielectric surface. The dielectric surface of the substrate can be selectively passivated relative to the metal or metal-containing surface, for example, by exposing the substrate to a silanizing agent. Subsequently, silicon oxide is selectively deposited on the metal or metal-containing surface relative to the passivated oxide surface by contacting the metal surface with a metal catalyst and a silicon precursor containing silanol.

Description

Technical Field

[0001] This disclosure generally relates to the selective deposition of silicon oxide on a metallic or metal-containing surface of a substrate relative to the dielectric surface of the substrate. Prior Technology

[0002] The ever-shrinking device sizes in semiconductor manufacturing necessitate new and innovative processing methods. Patterning in semiconductor processing is conventionally known to involve subtractive processes, in which a blanket layer is deposited, masked using photolithography, and etched through openings in the mask. Additive patterning is also known, in which a masking step is performed before the deposition of the material of interest, such as patterning using lift-off techniques or damascene processes. In most cases, expensive multi-step photolithography techniques are applied for patterning.

[0003] Patterning can be simplified using selective deposition, which has gained increasing attention among semiconductor manufacturers. Selective deposition offers significant advantages in various aspects. Notably, it allows for fewer lithography steps, reducing processing costs. Selective deposition also enables enhanced scaling in narrow structures.

[0004] Thin films containing silicon dioxide are used, for example, as dielectric materials in many different applications of microelectronic devices. Silicon dioxide is one of the most commonly used dielectric materials in silicon microelectronic devices. Summary of the Invention

[0005] In some embodiments, a method is provided for selectively depositing a silicon oxide film on a metal or metal-containing surface relative to a dielectric surface. In some embodiments, the method of selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of the substrate comprises, in sequence: contacting the substrate with a passivating agent; contacting the metal surface with a metal catalyst; and contacting the metal surface with a silicon reactant comprising silanol. In some embodiments, the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo. In some embodiments, the dielectric surface comprises silicon oxide. In some embodiments, contacting the substrate with the passivating agent results in selective passivation of the dielectric surface relative to the metal surface. In some embodiments, the passivating agent is a silanizing agent. In some embodiments, the silanizing agent comprises an alkylamine silane. In some embodiments, the alkylaminosilane has the formula (RI)3Si(NRII RIII), wherein RI is a straight-chain or branched C1 to C5 alkyl or a straight-chain or branched C1 to C4 alkyl, RII is a straight-chain or branched C1 to C5 alkyl, a straight-chain or branched C1 to C4 alkyl, or hydrogen, and RIII is a straight-chain or branched C1 to C5 alkyl or a straight-chain or branched C1 to C4 alkyl. In some embodiments, the silanizing agent comprises allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazolium (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

[0006] In some embodiments, the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylaluminum isopropoxy (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxy (TIPA), or triethylaluminum (TEA). In some embodiments, the metal catalyst is a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga. In some embodiments, the metal catalyst is a metal halide, an organometallic compound, or an organometallic compound.

[0007] In some embodiments, the silicon reactants comprise tris(tributoxy)silyl alcohol (TBS), tris(isopropoxy)silyl alcohol (TIS), or tris(tripentoxy)silyl alcohol (TPS).

[0008] In some embodiments, a passivation barrier layer is formed on a metal surface before the substrate is brought into contact with the passivating agent. In some embodiments, the passivation barrier layer comprises a polymer or a self-assembled monolayer (SAM).

[0009] In some embodiments, the deposition selectivity of silicon oxide on a catalytic metal surface is greater than about 50% relative to a passivated dielectric surface.

[0010] In some embodiments, selective deposition of silicon oxide on a metal surface of a substrate relative to the dielectric surface of the substrate comprises a deposition supercycle, which includes: contacting the substrate with a silanizing agent and performing one or more silicon oxide deposition subcycles, the subcycles comprising alternately and sequentially contacting the substrate with a metal catalyst and silanol. In some embodiments, the silanizing agent is N-(trimethylsilyl)dimethylamine. In some embodiments, the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tris(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA).

[0011] In some embodiments, the metal catalyst is a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga. In some embodiments, the metal catalyst is a metal halide, an organometallic compound, or an organometallic compound. In some embodiments, the silanol is tris(tripentoxy)silanol. In some embodiments, the silicon oxide deposition subcycle is repeated two or more times in the deposition supercycle. In some embodiments, the substrate is contacted with silanol two or more times in at least one silicon oxide deposition subcycle. In some embodiments, the deposition supercycle is repeated two or more times.

[0012] In some embodiments, a method for selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of the substrate comprises alternately and sequentially contacting the substrate with: a silanizing agent comprising allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA); trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tris(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA); and tris(tripentoxy)silyl alcohol (TPS). Simple Explanation of the Diagram

[0013] Figure 1 is a flowchart illustrating a deposition process for selectively depositing silicon oxide on a metal surface relative to a dielectric surface. Figure 2A is a schematic cross-sectional view of a portion of a substrate having a first dielectric surface and a second adjacent metal surface. Figure 2B is a schematic cross-sectional view of the substrate of Figure 2A after selective passivation of the dielectric surface. Figure 2C is a schematic cross-sectional view of the substrate in Figure 2B after aluminum catalyst is selectively deposited on the metal surface. Figure 2D is a schematic cross-sectional view of the substrate in Figure 2C after silicon oxide is selectively deposited on the metal surface. Figure 2E is a schematic cross-sectional view of the substrate in Figure 2D after the passivation material has been removed from the oxide surface. Implementation

[0014] Silicon oxide films (such as silicon dioxide films, e.g., SiO2 films) formed by the methods described herein can be used in a variety of contexts. For example, silicon oxide films (such as silicon dioxide films, e.g., SiO2 films) are used in a wide variety of semiconductor devices, including CMOS, DRAM, flash memory, and magnetic head applications. Silicon oxide (such as silicon dioxide, e.g., SiO2) is also commonly used as a gate dielectric for CMOS, as an electrical insulating layer, and as an interstitial filling layer. Silicon oxide films (such as silicon dioxide films, e.g., SiO2 films) can be deposited by exposing the surface to silanol containing a suitable catalyst. The catalyst is prepared to react with the silanol, resulting in catalytic growth of silicon oxide on the substrate surface.

[0015] In some embodiments, silicon oxide is selectively deposited over a first metal (or metal-containing) surface relative to a second dielectric surface (such as an oxide surface) using a passivating agent in combination with a catalyst. In some embodiments, the dielectric surface may be selectively passivated relative to the metal surface, for example, by silanization. Subsequently, the catalyst is selectively deposited on the metal surface relative to the dielectric surface. For example, the catalyst may be a metal catalyst as described in more detail below. Next, a silicon oxide layer is selectively deposited on the metal surface relative to the passivated dielectric surface by contacting the substrate with a silicon reactant (such as silanol). In some embodiments, the silicon oxide is deposited after passivation of the dielectric surface, and no catalyst is deposited on the metal surface. The silicon oxide layer may be deposited by a cyclic vapor deposition process, wherein the substrate is alternately contacted with the catalyst and silanol until a silicon oxide film of the desired thickness has been selectively deposited. In some embodiments, the passivation step may be omitted.

[0016] In some embodiments, the dielectric surface (such as the oxide surface) on the substrate is silanized with a silanizing agent such as allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA), and the metal catalyst as described herein is selectively deposited on the metal surface of the same substrate, and the silicon oxide is subsequently selectively deposited on the metal surface of the substrate relative to the passivated dielectric surface. For example, the silicon oxide layer can be selectively deposited on the metal surface relative to adjacent dielectric surfaces (such as metal oxide surfaces, silicon oxide surfaces, or low-k surfaces) by using, for example, allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA) as passivating agents; trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA) as aluminum catalysts; and silanols (such as tri(tripentoxy)silanol) as silicon reactants.

[0017] In some embodiments, the metal or metal-containing surface of the substrate comprises an elemental metal or metal alloy, and a second, different surface of the substrate comprises a dielectric material (such as an oxide). In some embodiments, the dielectric surface and the metal surface are adjacent to each other. Examples of feasible dielectric materials include silicon oxide-based materials, including grown or deposited silicon dioxide, doped and / or porous oxides, native oxides on silicon, etc. In some embodiments, the dielectric material comprises a metal oxide. In some embodiments, the dielectric material comprises a low-k material.

[0018] The surface of the dielectric material can be selectively passivated relative to a metal or metal-containing surface, for example, by selective silanization. In some embodiments, the dielectric surface is in contact with a vapor-phase passivating agent, such as fumed allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA). The substrate can be in contact with a sufficient amount of passivating agent for a sufficient period of time, such that the dielectric surface is selectively passivated with silicon species. In some embodiments, both surfaces are in contact with a vapor-phase passivating agent, and the dielectric surface is selectively passivated relative to a metal or metal-containing surface. In some embodiments, the dielectric surface is not passivated with a self-assembled monolayer (SAM).

[0019] Catalysts are selectively formed on a metal surface relative to a dielectric surface, such as by contacting a substrate with a metal catalyst compound. In some embodiments, the catalyst is a metal catalyst. In some embodiments, both the metal surface and the dielectric surface are in contact with a metal catalyst compound. The metal surface containing the catalyst species may be referred to herein as a "catalyzed metal surface". In some embodiments, the substrate is in contact with a metal catalyst as described below. The catalyst may be, for example, a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga. In some embodiments, the catalyst is a metal halide, an organometallic compound, or an organometallic compound. In some embodiments, the catalyst may be a metal oxide. In some embodiments, the catalyst is a compound comprising boron. In some embodiments, the metal catalyst is an aluminum catalyst comprising trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA). In some embodiments, the catalyst is a zirconium compound (such as Zr-DO4). In some embodiments, the catalyst is tetra(ethylmethylamino)zirconium (TEMAZ). In some embodiments, the catalyst is ZrCl4. In some embodiments, the catalyst is a lanthanum compound (such as tris(isopropyl-cyclopentadienyl)lanthanum (LA(iPrCp)3)). In some embodiments, the catalyst is a titanium compound (such as titanium isopropoxide (TTIP) or TiCl4). In some embodiments, the catalyst is a gallium compound (such as trimethylgallium (TMG)). In some embodiments, the catalyst is a hafnium compound (such as HfCl4 or Hf(NO3)4).

[0020] In some embodiments, the catalyst may preferentially deposit on the metal surface relative to the dielectric surface. In some embodiments, the catalyst may preferentially deposit on the metal surface relative to the passivated dielectric surface. In some embodiments, a passivating agent on the dielectric surface inhibits or prevents the deposition of aluminum catalyst on the dielectric surface. In some embodiments, a single exposure to the passivating agent may continuously prevent catalyst deposition on the dielectric surface for 1, 2, 5, 10, 20, 30, 40, or 50 or more cycles of contacting the substrate with the catalyst. In some embodiments, the dielectric surface is not passivated, and the catalyst is selectively deposited on the metal surface in the absence of passivating material on the dielectric surface. In some embodiments, for example, no catalyst is used when the metal or the metal containing the metal surface itself can catalyze the deposition of silicon oxide.

[0021] After the catalyst is deposited on a metal or metal-containing surface, a silicon oxide layer is selectively deposited on the metal or metal-containing surface relative to the passivated dielectric surface. For example, the substrate may be exposed to a silicon precursor (such as silanol). In some embodiments, the substrate is exposed to the silicon precursor alone, while in other embodiments, the substrate is exposed to both the silicon precursor and an oxygen precursor (such as H₂O). The silicon precursor may react with a surface containing an aluminum catalyst to form silicon oxide. For example, the substrate may be contacted with a silicon reactant containing silanol, causing the silanol to decompose at catalyst atoms on the metal or metal-containing surface, resulting in selective growth of silicon oxide on the metal or metal-containing surface relative to the dielectric surface.

[0022] In some embodiments, the substrate is contacted alternately and sequentially with a passivating agent, a catalyst, and a silanol reactant in one or more deposition supercycles. This deposition supercycle can be repeated multiple times to selectively deposit a silicon oxide film of desired thickness on the metal surface relative to the dielectric surface. Referring to Figure 1, in some embodiments, during a complete deposition supercycle...

[0100] In the middle, the initial system of the substrate and the passivating agent

[0110] (Such as silicon alkylating agents) contact. Excess passivating agent can be removed from the substrate surface. A silicon oxide deposition sub-cycle is implemented.

[0120] The substrate system and catalyst

[0130] and silicon precursors (such as silicol)

[0140] Contact. As mentioned above, in some embodiments, in addition to the silicon reactants, the substrate is contacted with oxygen reactants (such as H₂O). In each contact step...

[0130] and

[0140] Subsequently, excess catalyst and silanol can be removed from the substrate surface. In a single-deposition supercycle...

[0100] In this context, the sub-loop can be repeated.

[0150] Multiple times. In some embodiments, during each deposition supercycle.

[0100] One, two, three, or more silicon oxide deposition cycles are performed, wherein the substrate is alternately and sequentially reacted with the catalyst.

[0130] and silicone reactants

[0140] Contact. That is, the substrate contacts the passivating agent each time.

[0110] Multiple silicon oxide deposition sub-cycles can be performed upon contact.

[0120] In some embodiments, another deposition supercycle is initiated by contacting the substrate with a passivating agent.

[0100] Previously, silicon oxide deposition sub-cycle

[0120] This process is repeated up to fifty times. In some embodiments, after a deposition sub-cycle and before the substrate is contacted with the passivating agent 110, the passivation layer is removed, for example, by contacting the substrate with H2 plasma, such as by plasma etching. In this way, the passivation layer can be renewed one or more times during the deposition process. In some embodiments, the passivation layer is not renewed in each deposition supercycle.

[0100] Instead of removing it in the middle, it is removed only in one or more deposition supercycles (such as the last deposition supercycle). Repeatable deposition supercycle

[0100] , until a silicon oxide film of the desired thickness has been selectively formed on the metal surface. In some embodiments, the passivating agent is provided only once during the deposition process.

[0023] In some embodiments, a metal or metal-containing surface on which a metal oxide is selectively deposited is at least partially adjacent to a selectively passivated dielectric surface. For example, at least a portion of the metal or metal-containing surface may be adjacent to a dielectric surface (such as an oxide surface).

[0024] In some embodiments, a passivation barrier layer (such as a self-assembled monolayer (SAM)) may be provided on the metal or metal-containing surface prior to the formation of a passivation layer on the dielectric surface (such as an oxide surface). The passivation barrier layer may facilitate selectivity for passivation (such as silanization) of the dielectric surface, and the passivation barrier layer may be subsequently removed to allow selective deposition of metal catalysts and silicon oxides on the metal or metal-containing surface relative to the silanized dielectric surface.

[0025] A passivation layer (e.g., silanization) can be removed from a dielectric surface (such as an oxide surface) before selectively depositing a silicon oxide layer over a metallic or metal-containing surface. Conditions can be selected to avoid damaging surrounding materials on the substrate. In some embodiments, the passivation layer (e.g., silanization) on the dielectric surface can be removed and renewed at one or more intervals during the deposition of the silicon oxide layer. For example, the passivation layer can be removed at one or more intervals during the deposition process, such as by exposure to H2 plasma, and then re-exposed to the silanizing agent before proceeding to further oxide deposition. In some embodiments, the passivation layer is removed and renewed in each cycle.

[0026] Examples of suitable reactors that can be used in the selective deposition process described herein include commercially available atomic layer deposition (ALD) equipment. In addition to ALD reactors, many other types of reactors capable of growing organic passivation layers can be used, including chemical vapor deposition (CVD) reactors, vapor deposition polymerization (VDP) reactors, and molecular layer deposition (MLD) reactors. [Substrate Surface]

[0027] According to some embodiments of this disclosure, selective deposition can be used to preferentially deposit a film of interest (such as a silicon oxide film) on a metal or metal-containing surface relative to an oxide surface or other dielectric surface. This substrate is schematically illustrated in FIG. 2A. In some embodiments, the two surfaces are at least partially adjacent to each other on the substrate. Selective passivation of the oxide surface relative to the metal or metal-containing surface (such as selective silanization of the oxide surface) facilitates subsequent selective deposition of a metal catalyst on the metal or metal-containing surface, followed by selective deposition of a silicon oxide layer on the metal or metal-containing surface relative to the silanized oxide surface.

[0028] In some embodiments, one of the surfaces may be a conductive metal or metal-containing surface of the substrate, while the other dielectric surface may be a non-conductive oxide surface of the substrate. In some embodiments, the non-conductive oxide surface contains -OH groups (such as silicon oxide-based surfaces, for example, low-k materials, including grown and deposited silicon oxide materials and native oxides on silicon). The oxide surface may be selectively passivated relative to the metal or metal-containing surface by exposure to a silanizing agent. This is followed by exposure to a metal catalyst, and subsequently, silicon oxide may be selectively deposited on the metal or metal-containing surface relative to the silanized oxide surface.

[0029] The material difference between the two substrate surfaces allows vapor deposition methods to selectively passivate oxide surfaces relative to metal or metal-containing surfaces. In some embodiments, cyclic vapor deposition (e.g., cyclic chemical vapor deposition (CVD) or atomic layer deposition (ALD) processes) is used. In some embodiments, selectivity for the passivation layer can be achieved without a passivating / blocking agent (to receive less passivation layer) on the metal or metal-containing surface and / or without a catalyst on the dielectric layer surface to receive more passivation layer. For example, in embodiments where the first surface is oxide and the second surface is metal-containing, the oxide layer can be selectively silanized relative to the metal or metal-containing surface without pretreatment of the oxide surface or the metal or metal-containing surface.

[0030] In some embodiments, the metal or metal-containing surface is first treated to suppress passivation (such as silanization) of the surface. In some embodiments, the passivation barrier layer is a polymer layer. In some embodiments, a passivation barrier self-assembled monolayer (SAM) may be first formed above the metal or metal-containing surface relative to the oxide surface, facilitating the selective deposition of a passivation layer on the oxide surface relative to the SAM-covered metal-containing surface. The passivation inhibitor may be removed after selective passivation and before catalyst deposition and subsequent silicon oxide deposition. After the selective deposition of the passivation layer is completed, selective deposition of the material of interest (such as catalyst and / or silicon oxide) may be performed on the unpassivated metal or metal-containing surface relative to the passivated surface.

[0031] As used herein, unless otherwise specifically indicated, a surface referred to herein as a metallic surface may be a metallic surface or a surface containing metal. In some embodiments, a metallic or metallic surface may include surface oxidation. In some embodiments, the material of the metallic surface is conductive with or without surface oxidation. In some embodiments, the metallic surface comprises one or more transition metals. In some embodiments, the metallic surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, or Mo. In some embodiments, the metallic surface comprises Cu. In some embodiments, the metallic surface is a copper surface. In some embodiments, the metallic surface comprises titanium nitride. In some embodiments, the metallic surface comprises one or more noble metals (such as Ru). In some embodiments, the metallic surface comprises metal oxides (such as conductive metal oxides, metal nitrides, metal carbides, metal borides, or combinations thereof). For example, a metallic or metallic surface may comprise one or more of RuOx, NbCx, NbBx, NiOx, CoOx, NbOx, MoOx, WOx, WNCx, TaN, or TiN.

[0032] In some embodiments, a metal or metal-containing surface is acceptable or can be used on the surface of reactants in a selective deposition process of an aluminum catalyst, as described herein.

[0033] As mentioned above, in some embodiments, a passivation barrier layer may be included on the metal or metal-containing surface. That is, in some embodiments, the metal or metal-containing surface may contain a material (e.g., a self-assembled monolayer (SAM)) that inhibits the formation of the passivation layer on the metal or metal-containing surface. In some embodiments, the deposition process includes forming a passivation barrier layer on the metal or metal-containing surface but not on the surface to be passivated. After the passivation layer is formed on the dielectric surface, the passivation barrier layer may be removed if necessary or desired. [Passivation of substrate surface]

[0034] In some embodiments, the oxide surface or other dielectric surface of the substrate may be passivated. In some embodiments, passivation is selective for the oxide surface relative to another surface (such as a metal or metal-containing surface on the same substrate) (see, for example, FIG. 2B). In some embodiments, the oxide surface is silanized by exposure to a vapor-phase silanizing agent one or more times. For example, in the passivation step, the silanizing agent may be introduced into the reaction space and contact the substrate surface. The silanizing agent may be, for example, a chlorosilane, an alkoxysilane, a silyl halide, a silyl cyanate, a silyl azide, a silyl isocyanate, a silyl isothiocyanate, a silyl sulfonate, a silyl acetylamine, a silyl carbodiimide, an allyl silane, or a nitrogen-bearing silane (such as a silazane, an imidazole, or an amine). In some embodiments, the silanizing agent is allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA), and silanization includes exposing the substrate to one or more pulses of the silanizing agent. In some embodiments, both the metal or metal-containing surface and the oxide surface are contacted with the silanizing agent, such as allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA). In some embodiments, the oxide surface of the substrate is selectively silanized relative to the metal or metal-containing surface of the substrate.

[0035] In some embodiments, the silanizing agent is an alkylamine silane. For example, the oxide surface of the substrate may be contacted with an alkylamine silane having the formula (RI)3Si(NRII RIII), wherein RI is a straight-chain or branched C1 to C5 alkyl or a straight-chain or branched C1 to C4 alkyl, RII is a straight-chain or branched C1 to C5 alkyl, a straight-chain or branched C1 to C4 alkyl, or hydrogen, and RIII is a straight-chain or branched C1 to C5 alkyl or a straight-chain or branched C1 to C4 alkyl.

[0036] In some embodiments, the silanizing agent is a silane. For example, the oxide surface may be contacted with a silane having the general formula (RI)3SiA, wherein RI is a straight-chain or branched C1 to C5 alkyl or a straight-chain or branched C1 to C4 alkyl, and A is any ligand that is reactive with the silicon-containing surface.

[0037] The silanizing agent may be provided to the reaction chamber holding the substrate in a single pulse or in a sequence of multiple pulses. In some embodiments, the silanizing agent is provided in a single long pulse or a series of shorter pulses. The pulses may be provided sequentially. In some embodiments, the silanizing agent is provided in 1 to 25 pulses ranging from about 0.1 to about 60 seconds. In some embodiments, the silanizing agent is provided in a single pulse of about 0.1 to about 60 seconds, about 1 to about 30 seconds, or about 25 seconds. Between pulses, the silanizing agent may be removed from the reaction space. For example, the reaction chamber may be evacuated and / or flushed with an inert gas. Flushing may, for example, last for about 1 to about 30 seconds or longer. Flushing the reaction chamber means removing the gaseous passivating agent and / or gaseous byproducts (if any) from the reaction chamber, such as by evacuating the chamber with a vacuum pump and / or by replacing the gas in the reactor with an inert gas such as argon or nitrogen. In some embodiments, the substrate is moved from the reaction space containing the passivating agent.

[0038] In some embodiments, the temperature of the silanization process may be, for example, from about 50 to about 500°C or from about 100 to about 300°C. The pressure during the silanization process may be, for example, from about 10⁻⁵ to about 760 Torr, or in some embodiments, from about 1 to about 10 Torr or from about 0.1 to about 10 Torr.

[0039] In some embodiments, the silanization process can be performed in situ, that is, in the same reaction chamber as subsequent deposition processes (e.g., selective deposition of an aluminum catalyst on an unsilanized surface relative to the silanized surface and / or subsequent selective deposition of silicon oxide on an unsilanized surface relative to the silanized surface). However, in some embodiments, silanization can be performed in a reaction chamber separate from one or more subsequent processing steps. In some embodiments, the reaction chamber in which silanization is performed is part of a cluster tool comprising one or more additional reaction chambers. For example, this cluster tool may include additional reaction chambers for depositing an aluminum catalyst, depositing silicon oxide, and / or etching one or more layers. In some embodiments, the cluster tool includes separate modules for pretreatment, silanization of the oxide surface, selective deposition of the catalyst, selective deposition of silicon oxide, and subsequent post-deposition processing (such as etching to remove silanization or plasma post-deposition cleaning). In some embodiments, the same module may be used for two or more processes.

[0040] In some embodiments, the substrate may be pretreated or cleaned prior to or at the start of one or more of the passivation and / or selective deposition processes. In some embodiments, the substrate may be subjected to a plasma cleaning process prior to or at the start of the selective passivation and / or selective deposition processes. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. In some embodiments, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species prior to or at the start of the passivation and / or selective metal oxide deposition processes. In some embodiments, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species prior to or at the start of the selective passivation and / or selective metal oxide deposition processes.

[0041] In some embodiments, the dielectric surface is not passivated before the catalyst is selectively deposited on the metal surface relative to the dielectric surface. [Selective deposition of metal catalysts on metal or metal-containing surfaces relative to oxide surfaces]

[0042] The catalyst for subsequent silicon oxide deposition can be selectively deposited on a metallic or metal-containing surface of the substrate relative to the dielectric surface of the substrate. This surface containing the catalyst may be referred to as a catalytically deposited metallic surface. In some embodiments, passivation of the dielectric surface is not necessary, and the catalyst is selectively deposited on the metallic surface relative to the dielectric surface, wherein the dielectric surface is not passivated. However, in some embodiments, selective deposition of the catalyst is facilitated or improved by passivating the dielectric surface as described above. Therefore, in some embodiments, the catalyst is selectively deposited on a metallic or metal-containing surface relative to a passivated dielectric surface. As shown in FIG2C, in some embodiments, an aluminum catalyst is selectively deposited on a metallic surface relative to a dielectric surface that has been passivated using a silicon alkylation compound as described herein.

[0043] After selectively forming a passivation layer on the dielectric surface, in some embodiments, a catalyst is selectively deposited on a second surface by contacting the substrate with a catalyst compound. A molecular layer of catalyst reaching the catalytic sites is formed on the surface of the metal substrate. The catalyst compound preferably catalyzes the formation of silicon oxide from a gaseous silanol reactant, as described below. In short, the substrate is exposed to silanol (such as TPS) and a silicon oxide film (such as a silicon dioxide film, e.g., a SiO2 film) generally comprising multiple molecular layers is formed. Cycles of exposure to the catalyst and silanol can be repeated if necessary to deposit a silicon dioxide film of desired thickness. In some embodiments, the concentration of silanol can be controlled to achieve a desired deposition rate. In some embodiments, the temperature of the substrate can be controlled to achieve a desired deposition rate. In some embodiments, a catalyst is not necessary, and the metal surface itself catalyzes the deposition of silicon oxide from silanol.

[0044] In some embodiments, the catalyst is a metal catalyst. The catalyst may be, for example, a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga. In some embodiments, the catalyst is a metal halide, an organometallic compound, or an organometallic compound.

[0045] In some embodiments, the catalyst comprises boron. In some embodiments, the catalyst is an alkylaluminum, alkylboron, or alkylzinc compound capable of reacting with a hydrophobic surface. For example, the catalyst may comprise trimethylaluminum (TMA), triethylboron (TEB), or diethylzinc.

[0046] In some embodiments, the catalyst comprises a compound having the formula MRx A3-x, wherein x is from 1 to 3, R is a C1 to C5 alkyl ligand, M is a B, Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga, and A is a halide, alkylamine, amino, silica, or a derivative thereof. In some embodiments, R is a C1 to C3 alkyl ligand. In some embodiments, R is methyl or ethyl. In some embodiments, M is boron. In some embodiments, the catalyst is ZnRx A2-x, wherein x is from 1 to 2, R is a C1 to C5 alkyl ligand, and A is a halide, alkylamine, amino, silica, or a derivative thereof. In some embodiments, R is a C1 to C3 alkyl ligand. In some embodiments, R is methyl or ethyl.

[0047] In some embodiments, the catalyst is an aluminum catalyst. Examples of usable Al compounds include trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA). In some embodiments, the aluminum catalyst comprises an isocoordinated aluminum compound. In some embodiments, the isocoordinated aluminum compound comprises an alkyl group and another ligand (such as a halide, e.g., Cl). In some embodiments, the aluminum catalyst comprises dimethylaluminum chloride. In some embodiments, the aluminum catalyst comprises an alkyl precursor comprising two different alkyl groups as ligands. In some embodiments, the aluminum compound is isopropoxyaluminum. In some embodiments, the aluminum catalyst comprises an organometallic compound. In some embodiments, the aluminum catalyst comprises an organometallic compound. In some embodiments, the aluminum catalyst is an aluminum compound (such as trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA)).

[0048] In some embodiments, the catalyst is a zirconium compound (such as Zr-DO4). In some embodiments, the catalyst is tetra(ethylmethylamino)zirconium (TEMAZ). In some embodiments, the catalyst is ZrCl4.

[0049] In some embodiments, the catalyst is a lanthanum compound (such as tris(isopropyl-cyclopentadienyl)lanthanum (LA(iPrCp)3)).

[0050] In some embodiments, the catalyst is a titanium compound (such as titanium isopropoxide (TTIP) or TiCl4).

[0051] In some embodiments, the catalyst is a gallium compound (such as trimethylgallium (TMG)).

[0052] In some embodiments, the catalyst is a hafnium compound (such as HfCl4 or Hf(NO3)4).

[0053] The catalyst may be provided to the reaction chamber holding the substrate in a single pulse or in a sequence of multiple pulses. In some embodiments, the catalyst is provided in a single long pulse or a series of shorter pulses. The pulses may be provided sequentially. In some embodiments, the catalyst is provided in 1 to 25 pulses ranging from about 0.1 to about 60 seconds. In some embodiments, the catalyst is provided in a single pulse ranging from about 0.1 to about 60 seconds, about 1 to 30 seconds, or about 25 seconds. Between pulses, excess catalyst may be removed from the reaction space. For example, the reaction chamber may be evacuated and / or flushed with an inert gas. Flushing may, for example, last for about 1 to 30 seconds or longer. Flushing means removing the gaseous catalyst and / or gaseous byproducts (if any) from the reaction chamber, such as by evacuating the chamber with a vacuum pump and / or by replacing the gas in the reaction chamber with an inert gas. In some embodiments, the gaseous catalyst is removed from the substrate surface by moving the substrate from the reaction space containing the gaseous catalyst.

[0054] In some embodiments, the temperature for selective catalyst deposition may be, for example, from about 50 to about 500°C or from about 100 to about 300°C. In some embodiments, the deposition temperature is between about 50°C and about 400°C. In some embodiments, the deposition temperature is greater than about 100°C, and the catalytic chemical is an alkylaluminum compound (such as TMA). In some embodiments, the catalytic chemical is an alkylboron compound (such as TEB), and the deposition temperature is between about 50°C and about 400°C, between about 100°C and about 350°C, or between about 100°C and about 300°C. In some embodiments, the catalytic chemical is an alkylboron compound, and the temperature is greater than about 100°C. In some embodiments, the deposition temperature is greater than about 300°C, and the catalytic chemical is TEB.

[0055] In some embodiments, the catalyst comprises a metal compound, which is selectively deposited by contacting a substrate with a metal precursor and an oxygen reactant. In some embodiments, the catalyst comprises a metal oxide. In some embodiments, the metal compound is selectively deposited by an ALD process. In some embodiments, the substrate is contacted simultaneously or sequentially with a first metal precursor and an oxygen-containing second reactant in one, two, or more deposition cycles. In some embodiments, the deposition process comprises a plurality of deposition cycles in which the substrate is contacted alternately and sequentially with a first metal precursor and a second reactant.

[0056] In some embodiments, the first metal precursor is a hydrophobic Lewis acid. The hydrophobic metal reactant may contain at least one hydrophobic hydrocarbon ligand (such as alkyl, alkenyl, cyclic C3 to C8, or aryl). In some embodiments, the first metal precursor may be bis(methylcyclopentadienyl)methoxymethylzirconium.

[0057] In some embodiments, the first metal precursor comprises a transition metal. In some embodiments, the first precursor does not comprise a noble metal (such as Ru).

[0058] In some embodiments, the first metal precursor may comprise at least one alkyl ligand (such as a C1 to C4 alkyl ligand). In some embodiments, the first metal precursor may comprise an organometallic compound or an organometallic compound. In some embodiments, the first metal precursor may comprise at least one cyclopentadienyl (Cp) ligand. In some embodiments, the first metal precursor may comprise a formamidinyl or amidinyl compound. In some embodiments, the first metal precursor may comprise a β-diketone compound. In some embodiments, the first metal precursor may comprise an alkylamine compound (such as a dialkylamine compound). In some embodiments, the first metal precursor may comprise an alkylamine ligand (such as –NMe2, -NEt2, or -NEtMe).

[0059] In some embodiments, the first metal precursor may comprise magnesium. In some embodiments, the first metal precursor may be an organometallic or organometallic compound comprising magnesium. For example, in some embodiments, the first metal precursor may comprise Mg(Cp)₂ or a derivative thereof.

[0060] In some embodiments, the first metal precursor may comprise lanthanum. In some embodiments, the first metal precursor may be an organometallic compound comprising lanthanum. In some embodiments, the first metal precursor may comprise lanthanum formamidinium (La(FAMD)3).

[0061] In some embodiments, the first metal precursor may comprise hafnium. In some embodiments, the first metal precursor may comprise an organometallic compound comprising hafnium. For example, in some embodiments, the first metal precursor may comprise an alkylamine hafnium compound (such as tetratetra(ethylmethylamine)hafnium (TEMAH, Hf(NEtMe)4) or a derivative thereof).

[0062] In some embodiments, the first metal precursor has the following formula: MgL2 (I)

[0063] Wherein Mg is magnesium, and each L can be independently selected as a hydrocarbon group. In some embodiments, each L can be a straight-chain, branched, cyclic alkyl, or unsaturated hydrocarbon group (such as alkenyl, alkynyl, aromatic, cyclopentadienyl, phenyl, cyclooctadienyl, or cycloheptadienyl). In some embodiments, one or two L can be cyclopentadienyl. In some embodiments, one or two L can be bidentate ligands (such as β-diketone, guanidinyl, or amidine). In some embodiments, the β-diketone ligand can be acetylacetonate or 2,2,6,6-tetramethyl-3,5-heptanedione (THD).

[0064] In some embodiments, the first metal precursor is a cyclopentadienyl compound or a derivative thereof (such as an alkyl-substituted cyclopentadienyl compound) and has the following formula: Mg(R1 R2 R3 R4 R5 Cp)2 (II)

[0065] Each of the R1, R2, R3, R4, and R5 groups may be independently selected as hydrogen or a substituted or unsubstituted alkyl group. In some embodiments, each of the R1, R2, R3, R4, and R5 groups may be independently selected as hydrogen or a straight-chain or branched C1 to C5 alkyl group. In some embodiments, each of the R1, R2, R3, R4, and R5 groups may be independently selected as hydrogen or a C1 to C3 alkyl group (such as methyl, ethyl, n-propyl, or isopropyl). In some embodiments, the first precursor is Mg(Cp)2.

[0066] In some embodiments, the first metal precursor comprises one or more ligands (such as cyclopentadienyl (“Cp”) ligands). These first precursor compounds are selected from the group consisting of: (Cp)x La (III); (Cp)x Ly La (IV); (Cp)x Wn La (V); (CP)x Ly Wn La (VI); La-based lanthanum, Cp-based cyclopentadienyl or cyclooctadienyl, such that the Cp groups in formulas I to IV can be the same or different from each other; x represents the number of Cp ligands and is an integer from 1 to the oxidation state of La; it should be noted that cyclooctadiene is usually abbreviated as Cod, but here the single common abbreviation Cp is used for both cyclopentadienyl and cyclooctadienyl for simplification; Ly-type neutral adduct ligands bind from one or more of their atoms to the metal, where y represents the number of bound ligands; and The W-series has some other ligands with a valence one less than Cp, where n represents the number of ligands. In some embodiments, the W-series is amidine or formamidinium. In some embodiments, the W-series is β-diketone or its corresponding sulfur or nitrogen compound, halide, amide, alkoxide, carboxylate, or Schiff's base.

[0067] In chemical formulas I to IV, cyclopentadienyl and / or cyclooctadienyl can be in the same molecule such that there is a bridge between the two Cp groups, which consists of substituted or unsubstituted C1 to C6 chains that may contain heteroatoms selected from Si, N, P, Se, S, or B.

[0068] In some embodiments, the L series is selected independently: (i) Hydrocarbons, (ii) Hydrocarbons containing oxygen (iii) Hydrocarbons containing nitrogen (iv) Hydrocarbons containing sulfur (v) Hydrocarbons containing phosphorus, (vi) Hydrocarbons containing arsenic (vii) Hydrocarbons containing selenium, and / or (viii) Hydrocarbons containing tellurium

[0069] In some embodiments, the L series is selected independently: (a) amines or polyamines (b) Bipyridine, (c) Based on the following chemical diagram, the ligands: In formula V, G is —O—, —S—, or —NR1, where R1 is an independently chosen hydrogen atom or a substituted or unsubstituted cyclic, straight-chain or branched alkyl, alkenyl, aryl, alkylaryl, aralkyl, alkoxy, thio, cyano, or silyl group. The cyclic or aromatic ring in R1 may contain heteroatoms. Hydrogen or R1-type substituents may also be attached to a carbon atom in formula V, or... (d) Ethers or thioethers.

[0070] The cyclopentadienyl or cyclooctadienyl Cp in chemical formulas I to IV have the following forms: Cp′Rm Ha-m (VII) Where a is 8, m is integers from 0 to 8, and when a is 5, m is integers from 0 to 5. Cp' is a fused or separated cyclopentadienyl or cyclooctadienyl group, and R-series hydrocarbon segments containing 1 to 6 carbon atoms (such as C1 to C6 hydrocarbons) are selected independently.

[0071] In some embodiments, each R ligand may be identical to the other R ligands, or each R ligand may be different from the others. That is, each R ligand may be independently selected. In some embodiments, R may be substituted or unsubstituted, cyclic, straight-chain or branched alkyl, alkenyl, aryl, alkylaryl, aralkyl, alkoxy, thio, amino, cyano, or silyl. The cyclic or aromatic ring of the substituent may contain heteroatoms. Examples of substituents are methyl, ethyl, propyl, and isopropyl.

[0072] The neutral adduct ligand L shown in chemical equations II and IV can be an independently chosen ether, amine, or solvent molecule (such as tetrahydrofuran, which forms a bond to a metal with one atom). Examples of suitable neutral adduct ligands forming bonds to a metal with several atoms are polyethers and polyamines.

[0073] In some embodiments, the first metal precursor may contain at least one cyclopentadienyl ligand and may be written according to Formula VIII:

[0074] (R1 R2 R3 R4 R5 Cp)x —MR0 z —(R6)y (VIII) The M series consists of metals selected from the group composed of Mg, Sr, Ba, Sc, Y, and the lanthanides. Each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, and each of the R5 group may be independently selected from: i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); and iv. Heterocyclic group; The R6 series is independently selected from: i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); iv. Heterocyclic groups; and v. NR1 R2; and Where x and y are both ≥1 and z ≥0.

[0075] In some embodiments, the first metal precursor comprising a cyclopentadienyl compound includes at least one ligand bonded to the metal via a nitrogen bond, as described by Formula IX:

[0076] (R1 R2 R3 R4 R5 Cp)x —MR0 z —(NR1 R2 )y (IX) The M series refers to metals selected from the group consisting of Mg, Sr, Ba, Sc, Y, or the lanthanides; Each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, and each of the R5 group are independently selected from: i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); and iv. Heterocyclic groups; and Where x and y are both ≥1 and z ≥0.

[0077] In Formula IX, the alkyl, alkenyl, and alkynyl groups are selected from any straight-chain or branched alkyl, alkenyl, and alkynyl groups having 1 to 6 carbon atoms. Examples of such alkyl groups include methyl; ethyl; n- and isopropyl; n-, iso, and tert-butyl; n- and isopentyl; n- and isopentyl; n- and isohexyl; and 2,3-dimethyl-2-butyl. In some embodiments, alkyl groups are used. In other embodiments, C1-6 alkenyl and alkynyl groups comprising corresponding groups having corresponding degrees of unsaturation may be used.

[0078] In some embodiments, the first metal precursor is a compound having at least one cyclopentadienyl ligand and at least one chelating ligand (e.g., a bidentate ligand). In some embodiments, this compound is described by the formula X, (R1 R2 R3 R4 R5 Cp)x —MR0 z —(NR1 NR2 R)y as follows: (X) M is selected from metals in the group consisting of Mg, Sr, Ba, Sc, Y, or the lanthanides; R can be any straight-chain or branched C1 to C6 alkyl, alkenyl, or alkynyl group, which may be independently substituted or unsubstituted, and R may be bonded to two bridging nitrogen atoms at any point in the alkyl, alkenyl, or alkynyl group; each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, and each of the R5 group may be independently selected from: i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); and iv. Heterocyclic groups; and Where x and y are both ≥1 and z ≥0.

[0079] In some other embodiments, the first metal precursor can be described by the formula XI (R1 R2 R3 R4 R5 Cp)x —MR0 z —[(NR1 NR2 )CNR3 ]y as follows: The M series refers to metals selected from the group consisting of Mg, Sr, Ba, Sc, Y, or the lanthanides; Each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, and each of the R5 group can be independently selected. i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); and iv. Heterocyclic groups; and Where x and y are both ≥1 and z ≥1.

[0080] In a further embodiment, the first metal precursor system is described by the formula XII (R1 R2 R3 R4 R5 Cp)x —MR0 z —[(NR1 NR2 )CNR3 R4 ]y as follows: (XII) The M series refers to metals selected from the group consisting of Mg, Sr, Ba, Sc, Y, or the lanthanides; Each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, and each of the R5 group may be independently selected from: i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups); and iv. Heterocyclic groups; and Where x and y are both ≥1 and z ≥0.

[0081] In some embodiments, the first metal precursor as described in formulas VIII to XII may comprise R0, R1, R2, R3, R4, R5, and R6, wherein each of the R0 group, each of the R1 group, each of the R2 group, each of the R3 group, each of the R4 group, each of the R5 group, and each of the R6 group may be independently selected from... i. Hydrogen; ii. Straight-chain and branched C1 to C6 alkyl, alkenyl, and alkynyl groups, which may or may not be substituted independently; iii. Carbocyclic groups (such as aryl, phenyl, cyclopentadienyl, and alkylaryl); and iv. Heterocyclic groups

[0082] Optionally, the first metal precursor as described may comprise a modified cyclopentadienyl group. In some embodiments, the modified cyclopentadienyl group is selected from the group consisting of Me5Cp, MeCp, EtCp, and Me3SiCp. In a further embodiment, the first metal precursor may comprise anionic or dianionic guanidinoligands (such as triisopropylguanidinoligands).

[0083] In some embodiments, the second reactant comprises oxygen and may be referred to herein as an oxygen precursor, oxygen reactant, oxygen-containing precursor, or oxygen-containing reactant. In some embodiments, the second reactant comprises molecular oxygen (O2). In some embodiments, the second reactant does not comprise a compound containing oxygen other than O2. In some embodiments, the second reactant does not comprise O3 or H2O. In some embodiments, the second reactant does not comprise plasma (e.g., oxygen plasma). In some embodiments, the second reactant is supplied with or mixed with an inert gas system such as N2, He, or Ar.

[0084] In some embodiments, the second reactant comprises molecular oxygen and less than about 50%, 25%, 15%, 10%, 5%, 1%, or 0.1% of impurities other than inert gases.

[0085] In some embodiments, selective catalyst deposition can be performed in situ, that is, in the same reaction chamber as the previous passivation and / or subsequent deposition processes (e.g., subsequent selective deposition of silicon oxide on an unsilanized surface relative to a silanized surface). However, in some embodiments, selective catalyst deposition can be performed in a reaction chamber separate from one or more subsequent processing steps (e.g., in a chamber that is part of a clustering tool).

[0086] In some embodiments, the substrate and system metal surface may be pretreated or cleaned before or at the beginning of selective catalyst deposition. [Selective deposition of silicon oxide on catalyzed metal surfaces relative to dielectric surfaces]

[0087] Following passivation of the dielectric surface (if implemented) and selective deposition of the catalyst on the metal surface (if implemented), silicon oxide can be selectively deposited on the metal surface of the substrate relative to the dielectric surface. In some embodiments, silicon oxide is selectively deposited on the metal surface by contacting the substrate with a silicon reactant (such as silanol (see, e.g., FIG. 2D)). In some embodiments, the substrate surface is contacted with both a silicon reactant and an oxygen reactant (such as H₂O). The formation of silicon oxide is achieved by the presence of a catalyst on the metal surface or, if no catalyst is used, by the catalysis of the metal surface itself.

[0088] One or more silanols may be used as silicon reactants (such as alkoxysilanols or alkoxysilanediols). In some embodiments, the silicon reactant may comprise one or more of tris(trialkoxy)silanol, di(alkoxy)alkylsilanol, di(alkoxy)silanediol, or bis(trialkoxy)silanediol. In some embodiments, the silanol may be selected from one or more of tris(tributoxy)silanol (TBS), tris(isopropoxy)silanol (TIS), or tris(tripentoxy)silanol (TPS). Silanols are compounds comprising silicon bonded to one or more hydroxyl (OH) groups. In some embodiments, the silanol comprises more than one OH- group directly bonded to a silicon atom. Silicone compounds include, but are not limited to, alkoxysilanols, alkoxyalkylsilanols, and alkoxysilanediols. In some embodiments, the silicon precursor comprises TPS. In some embodiments, the silicon source is di(alkoxy)silanediol.

[0089] In some embodiments, a single silanol pulse is provided after the catalyst has been deposited on the metal surface. In some embodiments, the single silanol pulse is used to deposit a silica film on the substrate, which is measured to have a thickness of more than 5 angstroms on the top surface of the metal surface. As discussed above, in some embodiments, the substrate may be contacted with the catalyst and silanol in one or more silica deposition sub-cycles. The sub-cycles may be repeated until a silica film of the desired thickness has been selectively formed above the metal surface. In some embodiments, obtaining a silica film of the desired thickness may require only a single sub-cycle. In other embodiments, steps 2, 3, 4, 5, 6, 7, 8, 9, 10, or more times.

[0090] In some embodiments, more than one silanol pulse is provided in each deposition supercycle. For example, two, three, or more silanol pulses may follow a catalyst pulse. In some embodiments, two silanol pulses follow a catalyst pulse. The silanol pulses may be separated by a flushing step. In other embodiments, the silanol pulses are provided after a predetermined time delay without an intermediate flushing step.

[0091] Although typically described as beginning with catalyst supply, each silicon oxide deposition subcycle can begin with either reactant. However, as will be recognized by those skilled in the art, if the first subcycle begins with silanol reactants, deposition may not be able to begin prior to the second deposition supercycle.

[0092] For catalysts, surface saturation ensures that the catalyst occupies all available reaction sites (e.g., limited by size or steric hindrance), and thus ensures superior step coverage. However, in some embodiments, the catalyst can be supplied in unsaturated or subsaturated doses. For example, in deep trench structures, it is important to form a "collar," which is an etch stop layer that must only extend a portion of the path downwards along the trench. In this example, a subsaturated pulse of catalyst can be used to preferentially deposit the catalyst along the collar region, further down into the trench than the surface. As a result, silica deposition only occurs to the depth reached by the catalyst, and thus the extent of silica deposition is limited to the desired depth. Therefore, in some embodiments, the catalyst dose is metered to provide a predetermined amount of catalyst and a predetermined amount of silica deposition.

[0093] For the silanol reactant, in some embodiments, a saturation pulse of silanol is provided. However, since the growth rate of silica depends in part on the diffusion of the precursor through the growing film, the growth rate can be controlled, for example, by controlling the precursor dosage, rinsing time, and / or temperature. Therefore, in some embodiments, an unsaturated dosage of silanol can be provided. In some embodiments, the dosage and / or exposure time of the silanol reactant can be limited to provide silica of a specific thickness and / or depth in a given reaction cycle.

[0094] In some embodiments, a silicon dioxide thin film is selectively formed on the metal surface of a substrate relative to the dielectric surface by selecting a catalyst capable of reacting with the metal surface and performing a deposition process comprising one or more silicon dioxide deposition sub-cycles, each silicon dioxide deposition sub-cycle comprising: A first gaseous reactant comprising a metal catalyst is pulsed into a reaction chamber to form a monolayer of no more than about about the catalyst on the metal surface of a substrate; Remove excess catalyst from the reaction chamber; A second gaseous reactant containing silanol is pulsed into the reaction chamber; and Remove excess secondary reactant and reaction byproducts (if any) from the reaction chamber.

[0095] In some embodiments, silicon oxide thin films are selectively deposited on one or more metal or metal-containing surfaces (such as copper, cobalt, titanium nitride, or tungsten surfaces) relative to one or more dielectric surfaces.

[0096] The film thickness can be adjusted depending on the specific circumstances. In some embodiments, a silicon dioxide film ranging from several angstroms to several nanometers is deposited. In some embodiments, a silicon dioxide film less than about 2 nm is deposited. In some embodiments, a silicon dioxide film less than about 3 nm is deposited. In some embodiments, to obtain a film deposition of less than about 2 nm or less than about 3 nm, one or both of the catalyst and silanol are used in insufficient doses. The film can be deposited in one deposition supercycle or in multiple deposition supercycles.

[0097] Before film deposition begins, the substrate is typically heated to a suitable growth temperature. In some embodiments, the growth temperature of the silicon dioxide film is less than about 500°C, less than about 400°C, less than about 300°C, less than about 200°C, less than about 150°C, or even less than about 125°C. The temperature is generally selected so that the catalyst does not decompose. In some embodiments, the deposition process may be performed, for example, using TMA as a catalyst at a temperature greater than about 100°C.

[0098] In some embodiments, the pulse duration for the reactants may be from about 0.1 to about 10 seconds, and the rinsing time between reactant pulses may also be from about 0.1 to about 10 seconds.

[0099] The pressure in the reaction chamber is generally from about 0.1 mTorr to about 5 Torr, more preferably from about 0.1 mTorr to about 3 Torr, and most preferably from about 0.2 mTorr to about 3 Torr. However, in some cases, the pressure will be higher or lower than this range, as can be easily determined by a person of ordinary skill in the art.

[0100] In one embodiment, during a silicon oxide deposition subcycle, silicon oxide (such as silicon dioxide, e.g., SiO2) is deposited on the metal surface of the substrate relative to a passivated dielectric surface at a temperature of approximately 150°C. A TMA pulse is applied to the reaction chamber for 150 ms, followed by a 3-second rinse. A TPS pulse is then applied to the reaction chamber for 100 seconds, followed by a 90-second rinse. [Post-deposition treatment]

[0101] Following the selective deposition of the metal oxide, the substrate may undergo a post-deposition cleaning step to remove the passivation layer from the oxide surface, as mentioned above (see, for example, Figure 2E). In some embodiments, the cleaning step may include H2 plasma treatment. In some embodiments, the cleaning step is performed at a temperature of about room temperature to about 400°C. In some embodiments, a plasma power of about 25 to about 250 W may be used to generate plasma in flowing H2 at a flow rate of, for example, about 10 to about 500 sccm. In some embodiments, the cleaning time after the deposition of the metal oxide layer may be, for example, from about 0.1 to about 600 seconds or more.

[0102] In some embodiments, a thin silicon oxide film is selectively deposited on a three-dimensional metal or metal-containing surface relative to one or more passivated dielectric surfaces. The three-dimensional structure may include, for example, through-holes or trenches. In some embodiments, the dielectric surface may be selectively passivated and an aluminum catalyst may be deposited on the metal surface prior to the deposition of the silicon oxide film. [Passivation barrier layer]

[0103] Passivation barrier layers can facilitate the selective formation of passivation layers on dielectric materials relative to the passivation barrier layer. As described above, in some embodiments, self-assembled monolayers (SAMs) can act to suppress silanization of metals or metal-containing surfaces, thereby facilitating selective passivation of the dielectric surface. In some embodiments, passivation barrier layers are used in addition to SAMs. The term "blocking" is therefore merely a label and does not necessarily imply 100% deactivation of the passivation layer deposition. As described elsewhere herein, even incomplete selectivity can be sufficient to achieve a fully selective structure after, for example, an etch-back process. [Selective]

[0104] Selective passivation and / or selective deposition can be fully selective or partially selective. A partially selective process can be followed by post-deposition etching, which removes all deposited material from one surface but not from the second surface, resulting in a fully selective layer. Therefore, in some embodiments, selective deposition does not need to be fully selective to obtain the desired benefits.

[0105] The selectivity of deposition (or passivation) on the first surface (hereinafter referred to as surface A) relative to the second surface (referred to as surface B) can be given as a percentage calculated by [(deposition on surface A) - (deposition on surface B)] / (deposition on surface A). Deposition can be measured in any of a variety of ways. For example, deposition can be given as a measured thickness of the deposited material, or it can be given as a measured amount of the deposited material. In the embodiments described herein, the oxide surface (A) can be selectively passivated relative to the metal or metal-containing surface (B). For passivation, if the passivation is caused by a treatment of the substrate surface rather than the deposition of a layer, the amount of passivation can be a measurement of the available reactive sites on the substrate surface that have reacted with the passivating agent. Subsequently, a metal oxide layer can be selectively deposited on the metal or metal-containing surface (B) relative to the passivation layer above the oxide surface (A).

[0106] In some embodiments, the selectivity for selectively forming a passivation layer on a dielectric surface (relative to a metal or metal-containing surface) is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%.

[0107] In some embodiments, the catalyst deposited on the metal or metal-containing surface relative to the passivated dielectric surface is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%.

[0108] In some embodiments, the amount of catalyst deposited on a metal or metal-containing surface relative to an unpassivated dielectric surface is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%.

[0109] In some embodiments, the selectivity of depositing silicon oxide on a catalyzed metal or metal-containing surface (relative to a passivated or unpassivated dielectric surface) is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%.

[0110] In some embodiments, deposition occurs only on one surface and not on the other.

[0111] In some embodiments, the selectivity of passivating the dielectric surface by silanization relative to the metal or metal-containing surface of the substrate is at least about 80%. In some embodiments, the selectivity of the passivation process is at least about 50%. In some embodiments, the selectivity of the passivation process is at least about 10%. Those skilled in the art will understand that partially selective processes can achieve complete selective passivation of the oxide surface by post-deposition etching that removes any silanization from another surface.

[0112] In some embodiments, the selectivity of the catalyst deposited on the metal surface relative to the passivated dielectric surface of the substrate is at least about 80%. In some embodiments, the selectivity of the catalyst deposition process is at least about 50%. In some embodiments, the selectivity of the catalyst deposition process is at least about 10%. Those skilled in the art will understand that partially selective processes can achieve fully selective deposition on the metal surface by post-deposition etching that removes any catalyst from the dielectric surface.

[0113] In some embodiments, the selectivity for depositing silicon oxide on a catalytic metal or metal-containing surface of a substrate relative to the surface of a silanized oxide of the substrate is at least about 80%. In some embodiments, the selectivity for depositing silicon oxide on a catalytic metal or metal-containing surface of a substrate relative to the surface of a silanized oxide of the substrate is at least about 50%. In some embodiments, the selectivity for depositing silicon oxide on a catalytic metal or metal-containing surface of a substrate relative to the surface of a silanized oxide of the substrate is at least about 10%. Those skilled in the art will understand that post-deposition etching (or other processing) can follow a partially selective process, which essentially removes all the deposited material from above the silanized dielectric surface. Furthermore, post-deposition processing can also help to tailor the location and / or contour of the selectively deposited layer. Selective deposition of silicon oxide on metal or metal-containing surfaces.

[0114] Figures 2A to 2E schematically illustrate an embodiment for selectively passivating a first dielectric surface relative to a second metal or metal-containing surface, followed by selectively depositing silicon oxide on the second metal or metal-containing surface relative to the passivated first oxide surface.

[0115] Figure 2A illustrates a substrate with different exposed surfaces in terms of material. For example, the first surface may comprise or be defined by a dielectric material 220, such as a silicon oxide substrate or a silicon surface having a native oxide formed thereon. The second surface may comprise or be defined by a metal 210 (such as copper (Cu)).

[0116] Figure 2B shows the substrate of Figure 2A after selective passivation of the dielectric surface (such as by silanization). For example, the passivation layer 230 can be selectively formed on the dielectric surface 220 by exposing the substrate to a silanizing agent, such as allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

[0117] Figure 2C shows the substrate of Figure 2B after selective deposition of aluminum catalyst 240 on metal surface 210 relative to passivation layer 230 on dielectric surface 220. Aluminum catalyst 240 can be selectively formed on metal surface 210 by exposing the substrate to aluminum reactants such as trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylaluminum isopropoxy (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxy (TIPA), or triethylaluminum (TEA). Although illustrated as using an aluminum catalyst, in other embodiments, metal catalysts comprising other metals or other catalysts, as described herein, may be used.

[0118] Figure 2D shows the substrate of Figure 2C after selective deposition of silicon oxide 250 on the catalytic metal surface 210 relative to the dielectric surface 220. In some embodiments, silicon oxide 250 is formed by exposing the substrate to a silanol reactant (such as tris(tripentoxy)silanol). The silanol reactant can decompose on aluminum atoms on the catalytic metal surface, resulting in the deposition of silicon oxide on the metal surface.

[0119] As described above, any silicon oxide deposited on a dielectric layer (such as a passivated dielectric layer) can be removed by a post-deposition process (such as an etch-back process). This etch-back process can also remove silicon alkylation from the dielectric surface. Because silicon oxide is selectively deposited on metal surfaces, any silicon oxide remaining on the passivation surface will be thinner than the silicon oxide formed on the metal surface. Therefore, the post-deposition process can be controlled to remove all the silicon oxide above the dielectric surface without removing all of it from the metal surface. Repeating selective deposition and etch-back in this manner can result in an increase in the thickness of silicon oxide on the metal surface with each deposition and etching cycle. Repeating selective deposition and etch-back in this manner can also result in an overall increase in the selectivity of silicon oxide on the metal or metal-containing surface, because each deposition and etching cycle leaves behind a clean passivation layer on which the selectively deposited silicon oxide has not fully nucleated. In other embodiments, the silicon oxide above the dielectric surface can be removed during subsequent passivation layer removal. For example, either direct etching or stripping methods can be used to remove silicon oxide from the surface of the passivation layer in cyclic selective deposition and removal.

[0120] Figure 2E shows the post-deposition process to remove dielectric surface

[0220] Remove passivation layer

[0230] The substrate of Figure 2D after (e.g., via an etching process). In some embodiments, the etching process may include exposing the substrate to plasma. In some embodiments, the plasma may include oxygen atoms, oxygen radicals, oxygen plasma, or combinations thereof. In some embodiments, the plasma may include hydrogen atoms, hydrogen radicals, hydrogen plasma, or combinations thereof. In some embodiments, the plasma may include rare gas species (e.g., Ar or He species). In some embodiments, the plasma may consist substantially of rare gas species. In some cases, the plasma may include other species, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or combinations thereof. In some embodiments, the etching process may include exposing the substrate to an etchant containing oxygen (e.g., O3). In some embodiments, the substrate may be exposed to the etchant at a temperature between about 30°C and about 500°C or between about 100°C and about 400°C. In some embodiments, the etchant may be supplied in a single continuous pulse or in multiple pulses. As described above, in cyclic selective deposition and removal, passivation layer removal can be used to strip any remaining metal oxide from above the oxide layer, either by completely removing the passivation layer or by partially removing the passivation layer.

[0121] Additional treatments (such as thermal or chemical treatments) may be performed before, after, or between the aforementioned processes. For example, treatments may modify surfaces or remove portions of metal, silicon oxide, passivated, and metal oxide surfaces exposed at different stages of the process. In some embodiments, the substrate may be pretreated or cleaned before or at the beginning of the process. In some embodiments, the substrate may undergo a plasma cleaning process, as mentioned above.

[0122] Although certain embodiments and examples have been discussed, those skilled in the art will understand that the scope of this application extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses and obvious modifications and equivalents thereof.

[0123] 100: Deposition Supercycle 110: Passivating agent 120: Deposition Subcycle 130: Catalyst / Contact Step 140: Silicon precursors (such as silicol) / silicol reactants / contact steps 150: Sub-loops can be repeated multiple times. 210: Metal 220: Dielectric material 230: Passivation layer 240: Catalyst

Claims

1. A method for selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of a substrate, the method comprising: contacting the substrate with a passivating agent; contacting the substrate with a metal catalyst; and contacting the substrate with a silicon reactant comprising a silanol, wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.

2. The method as described in claim 1, wherein the dielectric surface comprises silicon monoxide.

3. The method as described in claim 1, wherein contacting the substrate with the passivating agent results in selective passivation of the dielectric surface relative to the metal surface.

4. The method as described in claim 1, wherein the passivating agent is a silanizing agent.

5. The method as described in claim 4, wherein the silanizing agent comprises an alkylamine silane.

6. The method as described in claim 4, wherein the silanizing agent comprises allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

7. The method as described in any one of claims 1 to 4, wherein the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA).

8. The method as described in any one of claims 1 to 4, wherein the silicon reactant comprises tris(tributoxy)silyl alcohol (TBS), tris(isopropoxy)silyl alcohol (TIS), or tris(tripentoxy)silyl alcohol (TPS).

9. The method as described in any one of claims 1 to 4, further comprising forming a passivation barrier layer on the metal surface before contacting the substrate with the passivating agent.

10. The method as described in claim 9, wherein the passivation barrier layer comprises a polymer or a self-assembled monolayer (SAM).

11. The method as described in any one of claims 1 to 4, wherein the deposition selectivity of silicon oxide on the catalytic metal surface is greater than about 50% relative to the passivated dielectric surface.

12. A method for selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of a substrate, comprising a deposition supercycle, the deposition supercycle comprising: contacting the substrate with a silanizing agent; and then performing one or more silicon oxide deposition subcycles, the subcycles comprising alternately and sequentially contacting the substrate with a metal catalyst and a silanol, wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.

13. The method as described in claim 12, wherein the silanizing agent is N-(trimethylsilyl)dimethylamine.

14. The method as claimed in claim 12, wherein the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA).

15. The method as described in claim 12, wherein the silanol is tris(tripentoxy)silanol.

16. The method as described in any one of claims 12 to 15, wherein the silicon oxide deposition subcycle is repeated two or more times in the deposition supercycle.

17. The method as claimed in claim 16, wherein the substrate is contacted with the silanol two or more times in at least one silicon oxide deposition subcycle.

18. The method as described in any one of claims 12 to 15, wherein the deposition supercycle is repeated two or more times.

19. A method for selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of a substrate, comprising alternately and sequentially contacting the substrate with: a silanizing agent comprising one of allyltrimethylsilane (TMS-A), trichlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA); trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl3), dimethylisopropoxyaluminum (DMAI), tri(tributyl)aluminum (TTBA), triisopropoxyaluminum (TIPA), or triethylaluminum (TEA); and tri(tripentoxy)silyl alcohol, wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.

Images