Improved regioselective deposition

Abstract

Methods, systems, and apparatus for selective deposition on a substrate, including providing a substrate in a reaction chamber, the substrate including a first surface and a second surface, where the first surface is a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, or a combination thereof, where the first surface is a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, or a combination thereof, and where the second surface is a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide. Wherein the second surface is a dielectric or metal, and contacting the substrate with a precursor comprising a hydrophobic compound to selectively deposit a passivation layer on the first surface relative to the second surface.

Description

Technical Field

[0001] The present disclosure relates to the deposition of organic thin films, including selective deposition on a first surface of a substrate relative to a second surface. Background Art

[0002] The shrinking of device dimensions in semiconductor manufacturing requires new and innovative processing methods. Traditionally, patterning in semiconductor processing involves subtractive processes, where a covering layer is deposited, masked by lithography techniques, and etched through the openings in the mask. Additive patterning is also known, where a masking step is performed before depositing the material of interest, such as patterning using a lift-off technique or an inlay process. In most cases, expensive multi-step lithography techniques are used for patterning.

[0003] Semiconductor manufacturers are increasingly interested in selective deposition, which can reduce the steps required for conventional patterning, thereby reducing processing costs. Selective deposition can also enhance the scaling of narrow structures. Various alternatives for achieving selective deposition have been proposed, and additional improvements are needed to expand the use of selective deposition in industrial-scale device manufacturing. More effective and reliable techniques are needed to increase the selectivity in selective deposition and reduce the defect rate.

[0004] Any discussion set forth in this section, including discussions of problems and solutions, has been included in the present disclosure solely to provide a background for the present disclosure. Such discussion should not be construed as an admission that any of the information was known at the time of conceiving the subject matter of the present disclosure or constitutes prior art. Summary of the Invention

[0005] The Summary of the Invention is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the following Detailed Description of the Example Embodiments. The Summary of the Invention is not intended to necessarily identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] In one aspect, a process for selectively depositing a metal on a substrate includes: a) providing a substrate in a reaction chamber, the substrate including a first surface, a second surface, and a third surface, b) contacting the substrate with a first precursor including a first alkylaminosilane to selectively deposit a first passivation layer on the first surface, c) contacting the substrate with a second precursor including a hydrophobic group to selectively deposit a second passivation layer on the second surface, d) contacting the substrate with a first inhibitor precursor including an amine, and e) contacting the substrate with a second inhibitor precursor including a dianhydride to selectively deposit an inhibitor layer on the third surface.

[0007] The process may further include f) purging the reaction chamber and performing at least one of operations b), c), d), e), or f) in any order until the first passivation layer, the second passivation layer, or the inhibitor layer, or a combination thereof, is deposited onto the corresponding surface of the first surface, the second surface, or the third surface, or a combination thereof.

[0008] The process may further include repeating performing at least one of operations b), c), d), e), or f) in any order until at least one of the following occurs: the first passivation layer reaches a first predetermined thickness, the second passivation layer reaches a second predetermined thickness, or the inhibitor layer reaches a third predetermined thickness, or a combination thereof.

[0009] The process may further include, wherein the first passivation layer has a fourth surface and is deposited relative to the second surface and the third surface, the second passivation layer has a fifth surface and is deposited relative to the third surface and the fourth surface, and the inhibitor layer has a sixth surface and is deposited relative to the fourth surface and the fifth surface.

[0010] The process may further include, wherein the first surface includes a dielectric surface. The process may further include, wherein the dielectric surface is a low-k material.

[0011] The process may further include, wherein the second surface includes a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, or a combination thereof. The process may further include, wherein the second surface includes AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, TaOx, TiOx, WOx, ZnOx, TiN, TaN, MoN, AlN, WN, TaON, SiCOx, SiOx, SiO2, SiC, SiOC, SiON, SiOCN, SiGe, SiN, or ZrOx, or any combination thereof.

[0012] The process may further include, wherein the third surface includes a metal. The process may further include, wherein the metal includes aluminum (Al), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), indium (In), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), niobium (Nb), ruthenium (Ru), tantalum (Ta), titanium (Ti), tungsten (W), vanadium (V), or zinc (Zn), or a combination thereof.

[0013] The process may further include, wherein the first alkylaminosilane is allyltrimethylsilane (TMS-A), trimethylchlorosilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), trimethylchlorosilane or 1,1,1-trimethoxy-N,N-dimethylsilylamine or a combination thereof.

[0014] The process may further include, wherein the second precursor includes tridecafluoro-1,1,2,2-tetrahydrooctylmethyl-bis(dimethylamino)silane.

[0015] The process may further include, wherein the dianhydride is pyromellitic dianhydride (PMDA) or pyromellitic dithioanhydride (PMDTA). The process may further include, wherein the amine is a diamine, triamine, tetraamine or a cyclic compound including at least two primary amines or a combination thereof.

[0016] The process may further include, wherein the second precursor includes a second alkylaminosilane, which includes a hydrophobic group partially or fully halogenated with one or more of fluorine, chlorine, bromine or iodine. The process may further include, wherein the second precursor includes a second alkylaminosilane, which includes a structure represented by the general formula (1):

[0017]

[0018] wherein, R1 and R2 each independently contain H or an alkyl group; wherein, R3 and R4 each independently contain H, an alkyl group or an amino group of the formula NR1R2; wherein, any two or more of R1, R2, R3 and R4 may contain the same alkyl group; and wherein, R5 is a hydrophobic halogenated hydrocarbon.

[0019] The process may further include, wherein the hydrophobic halohydrocarbon is a carbon chain comprising one or more of CH2, CHX, and CX2 units; wherein X is independently selected from fluorine, chlorine, bromine, or iodine. The process may further include, wherein the hydrophobic halohydrocarbon is non-chlorinated. The process may further include, wherein the hydrophobic halohydrocarbon is a fluorocarbon chain comprising CH2, CHF, or CF2 units or a combination thereof. The process may further include, wherein R5 comprises a C1-C100 chain, which comprises units independently selected from unhalogenated C, CX, CX2, or CX3, wherein X is independently selected from fluorine, chlorine, bromine, or iodine. The process may further include, wherein the second alkylaminosilane comprises a dialkylaminosilane, and the hydrophobic halohydrocarbon comprises 1-100 carbon atoms. The process may further include, wherein R1, R2, R3, and R4 each independently comprise an alkyl selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. The process may further include, wherein the remover is H2 plasma or O3. The process may further include, wherein R5 comprises an alkyl or an aryl or a combination thereof.

[0020] The process may further include exposing the substrate to a remover, and in response to the exposure to the remover, removing a portion of the first passivation layer, the second passivation layer, and the inhibitor layer. The process may further include depositing a film on a portion of the first surface, the second surface, or the third surface or a combination thereof after the removal. The process may further include, wherein the film comprises a metal, a metal nitride, a metal carbide, silicon oxynitride, or silicon oxycarbide or any combination thereof. The process may further include, wherein the film comprises Al, Cu, W, Co, Nb, Mo, Ru, Ti, Ta, V, AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, SiCOx, SiOx, TaOx, TiOx, WOx, ZnOx, ZrOx, TaN, MoNx, WNx, TiN, VCx, MoCx, NbCx, TaCx, TiCx, or WCx or any combination thereof. The process may further include removing the remaining portion of the inhibitor layer in response to exposing the substrate to the remover, and the remover may comprise H2 plasma or O3.

[0021] In one aspect, a method for selective deposition on a substrate includes: a) providing a substrate in a reaction chamber, the substrate including a first surface and a second surface, wherein the first surface is different from the second surface in material, wherein the first surface is a metal oxide, metal nitride, metal oxynitride, or metal carbide or a combination thereof, and wherein the second surface is a dielectric or a metal; and b) contacting the substrate with a precursor including a hydrophobic compound to selectively deposit a passivation layer on the first surface relative to the second surface. The method may further include c) purging the reaction chamber and performing at least one of operations b) and c) until the passivation layer is selectively deposited on the first surface relative to the second surface to a predetermined thickness. The method may further include, wherein the precursor includes an alkylaminosilane represented by the general formula (1):

[0022]

[0023] wherein R1 and R2 each independently include H or an alkyl group; wherein R3 and R4 each independently include H, an alkyl group, or an amino group of the formula NR1R2; wherein any two or more of R1, R2, R3, and R4 may include the same alkyl group; and wherein R5 is a hydrophobic halohydrocarbon. The method may further include, wherein the hydrophobic halohydrocarbon is a perfluorocarbon chain.

[0024] Other technical features will be apparent to those skilled in the art from the following drawings, description, and claims.

[0025] To summarize the present disclosure and the advantages achieved over the prior art, certain objects and advantages of the present disclosure have been described above. Of course, it should be understood that not all of these objects or advantages may be achieved according to any particular embodiment or example of the present disclosure. Thus, for example, those skilled in the art will recognize that the examples disclosed herein may be implemented in a manner that achieves or optimizes one or a group of the advantages taught or suggested herein, without necessarily achieving other objects or advantages taught or suggested herein.

[0026] All such examples are within the scope of the present disclosure. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain examples with reference to the drawings, and the present disclosure is not limited to any particular example discussed. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] To facilitate the discussion of any particular element or action, the most significant digit in the reference numeral refers to the figure number in which that element is first introduced.

[0028] Figure 1 A schematic diagram of a reactor system according to an example of the present technology is shown.

[0029] Figure 2A schematic diagram of a reactor system having multiple reaction chambers according to an example of the present technology is shown.

[0030] Figure 3 A simplified cross-sectional schematic diagram of a semiconductor structure formed during a cyclic selective deposition process according to an example of the present technology is shown.

[0031] Figure 4 A selective deposition process according to an example of the present technology is shown. Detailed Description

[0032] The following description of exemplary embodiments of methods, layers, structures, devices, and semiconductor processing components provided herein is merely exemplary and for illustrative purposes only. The following description is not intended to limit the scope of the present disclosure or the claims. Additionally, the recitation of multiple embodiments having the indicated features is not intended to exclude other embodiments having additional features or other embodiments combining different combinations of the recited features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise stated, the exemplary embodiments or their components may be combined or may be applied separately from each other.

[0033] The headings (if any) provided herein are for convenience only and do not necessarily affect the scope or meaning of the claimed subject matter.

[0034] As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous material, such as a material deposited by the methods disclosed herein. For example, a layer and / or film can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or full molecular layers or partial or full atomic layers or atomic and / or molecular clusters. A film or layer can include a material or layer having pinholes and can be at least partially continuous. In some embodiments, a layer according to the present disclosure is substantially continuous. In some embodiments, a layer according to the present disclosure is continuous.

[0035] In the present disclosure, "gas" can include materials that are gases at normal temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and can consist of a single gas or a gas mixture depending on the context. Reactants and precursors according to the present disclosure can be provided to the reaction chamber in the gas phase. The term "inert gas" can refer to a gas that does not participate in a chemical reaction and / or does not become part of a layer to a perceptible extent. Exemplary inert gases include He and Ar and any combination thereof. In certain cases, molecular nitrogen and / or hydrogen can be inert gases. Gases other than the process gases, i.e., gases that are not introduced through a precursor injector system, other gas distribution devices, etc., can be used, for example, to seal the reaction chamber and can include sealing gases.

[0036] The term "dielectric" is used in the description herein to simplify the distinction from metal or metallic surfaces. Those skilled in the art will understand that not all non-conductive surfaces are dielectric surfaces. For example, a metal or metallic surface can include an oxidized metal surface that is non-conductive or has a very high resistivity.

[0037] The terms "precursor" and "reactant" can refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction to produce another compound or element. A precursor typically contains at least a portion that is incorporated into the compound or element produced by the chemical reaction. The resulting compound or element can be deposited on a substrate. In some cases, a reactant is a precursor. A reactant can also be a molecule that binds (e.g., chemisorbs) to the substrate surface without undergoing a further chemical reaction with additional precursors and / or reactants at the surface. The reactant on the substrate surface can be modified, for example, by heat treatment or plasma treatment.

[0038] In some embodiments, the precursor or reactant is provided as a mixture of two or more compounds. In the mixture, other compounds in addition to the precursor can be inert compounds or elements. In some embodiments, the precursor or reactant is provided in a composition. The composition can be a solution or a gas under standard conditions.

[0039] As used herein, the term "comprising" means including certain features, but does not exclude the presence of other features, provided that they do not render the claim infeasible. In some embodiments, the term "comprising" encompasses "consisting of".

[0040] As used herein, the term "consisting of" means that no other features are present in the device / method / product except for the features that follow the phrase. When the term "consisting of" is used to refer to a chemical compound, substance, or composition of matter, it means that the chemical compound, substance, or composition of matter contains only the listed components. Similarly, when the term "consisting essentially of" is used to refer to a chemical compound, substance, or composition of matter, it means that the chemical compound, substance, or composition of matter contains the listed components, but may also contain trace elements and / or impurities that do not significantly affect the characteristics of the chemical compound, substance, or composition of matter. Nevertheless, in some embodiments, the chemical compound, substance, or composition of matter can include other components as trace elements or impurities in addition to the listed components.

[0041] In addition, in the present disclosure, any two numbers of a variable can form a feasible range of the variable, and any indicated range may or may not include endpoints. Further, any value of the indicated variable (whether or not denoted by "about") may refer to an exact value or an approximate value, and includes equivalents, and may refer to an average value, a median value, a representative value, a majority value, etc. In addition, in the present disclosure, the terms "comprising", "consisting of", and "having" independently refer to "generally or broadly comprising", "including", "substantially consisting of", or "consisting of" in some embodiments. In the present disclosure, in some embodiments, any defined meaning does not necessarily exclude the ordinary and customary meaning.

[0042] In the specification, it should be understood that the terms "on" or "above" can be used to describe a relative positional relationship. Another element, film, or layer may be directly on the layer, or another layer (intermediate layer) or element may be inserted therebetween, or a layer may be disposed on the layer but not completely cover the surface of the layer. Thus, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it should be understood that the terms "under", "below", or "beneath" will be interpreted as relative concepts.

[0043] Substrate

[0044] The deposition method according to the present invention includes providing a substrate in a reaction chamber. The substrate may be any one or more underlying materials that can be used to form or on which a structure, device, circuit, or layer can be formed. The substrate may include a bulk material, such as silicon (e.g., single-crystalline silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as II-VI or III-V semiconductor materials, and may include one or more layers covering or underlying the bulk material. In addition, the substrate may include various features, such as recesses, protrusions, etc. formed within or on at least a portion of the layers of the substrate. For example, the substrate may include a bulk semiconductor material and a layer of insulating or dielectric material covering at least a portion of the bulk semiconductor material. The substrate may include nitrides, such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single-crystalline materials. In some embodiments of the present disclosure, the substrate includes silicon. As described above, in addition to silicon, the substrate may include other materials. The other materials may form layers. Specifically, the substrate may include a partially fabricated semiconductor device.

[0045] Substrates according to various embodiments of the present disclosure include a first surface and a second surface. The first surface and the second surface have different material properties, allowing for selective deposition of a passivation material on the first surface and optionally selective deposition of an organic polymer (such as an inhibitor) on the second surface. In some embodiments, the first surface and the second surface are adjacent to each other. In some embodiments, the first surface and the second surface are on the same side of a silicon wafer.

[0046] Alternatively or additionally, embodiments of the present disclosure include first, second, and third surfaces. The first, second, and third surfaces have different material properties, allowing for selective deposition of a first passivation material on the first surface, selective deposition of a second passivation material on the second surface, and selective deposition of an inhibitor on the third surface. In some embodiments, the first, second, and third surfaces are adjacent to each other. In some embodiments, the first, second, and third surfaces are on the same side of a silicon wafer.

[0047] In some embodiments, the substrate may be pretreated or cleaned before or at the start of the selective deposition process according to the present disclosure. In some embodiments, the substrate may be subjected to a plasma cleaning process before or at the start of the selective deposition process. In some embodiments, the plasma cleaning process may include ion bombardment, exposure to plasma, radicals, excited species, and / or atomic species before or at the start of the selective deposition process. In some embodiments, the substrate surface may be exposed to a hydrogen plasma, radicals, or atomic species before or at the start of the selective deposition process. In some embodiments, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition process. However, in some embodiments, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0048] Reaction chamber

[0049] A method of depositing one or more passivation layers and / or inhibitor materials according to the present invention includes providing a substrate in a reaction chamber. In other words, the substrate is in a space where deposition conditions can be controlled. The reaction chamber may be a single-wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a gas-phase processing assembly for manufacturing semiconductor devices, such as a semiconductor processing assembly. The semiconductor processing assembly may include one or more multi-station processing chambers. The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. Each stage of the method according to the present disclosure, such as the method of depositing the first passivation layer, the second passivation layer, the organic polymer, or the method of depositing metal, metallic, and / or dielectric materials, may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chambers of a cluster tool or the deposition stations of a multi-station processing chamber.

[0050] In some embodiments, the reaction chamber can be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber can be a showerhead reactor. In some embodiments, the reaction chamber can be a hot-wall reactor. In some embodiments, the reaction chamber can be a spatially separated reactor. In some embodiments, the reaction chamber can be a single-wafer ALD reactor. In some embodiments, the reaction chamber can be a large-scale manufactured single-wafer ALD reactor. In some embodiments, the reaction chamber can be a batch reactor for simultaneously manufacturing multiple substrates.

[0051] The reaction chamber of the present disclosure can form part of an atomic layer deposition (ALD) assembly. The reaction chamber can form part of a chemical vapor deposition (CVD) assembly. The processing assembly can be an ALD or CVD processing assembly. In certain parts of the deposition process flow, molecular layer deposition (MLD) can be employed. In some embodiments, the method is performed in a single reaction chamber of a combined tool, but other, previous, or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same combined tool. Optionally, the semiconductor processing assembly including the reaction chamber can be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or reactants and / or precursors.

[0052] Cyclic vapor deposition

[0053] In some methods according to the present disclosure, particularly in methods for depositing organic polymers and dielectric materials, a cyclic vapor deposition method can be used. The cyclic deposition in the present disclosure refers to a vapor deposition process in which deposition cycles (usually multiple consecutive deposition cycles) are performed in a processing chamber.

[0054] Typically, in a cyclic deposition process according to the present disclosure, such as atomic layer deposition (ALD) and molecular layer deposition (MLD), during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the substrate surface (e.g., a substrate surface that may include previously deposited material or other materials from a previous deposition cycle). In some embodiments, the precursor on the substrate surface does not readily react with additional precursor (i.e., the deposition of the precursor can be a partial or fully self-limiting reaction). Thereafter, another precursor or reactant can be introduced into the reaction chamber for converting the chemisorbed precursor into the desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. During one or more cycles, e.g., during each step of each cycle, a purge step can be utilized to remove any excess precursor and / or any excess reactant and / or reaction by-products from the processing chamber. Thus, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor to the reaction chamber. Without limiting the present disclosure to any particular theory, ALD and MLD can be similar processes in terms of self-limiting reactions and a slower and more controllable layer growth rate compared to CVD. Typically, ALD is used to deposit inorganic materials, such as dielectric materials, while in MLD, the precursors can be fully organic molecules, such as when depositing an organic polymer.

[0055] In some embodiments, the process according to the present disclosure can include a CVD component. CVD-type processes are characterized by vapor deposition, which is not self-limiting. They generally involve gas-phase reactions between two or more precursors and / or reactants. The precursors and reactants can be provided to the reaction chamber or substrate simultaneously, or in partially or fully separated pulses. However, CVD can be carried out with a single precursor or two or more precursors that do not react with each other. The single precursor can decompose into reactive components that deposit on the substrate surface. For example, the decomposition can be carried out by plasma or thermal methods. The substrate and / or the reaction chamber can be heated to facilitate the reaction between the gaseous precursor and / or reactant. In some embodiments, the precursors and reactants are provided until a layer of a desired thickness is deposited. In some embodiments, a cyclic CVD process can use multiple cycles to deposit a thin film of a desired thickness. In a cyclic CVD process, the precursors and / or reactants can be provided to the reaction chamber in non-overlapping or partially or fully overlapping pulse forms. The process can include one or more cyclic stages. In some embodiments, the process includes one or more non-cyclic (i.e., continuous) stages. An example of a continuous stage can be a pretreatment with a single reactant. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In some embodiments, one or more precursors are continuously provided in the reaction chamber.

[0056] In some aspects of the present disclosure, selective deposition can be used to deposit a material on a first surface relative to a second surface. The two surfaces can have different material properties. In some aspects of the present disclosure, selective deposition can be used to deposit a material on a first surface relative to second and third surfaces. The three surfaces can have different material properties.

[0057] In some examples, an organic material such as polyamide or polyimide is selectively deposited on a first conductive (e.g., metal or metallic) surface of a substrate relative to different surfaces of the substrate (e.g., second and / or third surfaces). In some examples, polyamide or polyimide is selectively deposited on a first conductive (e.g., metal or metallic) surface, and the different surfaces can include OH groups, such as a silica-based surface. In some examples, the different surfaces can additionally include -H terminations, such as an HF-etched Si or HF-etched Ge surface. In some examples, polyamide or polyimide is selectively deposited on a first conductive (e.g., metal or metallic) surface, and the different surfaces include a passivation material (e.g., first passivation layer 324 or second passivation layer 330 discussed in more detail below). In some examples, the dielectric has different compositions (e.g., silicon, silicon nitride, carbon, silica, silicon oxynitride, germanium oxide). In other such examples, the dielectric can have the same basic composition (e.g., silica-based layer), but have different material properties due to the manner of formation (e.g., thermal oxide, native oxide, deposited oxide). In some examples, a vapor deposition method is used. In some examples, cyclic vapor deposition is used, such as using a cyclic CVD or atomic layer deposition (ALD) process. After the selective deposition of the organic material is complete, further processing can be performed to form the desired structure.

[0058] For example, one surface contains metal while one or more other surfaces do not contain metal. Unless otherwise specified, if a surface is referred to as a metal surface herein, it can be a metallic surface or a metal-like surface. In some examples, the metal or metal-like surface can include metal, metal oxide, and / or a mixture thereof. In some examples, the metal or metal-like surface can include surface oxidation. In some examples, the metal or metal-like surface of the metal or metal-like material is conductive with or without surface oxidation. In some examples, the metal or metal-like surface contains one or more transition metals. In some examples, the metal or metal-like surface contains one or more of the following: aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr), or vanadium (V), or a combination thereof. In some examples, the metal-like surface includes titanium nitride. In some examples, the metal or metal-like surface contains one or more noble metals, such as Ru. In some examples, the metal or metal-like surface includes a conductive metal oxide, nitride, carbide, boride, or a combination thereof. For example, the metal or metal-like surface can include RuO x , NbC x , NbB x , NiO x , CoO x , NbO x , one or more of WNCx, TaN, MoNx, WNx, AlOx, and / or TiN.

[0059] In some examples, the metal or metal-like surface can contain Zn, Fe, Mn, or Mo. In some examples, the metal or metal-like surface can be any surface that is capable of accepting or coordinating with the first or second precursor used in the selective deposition process as described herein.

[0060] In some examples, an organic material is selectively deposited on a metal oxide surface relative to other surfaces. The metal oxide surface can be, for example, WO x , HfO x , TiO x , AlO x or ZrO x surface. In some examples, the metal oxide surface is an oxidized surface of a metal-like material. In some examples, the metal oxide surface is produced by oxidizing at least the surface of a metal material using an oxygen-containing compound, such as a compound containing O3, H2O, H2O2, O2, oxygen atoms, plasma, or radicals, or a mixture thereof. In some examples, the metal oxide surface is a natural oxide formed on a metal material.

[0061] In some examples, the organic material is selectively deposited on a metallic or metallized surface of a substrate relative to the dielectric surface of the substrate. In some examples, the selectively deposited organic material is a polyamide, a polyimide, or other polymeric material. The term dielectric is used in the description herein to simplify the distinction from other surfaces (i.e., metallic or metallized surfaces). Those skilled in the art will understand that not all non-conductive surfaces are dielectric surfaces. For example, a metallic or metallized surface can include an oxidized metal surface that is non-conductive or has a very high resistivity. The selective deposition process taught herein can deposit on such non-conductive metal surfaces with minimal deposition on adjacent dielectric surfaces.

[0062] In some examples, the organic material is selectively deposited on a metal oxide surface of a substrate relative to the SiO2 surface. In some examples, the metal oxide surface can be, for example, WO x , HfO x , TiO x , AlO x or ZrO x surface. In some examples, the organic material is deposited on a dielectric surface relative to the SiO2 surface. In some examples, the SiO2 surface can be, for example, a native oxide, a thermal oxide, or a chemical oxide.

[0063] In some examples, a substrate including a metallic or metallized surface, a metal oxide surface, and a dielectric surface is provided. In some examples, the dielectric surface can be a SiO2-based surface. In some examples, the dielectric surface can include Si-O bonds. In some examples, the dielectric surface can include a SiO2-based low-k material. In some examples, the dielectric surface can contain greater than about 30% or greater than about 50% SiO2. In some examples, the dielectric surface can include GeO2.

[0064] In some examples, the substrate can be pretreated or cleaned before or at the start of the selective deposition process. In some examples, before or at the start of the selective deposition process, the substrate can be subjected to a plasma cleaning process. In some examples, before or at the start of the selective deposition process, the plasma cleaning process can include ion bombardment, exposure to plasma, radicals, excited species, and / or atomic species. In some examples, before or at the start of the selective deposition process, the substrate surface can be exposed to a hydrogen plasma, radicals, or atomic species. In some examples, the pretreatment or cleaning process can be carried out in the same reaction chamber as the selective deposition process, however, in some examples, the pretreatment or cleaning process can be carried out in a separate reaction chamber.

[0065] The term "about" is used herein to mean within the standard measurement accuracy.

[0066] Selective deposition using the methods described herein can be advantageously achieved by processes such as passivating the surface to prevent deposition thereon and / or by treating the surface (whether a metallic surface or a different dielectric surface) to catalyze deposition. In some examples, a passivation layer (e.g., a self-assembled monolayer (SAM)) and / or an inhibitor layer can be deposited on the respective surfaces of the substrate, which can prevent the corresponding top surfaces of the substrate from being exposed to the deposition processes described herein. Thus, in some examples, selectivity is achieved by using a capping agent or a catalyst, where the passivated or inhibited surface is not directly exposed to the deposition reactants.

[0067] Vapor deposition techniques can be applied to organic films and polymers such as polyimide films, polyamide films, polyurea films, polyurethane films, polythiophene films, etc. CVD of polymer films can result in better thickness control, mechanical flexibility, conformal coverage, and biocompatibility compared to liquid applied precursors. Sequential deposition processes of polymers can result in high growth rates in small research scale reactors. Similar to CVD, sequential deposition processes can result in better thickness control, mechanical flexibility, and conformality. The terms "sequential deposition" and "cyclic deposition" are used herein to refer to the process of alternately or sequentially exposing a substrate to different precursors, regardless of whether the reaction mechanism is similar to ALD, CVD, MLD, or a mixture thereof.

[0068] In some examples, the processes described herein can be batch processes, that is, these processes can be carried out simultaneously on two or more substrates. In some examples, the processes described herein can be carried out simultaneously on two or more, five or more, 10 or more, 25 or more, 50 or more, or 100 or more substrates. In some examples, the substrate can include a wafer, such as a semiconductor or silicon wafer. In some examples, the substrate can have a diameter of 100 mm or greater, 200 mm or greater, or 300 mm or greater. In certain cases, substrates with a diameter of 450 mm or greater may be desirable.

[0069] Selectivity

[0070] Selectivity can be given as a percentage calculated by [(deposition on surface A) - (deposition on surface B)] / (deposition on surface A), where surface A and surface B are composed of different materials. Deposition can be measured by any of a variety of methods. In some examples, deposition can be given as the measured thickness of the deposited material. In some examples, deposition can be given as the measured amount of the deposited material.

[0071] In some examples, the selectivity 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%. In the examples described herein, the selectivity can vary with the duration or thickness of the deposition.

[0072] In some examples, deposition occurs only on surface A and not on surface B. In some examples, the deposition on surface A of the substrate has at least about 80% selectivity relative to surface B of the substrate, which may be sufficient selectivity for some specific applications. In some examples, the deposition on surface A of the substrate has at least about 50% selectivity relative to surface B of the substrate, which may be sufficient selectivity for some specific applications. In some examples, the deposition on surface A of the substrate has at least about 10% selectivity relative to surface B of the substrate, which may be sufficient selectivity for some specific applications. In some examples, the deposition on the first surface of the substrate has at least about 80% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some examples, the deposition on the first surface of the substrate has at least about 50% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some examples, the deposition on the first surface of the substrate has at least about 10% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications.

[0073] In some examples, the thickness of the organic film deposited on the first surface of the substrate can be less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm or less than about 1 nm, while the material ratio of the deposition on the first surface of the substrate relative to the second surface of the substrate can be greater than or equal to about 2:1, greater than or equal to about 20:1, greater than or equal to about 15:1, greater than or equal to about 10:1, greater than or equal to about 5:1, greater than or equal to about 3:1 or greater than or equal to about 2:1.

[0074] In some examples, the substrate can include more than two surfaces that are different in material (e.g., a first surface 304, a second surface 306, and a third surface 308, as Figure 3as shown). In such examples, the deposition can occur at different selectivity levels depending on the surfaces being compared. For example, the selectivity of the first surface 304 relative to the second surface 306 can be 50%, while the selectivity of the third surface 308 relative to the second surface 306 can be 80%. Similarly, the ratio of the material deposited can be different depending on the surfaces being compared. For example, the ratio of the material deposited on the first surface 304 relative to the second surface 306 can be greater than or equal to about 2:1, while the ratio of the material deposited on the third surface 308 relative to the second surface 306 can be greater than or equal to about 20:1.

[0075] In some examples, the selectivity of the selective deposition process described herein can depend on the materials of the first, second, and third surfaces of the substrate. The selectivity of the deposited material can be described as a percentage or ratio of deposition on the first surface to that on the second surface, even when there are multiple exposed surface materials on a single substrate.

[0076] In some examples of metal inhibitor deposition, where the first surface contains W and the second surface contains a low-k silica surface, the selectivity of the inhibitor on W to that on the low-k material can be greater than about 8:1 or greater than about 15:1. In some examples where the first surface contains a metal or metal oxide and the second surface contains a native or chemical silica surface, the selectivity can be greater than about 5:1 or greater than about 10:1. In some examples where the first surface contains a chemical or native silica surface and the second surface contains a thermal silica surface, the selectivity can be greater than about 5:1 or greater than about 10:1.

[0077] Figure 1 A deposition assembly 100 in accordance with the present disclosure is shown schematically. The deposition assembly 100 can be used to perform the methods described herein and / or selectively deposit the organic materials described herein. In yet another aspect, the semiconductor processing assembly 100 can be configured to selectively deposit a passivation and / or inhibitor material on the first, second, and / or third surfaces of a substrate 128.

[0078] In the example shown, the deposition assembly 100 includes one or more reaction chambers 102, a precursor injection system 101, a first precursor container 104, a second precursor container 106, a third precursor container 107, a fourth precursor container 108, a scavenger container 111, an exhaust source 144, a remote plasma source 146, a direct plasma source 147, and a controller 145. The deposition assembly 100 can include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source. The reaction chamber 102 can include any suitable reaction chamber, such as the ALD or CVD reaction chambers described herein.

[0079] The first precursor container 104 may include a container and one or more first precursors 110 as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). The second precursor container 106 may include a container and one or more second precursors 112 as described herein—either alone or mixed with one or more carrier gases. The third precursor container 107 may include a container and one or more inhibitor precursors 115 as described herein—either alone or mixed with one or more carrier gases. The fourth precursor container 108 may include a container and one or more inhibitor precursors 120 as described herein—either alone or mixed with one or more carrier gases. The scavenger container 111 may include a container and one or more scavengers 121 as described herein—either alone or mixed with one or more carrier gases. Although four source containers 104, 106, 107, 108, and 111 are shown, the deposition assembly 100 may include any suitable number of source containers. The source containers 104, 106, 107, 108, and 111 may be coupled to the reaction chamber 102 via respective lines 114, 116, 118, 119, and 122, which may each include a flow controller, valve, heater, etc. In some examples, the first precursor 110 may be stored in the first precursor container 104, the second precursor 112 may be stored in the second precursor container 106, the first inhibitor precursor 115 may be stored in the third precursor container 107, the second inhibitor precursor 120 may be stored in the second inhibitor precursor container 108, and the scavenger 121 may be stored in the scavenger container 111. The source containers 104, 106, 107, 108, and 111 may be heated.

[0080] The exhaust source 144 may include one or more vacuum pumps. The controller 145 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the deposition assembly 100. Such circuitry and components are used to introduce precursors, reactants, and purge gases from the respective sources.

[0081] The controller 145 may control the timing of the gas pulse sequence, the temperature of the substrate and / or the reaction chamber 102, the pressure within the reaction chamber 102, and various other operations to provide proper operation of the deposition assembly 100. The controller 145 may include control software to control valves, either electrically or pneumatically, to control the flow of precursors, reactants, and purge gases into and out of the reaction chamber 102. The controller 145 may include modules that perform specific tasks, such as software or hardware components. The modules may be configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0082] Other configurations of the deposition assembly 100 are possible, including different numbers and types of precursor and reactant sources. In addition, it should be understood that many arrangements of valves, conduits, precursor sources, and auxiliary reactant sources can be used to achieve the goal of selectively and in a coordinated manner supplying gases to the reaction chamber 102. In addition, as a schematic representation of the deposition assembly, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0083] During operation of the deposition assembly 100, a substrate such as a semiconductor wafer (e.g., substrate 128) is transferred from, for example, a substrate handling system to the reaction chamber 102. Once the substrate is transferred to the reaction chamber 102, one or more gases from a gas source, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into the reaction chamber 102.

[0084] In an example, the first precursor 110 can include an alkylaminosilane material for depositing a passivation layer, as described in more detail herein. In an example, the second precursor 112 can include a hydrophobic material, as described in more detail herein.

[0085] In one example, the first inhibitor precursor 115 can include an amine (e.g., a diamine, a triamine, a tetraamine, and / or a cyclic compound including at least two primary amine groups), as described in more detail herein. In one example, the second inhibitor precursor 120 can include an anhydride, such as furan-2,5-dione (maleic anhydride), a dianhydride (e.g., pyromellitic dianhydride (PMDA)), and / or a dianhydride including at least one thioanhydride group (e.g., 1,2,4,55-tetrathio-cyclo-1,2:4,5-bis(dehydrosulfide)1,2,4,5-benzenetetracarboxylic acid (pyromellitic dithioanhydride (PMDTA)), as described in more detail herein.

[0086] In some examples, a reactor system (e.g., reactor system 100) can include multiple reaction chambers. Figure 2 In the reactor system 200 shown, a plurality of reaction chambers 204 (each reaction chamber can be Figure 1 2 (for example, any of the reaction chambers 102 in FIG. 1 ) can be disposed around and / or coupled to a transfer chamber 280 including a transfer tool 285 for transferring substrates between reaction chambers 204. The substrate can be transferred between the load lock chamber 212 and the reaction chamber 204 (e.g., via the transfer chamber 280). For example, for different steps of the semiconductor manufacturing process, the substrate 128 can be disposed in different chambers (e.g., surface cleaning, passivation, inhibition, film removal, etching, oxidation, and / or deposition steps can each be performed in the same or different chambers).

[0087] Selective deposition

[0088] Figure 3 Process 300 for selective deposition on substrate 128 is shown, where the operations of process 300 are shown in a cross-sectional view of substrate 128.

[0089] In one example, substrate 128 includes a first material 310 having a first surface 304, a second material 312 having a second surface 306, and a third material 314 having a third surface 308. In one example, the first material 310, the second material 312, and the third material 314 may be different materials.

[0090] In one example, the first material 310 and / or the first surface 304 may include an inorganic dielectric, such as a low-k layer (typically a silicon oxide-based layer) or a silicon surface with a native oxide (also a form of silicon oxide) formed thereon. For example, the first material 310 and / or the first surface 304 may include SiCOx, SiOx, SiO2, SiC, SiOC, SiON, SiOCN, SiGe, SiN, Si, high-k materials, low-k materials, etc. or a combination thereof.

[0091] In some examples, the second material 312 and / or the second surface 306 may include a metal oxide, a metal nitride, a metal oxynitride, a metal carboxide, or a combination thereof, or be defined thereby. In some examples, the second material 312 may include AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, SiCOx, SiOx, TaOx, TiOx, WOx, ZnOx, TiN, TaN, MoN, AlN, WN, TaON, SiCOx, SiOx, SiO2, SiC, SiOC, SiON, SiOCN, SiGe, SiN, or ZrOx, etc. or a combination thereof.

[0092] In some examples, the third material 314 and / or the third surface 308 may include a metallic material, an elemental metal, a metallic surface, or a combination thereof, or be defined thereby. In some examples, the second surface 308 may include aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr), or vanadium (V), etc. or a combination thereof.

[0093] The following description of process 300 refers to Figures 1 to 3 In one example, process 300 begins with operation 320, where substrate 128 having a first surface 304, a second surface 306, and a third surface 308 is supported in reaction chamber 102 (see Figure 1)。In some examples, the first material 310, the second material 312, and the third material 314 of the substrate 128 can be different in material, so the exposed first surface 304, second surface 306, and third surface 308 can be different in material.

[0094] Process 300 can proceed to operation 322, where selective deposition of the first passivation layer 324 can be performed on the first surface 304. The passivation layer 324 having a fourth surface 326 can be selectively formed on the first surface 304 relative to the second surface 306 and the third surface 308.

[0095] In one example, selectively depositing the first passivation layer includes contacting the substrate 128 with a first precursor including an alkylaminosilane (e.g., the first precursor 110). In one example, the first precursor 110 can include allyltrimethylsilane (TMS-A), 1,1,1-trimethoxy-N,N-dimethylsilanamine, trimethylchlorosilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), 1,1,1-trimethoxy-N,N-dimethylsilanamine, or trimethylchlorosilane, or a combination thereof.

[0096] In one example, the first precursor 110 can be provided to a reaction chamber containing the substrate 128 to contact the substrate 128 with a single pulse or a sequence of multiple pulses. In some embodiments, the first precursor 110 is provided in a single long pulse or multiple short pulses. The pulses can be provided sequentially. In some embodiments, the first precursor 110 is provided with 1 to 1000 pulses or any appropriate number of pulses of any appropriate duration from about 0.01 seconds to about 600 seconds. Between pulses, the first precursor 110 can be removed from the reaction space. For example, the reaction chamber can be evacuated and / or purged with an inert gas. The purge can last, for example, from about 0.01 to 600 seconds, or any suitable pulse period.

[0097] In some embodiments, the temperature of the passivation process can be, for example, from about 25°C to 500°C, or from about 100°C to about 300°C, or any suitable temperature. The pressure during the passivation process can be, for example, from about 0.01 to about 760 Torr, or in some embodiments from about 1 to 10 Torr or from about 0.1 to about 10 Torr.

[0098] Process 300 can proceed to operation 328, where selective deposition of a second passivation layer 330 can be performed on the second surface 306. The second passivation layer 330 having a fifth surface 332 can be selectively formed on the second surface 306 relative to the fourth surface 326 and the third surface 308. The second passivation layer 330 can include a hydrophobic alkylsilane capable of bonding to the hydroxyl groups present on the surface 306.

[0099] In one example, the second passivation layer 330 can include an alkylaminosilane.

[0100] In one example, the second passivation layer 330 can include an alkylaminosilane that includes a hydrophobic group that is unhalogenated or partially halogenated or fully halogenated.

[0101] In one example, the second passivation layer 330 can include an alkylaminosilane that includes a hydrophobic group that is partially halogenated or fully halogenated by one or more of fluorine, chlorine, bromine, or iodine.

[0102] In some examples, the alkylaminosilane can include a hydrophobic group that is partially halogenated or fully halogenated with fluorine.

[0103] In one example, selectively depositing the second passivation layer 330 includes contacting the substrate 128 with a second precursor (e.g., second precursor 112) that includes a non-chlorinated hydrophobic alkylsilane. The non-chlorinated hydrophobic alkylsilane can be an alkylaminosilane, a dialkylaminosilane, or a trialkylaminosilane.

[0104] In some examples, the alkylaminosilane can include a hydrophobic group that includes an alkyl and / or aryl group.

[0105] In some examples, the alkylaminosilane can include a hydrophobic group that includes a hydrophobic halogenated hydrocarbon that includes one or more of CH2, CHX, and / or CX2 units, where X is independently selected from fluorine, chlorine, bromine, or iodine.

[0106] In some examples, the alkylaminosilane can include a hydrophobic group that includes a non-chlorinated hydrophobic halogenated hydrocarbon that includes one or more of CH2, CHX, and / or CX2 units, where X is independently selected from fluorine, bromine, or iodine.

[0107] In some examples, the alkylaminosilane can include a hydrophobic group that includes a hydrophobic fluorocarbon chain that includes one or more of CH2, CHF, and / or CF2 units.

[0108] In some examples, the hydrophobic group can include an alkyl and / or aryl group having 100 or fewer carbon atoms, or 75 or fewer carbon atoms, or 50 or fewer carbon atoms, or 25 or fewer carbon atoms, or any suitable number of carbon atoms.

[0109] In some examples, the second precursor 112 can be an alkylaminosilane comprising a structure represented by general formula (1):

[0110]

[0111] wherein, R1 and R2 each independently comprise H or an alkyl group; wherein, R3 and R4 each independently comprise H, an alkyl group or an amino group of the formula NR1R2; wherein, any two or more of R1, R2, R3 and R4 can comprise the same alkyl group; and wherein, R5 is a hydrophobic halogenated hydrocarbon.

[0112] In some examples, R5 is a hydrophobic group comprising an alkyl group and / or an aryl group.

[0113] In some examples, R5 is a hydrophobic group comprising a hydrophobic halogenated hydrocarbon comprising one or more of CH2, CHX and / or CX2 units, wherein X is independently selected from fluorine, chlorine, bromine or iodine.

[0114] In some examples, R5 is a hydrophobic group comprising a non-chlorinated hydrophobic halogenated hydrocarbon comprising one or more of CH2, CHX and / or CX2 units, wherein X is independently selected from fluorine, bromine or iodine.

[0115] In some examples, R5 is a hydrophobic group comprising a hydrophobic fluorocarbon chain comprising CH2, CHF and / or CF2 units.

[0116] In some examples, R5 comprises a C1-C100 chain comprising units independently selected from unhalogenated C, CX, CX2 or CX3, wherein X is independently selected from fluorine, chlorine, bromine or iodine.

[0117] In some examples, R5 comprises a C1-C100 chain comprising units independently selected from unfluorinated C, CF, CF2 or CF3.

[0118] In some examples, R1, R2, R3 and R4 can each independently comprise an alkyl group selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or sec-butyl.

[0119] In some examples, the alkylaminosilane can be tridecafluoro-1,1,2,2-tetrahydrooctylmethyl-bis(dimethylamino)silane.

[0120] In one example, a second precursor 112 may be provided to a reaction chamber that holds a substrate 128 to contact the substrate 128 with a single pulse or a sequence of multiple pulses. In some embodiments, the second precursor 112 is provided as a single long pulse or multiple short pulses. Pulses may be provided sequentially. In some embodiments, the first precursor 112 is provided with 1 to 1000 pulses from about 0.01 seconds to about 600 seconds, or any appropriate number of pulses of any appropriate duration (e.g., a longer period depending on temperature). Between pulses, the second precursor 112 may be removed from the reaction space. For example, the reaction chamber may be evacuated and / or purged with an inert gas. The purge may last, for example, about 0.01 to 600 seconds or longer.

[0121] In some embodiments, the temperature of the passivation process may be, for example, from about 25 °C to 500 °C, or about 100 °C to about 300 °C. The pressure during the passivation process may be, for example, from about 0.01 to about 760 Torr, or in some embodiments from about 1 to 10 Torr or about 0.1 to about 10 Torr.

[0122] In one example, process 300 may proceed to operation 334, where selective deposition of an inhibitor layer 336 on a third surface 308 may be performed. The inhibitor layer 336 having a surface 338 may be selectively formed on the third surface 308 relative to a fourth surface 326 and a fifth surface 332. The inhibitor layer 336 may include polyamides, polyimides, dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, and other polymers capable of preferentially forming on the metal surface 308.

[0123] In one example, selectively depositing inhibitor layer 336 includes contacting substrate 128 with a first inhibitor precursor comprising an amine, such as first inhibitor precursor 115, the amine being, for example, a diamine (such as 1,6-diamantane (DAH)), a triamine (such as tris(aminoethyl)methylsilane), a tetraamine (such as 2,2-bis(aminomethyl)-1,3-propanediamine), and / or a cyclic compound comprising at least two primary amine groups, and contacting the substrate with a second inhibitor precursor, such as second inhibitor precursor 120, comprising an acid anhydride, such as furan-2,5-dione (maleic anhydride), a dianhydride (such as pyromellitic dianhydride (PMDA) and / or pyromellitic dithioanhydride (PMDTA)), or any other substance having two reactive groups that will react with the first inhibitor precursor. Such first and second inhibitor precursors are disclosed in U.S. Patent Application Serial No. 63 / 546,475, filed Oct. 30, 2023, the entire disclosure of which is incorporated herein by reference. Additional or alternative example processes for selectively depositing such inhibitor layer 336 comprising a polyamide or polyimide by a vapor deposition technique are included in U.S. Patent No. 10,373,820, issued Aug. 6, 2019, the entire disclosure of which is incorporated herein by reference.

[0124] In one example, process 300 can proceed to operation 340, where a portion of passivation layer 324, passivation layer 330, and / or inhibitor layer 336 can be removed. In one example, passivation layer 324 and passivation layer 330 can be removed by performing a heat treatment at a temperature lower than the temperature at which the polymer layer comprising inhibitor layer 336 is removed.

[0125] In another example, passivation layer 324 and passivation layer 330 can be completely or almost completely removed by exposing substrate 128 to a remover, such as remover 121. In certain examples, the remover can be a plasma or O3. An advantage of using O3 can be that the removal of the passivation layer and the inhibitor layer can be accomplished in the same chamber as the previous deposition process.

[0126] More specifically, after removing the passivation layer 324 from the first surface 304, removing the passivation layer 330 from the second surface 306, and removing a portion of the inhibitor layer 336 from the third surface 308, the substrate 128 is shown in operation 340. In some examples, an etching process can be employed to remove the passivation layer 324, the passivation layer 330, and / or a portion of the inhibitor layer 336, including exposing the substrate to a plasma. In some examples, the plasma can include oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof. In some examples, the plasma can include hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. In some examples, the plasma can include NH3 molecules, NH3 plasma, or a combination thereof. In some examples, the plasma can further include an inert gas species, such as an Ar, N2, or He species. In some examples, the plasma can consist essentially of an inert gas species. In some cases, the plasma can include other species, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or a combination thereof.

[0127] In some examples, the etching process can include exposing the substrate to an etchant containing oxygen (such as O3). In some examples, the substrate can be exposed to an etchant at a temperature between about 25°C and about 500°C, preferably between about 100°C and about 400°C. In some examples, the etchant can be supplied in a continuous pulse or in multiple shorter pulses.

[0128] As described above, in some examples, O3 (such as O3 / N2) can be used in the etching process to remove the passivation layer 324, the passivation layer 330, and / or a portion of the inhibitor layer 336. In some examples, the etching process can be performed at a substrate temperature between about 25°C and about 500°C.

[0129] In some examples, the etching process can proceed at a rate from about 0.001 nm / minute to about 500.0 nm / minute. In some examples, the etching process can proceed at a rate from about 0.1 nm / minute to about 5.0 nm / minute. In some examples for single wafer or small batch (such as 5 wafers or less) processing, a low O3 concentration etching process can be used, where the low O3 concentration etching process is performed at 0.01 Torr to 760 Torr, more specifically about 0.1 Torr to 100 Torr (such as 2 Torr). The etchant pulse can be between 0.001 seconds and 1800 seconds, particularly between 1 second and 50 seconds. The O3 flow rate can range from 0.001 slm to 50 slm, more specifically from 0.1 slm to 1 slm. The inert (such as N2) carrier gas flow rate can range from 0.001 slm to 50 slm, more specifically from 0.1 slm to 1 slm.

[0130] Process 300 may proceed to operation 342, in which a material layer 344 is deposited on a portion of the first surface 304, the second surface 306, or the third surface 308 (if exposed), or a combination thereof. Most of the surface 308 may remain covered by the inhibitor layer 336, such that the material layer 344 will not cover the unexposed regions of the third surface 308. The material layer 344 may include the same material as material 310, or may be any one of a variety of different materials. For example, the material layer 344 may be a different metal oxide (e.g., any metal oxide, including but not limited to AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, SiCOx, SiOx, TaOx, TiOx, WOx, ZnOx, or ZrOx, or any combination thereof), a metal nitride (e.g., a metal nitride, including but not limited to TaN, MoNx, WNx, or TiN, or any combination thereof), a metal (e.g., including but not limited to Al, Cu, W, Co, Nb, Mo, Ru, Ti, Ta, or V, or any combination thereof), a metal carbide (e.g., a metal carbide, including but not limited to VCx, MoCx, NbCx, TaCx, TiCx, or WCx, or any combination thereof), silicon oxynitride or silicon carbonitride, or any combination thereof, or any other suitable material.

[0131] In one example, process 300 may proceed to operation 346, in which the inhibitor layer 336 may be completely removed. In one example, the remaining portion of the inhibitor layer 336 may be completely or almost completely removed by exposing the substrate 128 to a remover (e.g., remover 121) at an appropriate temperature and pressure. In certain examples, the remover may be an H2 plasma or O3, or the same or a similar method as described above with respect to operation 340 for removing the passivation layer. Again, the advantage of using O3 to remove the inhibitor layer may be that the removal of the first and second passivation layers and the inhibitor layer may be accomplished in the same chamber as the previous deposition process. Removing layer 336 requires additional time and energy.

[0132] In a particular embodiment, the surfaces 304, 306, and 308 may include various topologies within the device, including but not limited to 2D or 3D structures within gap features, where the surfaces 304, 306, and 308 are parallel, and / or at various angles to each other, and / or adjacent to each other, and / or in a repeating pattern, etc., or a combination thereof.

[0133] Figure 4 An example process 400 for selectively depositing a metal on a substrate in accordance with embodiments of the present disclosure is shown. In one example, process 400 may include providing a substrate (e.g., Figure 1 in the reaction chamber 102 as shown in Figure 3the substrate 128) shown in, where the substrate includes a first surface (e.g., Figure 3 the first surface 304) shown in, a second surface (e.g., Figure 3 the second surface 306) shown in, and / or a third surface (e.g., Figure 3 the third surface 308) shown in, or a combination thereof. The first surface, the second surface, and / or the third surface may include different substances on the material. The selective deposition process 400 may further include depositing a first passivation layer having a fourth surface (e.g., Figure 3 the fourth surface 326) shown in, (e.g., Figure 3 the first passivation layer 324) shown in, depositing a second passivation layer having a fifth surface (e.g., Figure 3 the fifth surface 332) shown in, (e.g., Figure 3 the first passivation layer 330) shown in, and / or depositing an inhibitor layer having a sixth surface (e.g., Figure 3 the sixth surface 338) shown in, (e.g., Figure 3 the inhibitor layer 336) shown in. The fourth surface, the fifth surface, and the sixth surface may be different substances on the material. In one example, the selective deposition of the first passivation layer, the second passivation layer, and / or the inhibitor layer may occur in any order, and the claimed subject matter is not limited thereto.

[0134] The selective deposition process 400 may further include removing the first passivation layer, removing the second passivation layer, and / or removing the inhibitor layer. The selective deposition process 400 may further include depositing a metal layer (e.g., Figure 3 the metal layer 344) shown in on the first surface, the second surface, and / or the third surface, or a combination thereof. In one example, the selective removal of the first passivation layer, the second passivation layer, and / or the inhibitor layer may occur in any order, and the claimed subject matter is not limited thereto. In one example, the process 400 may start with operation 420, where a substrate may be provided in a reaction chamber. In one example, the substrate may include two or more of the first surface, the second surface, and / or the third surface.

[0135] The process 400 may proceed to operation 422, where a first precursor including an alkylaminosilane (e.g., Figure 1The first precursor (e.g., the first precursor 110 shown in ) can contact the substrate to selectively deposit a first passivation layer on the first surface relative to the second surface and / or the third surface (e.g., where the first passivation layer 324 is deposited before the second passivation layer 330 and the inhibitor layer 336). Alternatively, the first precursor can contact the substrate to selectively deposit a first passivation layer on the first surface relative to the fifth surface of the second passivation layer and / or the third surface of the substrate (e.g., where the second passivation layer 330 is deposited before depositing the first passivation layer 324 and / or the inhibitor layer 336). Alternatively, the first precursor can contact the substrate to selectively deposit a first passivation layer on the first surface relative to the fifth surface of the second passivation layer and / or the sixth surface of the inhibitor layer (e.g., where the second passivation layer 330 and the inhibitor layer 336 are deposited before depositing the first passivation layer 324). For the sake of brevity, the above examples are intended to be illustrative. An exhaustive list of all possible combinations of the deposition patterns of the first passivation layer on the various surfaces of the substrate relative to various other surfaces of the substrate or layers deposited thereon is not specifically enumerated herein, and the claimed subject matter is not limited thereto.

[0136] Process 400 can proceed to operation 424, where a second precursor (e.g., Figure 1 the second precursor 112 shown in ) that includes a hydrophobic compound can contact the substrate to selectively deposit a second passivation layer on the second surface relative to the third surface of the substrate and the fourth surface of the first passivation layer (e.g., where the second passivation layer 330 is deposited after depositing the first passivation layer 324 and before depositing the inhibitor layer 336). Alternatively, the second precursor can contact the substrate to selectively deposit a second passivation layer on the second surface relative to the first surface of the substrate and the third surface of the substrate (e.g., the second passivation layer 330 is deposited before depositing the first passivation layer 324 and the inhibitor layer 336).

[0137] Alternatively, the second precursor can contact the substrate to selectively deposit a second passivation layer on the second surface relative to the fourth surface of the first passivation layer and the sixth surface of the inhibitor layer (e.g., the second passivation layer 330 is deposited after depositing the first passivation layer 324 and the inhibitor layer 336). For the sake of brevity, the above examples are intended to be illustrative. An exhaustive list of all possible combinations of the deposition patterns of the second passivation layer on the various surfaces of the substrate relative to various other surfaces of the substrate or layers deposited thereon is not specifically enumerated herein, and the claimed subject matter is not limited thereto.

[0138] In one example, process 400 can proceed to operations 426 and 428, where a first inhibitor precursor (e.g., Figure 1 the first inhibitor precursor 115 shown in ) that includes an amine can contact the substrate, and a second inhibitor precursor (e.g., Figure 1The second inhibitor precursor shown (120) can contact the substrate to selectively deposit an inhibitor layer on the third surface of the substrate relative to the fourth surface of the first passivation layer and the fifth surface of the second passivation layer (e.g., where the inhibitor layer 336 is deposited after depositing the first passivation layer 324 and the second passivation layer 330). Alternatively, the first inhibitor precursor and the second inhibitor precursor can contact the substrate to selectively deposit an inhibitor layer on the third surface of the substrate relative to the first surface of the substrate and the fifth surface of the second passivation layer (e.g., where the inhibitor layer is deposited after depositing the second passivation layer 330 and before depositing the first passivation layer 324). Alternatively, the first inhibitor precursor and the second inhibitor precursor can contact the substrate to selectively deposit an inhibitor layer on the third surface of the substrate relative to the fourth surface of the first passivation layer and the second surface of the substrate (e.g., where the inhibitor layer is deposited after depositing the first passivation layer 324 and before depositing the second passivation layer 330). For the sake of brevity, the above examples are intended to be illustrative. An exhaustive list of all possible combinations of the deposition patterns of the inhibitor layer on the various surfaces of the substrate relative to various other surfaces of the substrate or layers deposited thereon is not specifically enumerated herein, and the claimed subject matter is not limited thereto.

[0139] In addition, process 400 can be performed to deposit the first passivation layer, the second passivation layer, and the inhibitor layer. Alternatively, the second passivation layer can be deposited on the surface of the substrate having the first passivation layer 324 or the inhibitor layer 336 or both the first passivation layer 324 and the inhibitor layer 336, as indicated by the dashed lines at operation blocks 422, 426, and 428.

[0140] In one example, process 400 can proceed to operation 430, where the reaction chamber can be purged by pulsing a purge gas into the reaction chamber. In one example, the cyclic deposition process 400 as described herein can include one or more pulses. As indicated by the dashed line 454, one or more purges can be before, separate from, and / or after one or more of operations 420, 422, 424, 426, and / or 428. The purge can intermittently expose the substrate to the purge gas. Suitable purge gases include inert or substantially inert gases. In some embodiments, the purge gas includes one or more of N2 and / or noble gases. Suitable noble gases include He, Ne, Ar, Kr, and Xe.

[0141] In one example, process 400 may include performing operations 422, 424, 426, 428, or 430, or any combination thereof, in any order, any number of times, until the respective first passivation layer, second passivation layer, and / or inhibitor layer reaches a predetermined thickness. Operations 422, 424, 426, 428, and / or 430, or any combination thereof, may be performed in a loop until each respective first passivation layer, second passivation layer, and / or inhibitor layer reaches a predetermined thickness. This is represented by dashed line 452.

[0142] In one example, process 400 may proceed to operation 442, where the substrate may be exposed to a remover to remove a portion of the first passivation layer, second passivation layer, and / or inhibitor layer in response to the exposure to the remover. In one example, the remover may be any one of the various removers discussed in more detail above. Additionally, an advantage of using O3 may be that the removal of the passivation layer and inhibitor layer can be done in the same chamber as the previous deposition process.

[0143] In one example, process 400 may proceed to operation 444, where a layer may be deposited on the first surface, the second surface, and a portion of the third surface. The layer may include a variety of materials as described in more detail above.

[0144] In one example, process 400 may proceed to operation 446, where the substrate may be exposed to a remover to remove a portion of the first passivation layer, second passivation layer, and / or inhibitor layer in response to the exposure to the remover. In one example, the remover may be any one of the various removers discussed in more detail above.

[0145] In one example, process 400 may proceed to operation 450, where the process may end.

[0146] One skilled in the art can readily determine the optimal exposure time, temperature, and power for removing the desired amount of deposited organic material from the substrate.

[0147] Although exemplary examples of the present disclosure are set forth herein, it should be understood that the present disclosure is not limited thereto. Various modifications, variations, and enhancements may be made to the systems and methods set forth herein without departing from the spirit and scope of the present disclosure.

[0148] The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of various processes, systems, and configurations, as well as other features, functions, acts, and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A process for selectively depositing a metal on a substrate, comprising: a) providing a substrate in a reaction chamber, the substrate comprising a first surface, a second surface and a third surface; b) contacting the substrate with a first precursor comprising a first alkylaminosilane to selectively deposit a first passivation layer on the first surface; c) contacting the substrate with a second precursor comprising a hydrophobic group to selectively deposit a second passivation layer on the second surface; d) contacting the substrate with a first inhibitor precursor comprising an amine, and e) contacting the substrate with a second inhibitor precursor comprising a dianhydride to selectively deposit an inhibitor layer on the third surface.

2. The process of claim 1, further comprising: f) purging the reaction chamber; and At least one of operations b), c), d), e) or f) is performed in any order until the first passivation layer, the second passivation layer or the inhibitor layer, or a combination thereof, is deposited onto a respective surface of the first surface, the second surface or the third surface, or a combination thereof.

3. The process of claim 2, further comprising: Repeat at least one of operations b), c), d), e) or f) in any order until at least one of: the first passivation layer reaches a first predetermined thickness, the second passivation layer reaches a second predetermined thickness, or the inhibitor layer reaches a third predetermined thickness, or a combination thereof.

4. The process of claim 1, wherein: The first passivation layer has a fourth surface and is deposited relative to the second surface and the third surface; The second passivation layer has a fifth surface and is deposited relative to the third surface and the fourth surface; and The inhibitor layer has a sixth surface and is deposited opposite the fourth surface and the fifth surface.

5. The process of claim 1, wherein: The first surface comprises a dielectric surface.

6. The process of claim 5, wherein: The dielectric surface is a low-k material.

7. The process of claim 1, wherein: The second surface comprises metal oxide, metal nitride, metal oxynitride or metal carbide or a combination thereof.

8. The process of claim 7, wherein: The second surface comprises AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, TaOx, TiOx, WOx, ZnOx, TiN, TaN, MoN, AlN, WN, TaON, SiCOx, SiOx, SiO2, SiC, SiOC, SiON, SiOCN, SiGe, SiN or ZrOx or any combination thereof.

9. The process of claim 1, wherein: The third surface includes metal.

10. The process of claim 9, wherein: The metal includes aluminum (Al), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), indium (In), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), niobium (Nb), ruthenium (Ru), tantalum (Ta), titanium (Ti), tungsten (W), vanadium (V) or zinc (Zn) or a combination thereof.

11. The process of claim 1, wherein: The first alkylaminosilane is allyltrimethylsilane (TMS-A), trimethylchlorosilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), N-(trimethylsilyl)dimethylamine (TMSDMA), trimethylchlorosilane or 1,1,1-trimethoxy-N,N-dimethylsilylamine or a combination thereof.

12. The process of claim 1, wherein: The second precursor comprises a second alkylaminosilane comprising a hydrophobic group that is partially or fully halogenated with one or more of fluorine, chlorine, bromine, or iodine.

13. The process of claim 1, wherein: The second precursor comprises a second alkylaminosilane comprising a structure represented by the general formula (1): wherein R1 and R2 each independently comprise H or an alkyl group; wherein R3 and R4 each independently comprise H, an alkyl group or an amino group of the formula NR1R2; wherein any two or more of R1, R2, R3 and R4 may comprise the same alkyl group; and wherein R5 is a hydrophobic halogenated hydrocarbon.

14. The process of claim 13, wherein: R5 includes an alkyl group or an aryl group or a combination thereof.

15. The process of claim 13, wherein: The hydrophobic halogenated hydrocarbon is a carbon chain comprising one or more of CH2, CHX and CX2 units; wherein X is independently selected from fluorine, chlorine, bromine or iodine.

16. The process of claim 15, wherein: The hydrophobic halogenated hydrocarbon is non-chlorinated.

17. The process of claim 13, wherein: The hydrophobic halogenated hydrocarbon is a fluorocarbon chain containing CH2, CHF or CF2 units or a combination thereof.

18. The process of claim 13, wherein: R5 comprises a C1-C100 chain comprising units independently selected from unhalogenated C, CX, CX2 or CX3, wherein X is independently selected from fluorine, chlorine, bromine or iodine.

19. The process of claim 13, wherein: The second alkylaminosilane includes dialkylaminosilane, and the hydrophobic halogenated hydrocarbon includes 1 to 100 carbon atoms.

20. The process of claim 13, wherein: R1, R2, R3 and R4 each independently comprise an alkyl group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or sec-butyl.

21. The process of claim 1, wherein: The second precursor includes tridecafluoro-1,1,2,2-tetrahydrooctylmethyl-bis(dimethylamino)silane.

22. The process of claim 1, wherein: The amine is a diamine, a triamine, a tetraamine or a cyclic compound containing at least two primary amines, or a combination thereof.

23. The process of claim 1, wherein: The dianhydride is pyromellitic dianhydride (PMDA) or pyromellitic dithioanhydride (PMDTA).

24. The process of claim 1 further comprising: exposing the substrate to a remover; as well as In response to exposure to the remover, the first passivation layer, the second passivation layer, and a portion of the inhibitor layer are removed.

25. The process of claim 24, wherein: The remover is H2 plasma or O3.

26. The process of claim 24, further comprising depositing a film on a portion of the first surface, the second surface, or the third surface, or a combination thereof, after the removing.

27. The process of claim 26, wherein: The film includes a metal, a metal nitride, a metal carbide, silicon oxynitride or silicon oxycarbide, or any combination thereof.

28. The process of claim 27, wherein: The film contains Al, Cu, W, Co, Nb, Mo, Ru, Ti, Ta, V, AlOx, CoOx, CrOx, GaOx, HfOx, MnOx, MoOx, NbOx, NiOx, RuOx, SiCOx, SiOx, TaOx, TiOx, WOx, ZnOx, ZrOx, TaN, MoNx, WNx, TiN, VCx, MoCx, NbCx, TaCx, TiCx or WCx or any combination thereof.

29. The process of claim 26, further comprising removing a remaining portion of the inhibitor layer in response to exposing the substrate to a remover comprising H2 plasma or O3.

30. A method for selective deposition on a substrate, comprising: a) providing a substrate in a reaction chamber, the substrate comprising a first surface and a second surface, wherein the first surface is different from the second surface in material, wherein the first surface is a metal oxide, a metal nitride, a metal oxynitride or a metal carbide or a combination thereof, wherein the second surface is a dielectric or a metal; as well as b) contacting the substrate with a precursor comprising a hydrophobic compound to selectively deposit a passivation layer on the first surface relative to the second surface.

31. The method of claim 30, further comprising: c) purging the reaction chamber; as well as At least one of operations b) and c) is performed until the passivation layer is selectively deposited on the first surface with respect to the second surface to a predetermined thickness.

32. The method according to claim 31, wherein: The precursor includes an alkylaminosilane comprising a structure represented by the general formula (1): wherein R1 and R2 each independently comprise H or an alkyl group; wherein R3 and R4 each independently comprise H, an alkyl group or an amino group of the formula NR1R2; wherein any two or more of R1, R2, R3 and R4 may comprise the same alkyl group; and wherein R5 is a hydrophobic halogenated hydrocarbon.

33. The method of claim 32, wherein: The hydrophobic halogenated hydrocarbon is a fluorocarbon chain.

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