Selective deposition of inhibitor material and deposition assembly

Abstract

The present disclosure relates to methods, processing assemblies, reactants and vapor deposition containers for selective vapor deposition of inhibitor materials on a substrate comprising two surfaces. In some embodiments of the present disclosure, an inhibiting material is deposited on the first surface of the substrate, without substantially any inhibiting material being deposited on the second surface of the substrate. The inhibitor material is formed by contacting the substrate with a gas phase inhibitor reactant comprising a silicon atom bonded to an oxygen atom and a second atom selected from nitrogen and halogen.

Description

Technical Field

[0001] The present disclosure generally relates to methods and assemblies for selectively depositing materials on substrates. Such methods can be used, for example, to process semiconductor substrates. More specifically, the present disclosure relates to methods and assemblies for selectively depositing inhibitor materials on substrates, as well as methods for depositing target materials. Background Art

[0002] Semiconductor device manufacturing processes often use advanced vapor deposition methods. Patterning is often used to deposit different materials on semiconductor substrates. 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 allow for enhanced scaling of narrow structures. Various alternatives to achieve selective deposition have been proposed, and additional improvements are needed to expand the use of selective deposition in industrial-scale device manufacturing.

[0003] Various materials, such as metal oxides, metal nitrides, elemental metals, and silicon-containing materials, such as silicon oxide, silicon nitride, and such materials combined with additional elements such as carbon, can be used for various purposes in semiconductor devices. The ability to choose the deposition surface between dielectric materials and conductive materials (such as metals or conductive metal nitrides) can simplify the device manufacturing process flow, allowing for the deposition of more sensitive materials, potentially more precisely because the need for patterning and etching steps can be reduced. Thermal deposition methods may be preferred over plasma enhanced methods due to better compatibility with sensitive materials. However, advanced semiconductor manufacturing techniques may combine thermal and plasma enhanced deposition, as well as steps that utilize plasma in the optimized deposition process.

[0004] Any discussion set forth in this section, including discussion of problems and solutions, has been included in the present disclosure merely to provide context for the present disclosure. Such discussion should not be considered as an admission that any information was known or constituted prior art when the subject matter of the present disclosure was conceived. Summary of the invention

[0005] This summary may introduce some concepts in a simplified form, which are further described in detail below. This summary is not intended to necessarily identify 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. Various embodiments of the present disclosure are directed to methods of depositing inhibitor materials, passivation materials, and various target materials; in particular, selectively depositing inhibitor materials, passivation materials, and various target materials. Embodiments of the present disclosure also relate to methods of manufacturing semiconductor devices, and semiconductor processing assemblies.

[0006] In one aspect, a method for selectively depositing an inhibitor material on a first surface of a substrate relative to a second surface of the substrate is disclosed. The method includes providing a substrate comprising a first surface and a second surface in a reaction chamber, and contacting the substrate with a gas phase inhibitor reactant, the inhibitor reactant comprising a silicon atom bonded to a first atom and a second atom. In the inhibitor reactant, the first atom is oxygen, the second atom is selected from nitrogen and a halogen, and the inhibitor reactant selectively forms an inhibitor material on the first surface. The inhibitor material in the present disclosure refers to a substance that reduces or prevents the deposition of an organic polymer. In some embodiments, the inhibitor material can reduce or prevent the deposition of a target material. The passivation material in the present disclosure refers to a substance that reduces or prevents the deposition of a target material.

[0007] In some embodiments, the first surface comprises a dielectric material. In some embodiments, the dielectric material comprises silicon. In some embodiments, the first surface comprises a material selected from SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, and combinations thereof. In some embodiments, the dielectric material on the first surface comprises a metal oxide or a metal nitride. In some embodiments, the dielectric material on the first surface is selected from aluminum oxide, hafnium oxide, zirconium oxide, aluminum nitride, tantalum nitride, and combinations thereof.

[0008] In some embodiments, the second surface is a conductive surface. In some embodiments, the second surface comprises a material selected from metals, amorphous carbon, metal oxides, and metal nitrides. In some embodiments, the second surface comprises a transition metal. In some embodiments, the second surface comprises a metal selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ru, and Al. In some embodiments, the second surface comprises an elemental metal.

[0009] In some embodiments, the first atom in the inhibitor reactant is an oxygen of an alkoxy group. In some embodiments, a silicon atom is bonded to at least one alkoxy group. For clarity, at least one alkoxy group is bonded to a silicon atom through an oxygen ("alkoxy oxygen").

[0010] In some embodiments, the silicon atom is bonded to at least two alkoxy oxygens. Thus, in some embodiments, the silicon atom is bonded to at least two oxygen atoms, and each oxygen atom is an oxygen of an alkoxy group.

[0011] In some embodiments, the second atom is a nitrogen atom of an amine group. In some embodiments, the amine group is a tertiary amine. In some embodiments, the second atom is a halogen selected from F, Cl, Br and I.

[0012] In some embodiments, the inhibitor reactant is of the formula Si(OR) a X b R' crepresents, wherein each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl; each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl; X is selected from halogen or NR'2; a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4.

[0013] In some embodiments, all R and R' are C1 to C4 alkyl. In some embodiments, each R is methyl or ethyl. In some embodiments, all R are methyl or ethyl. In some embodiments, all R' are methyl or ethyl. In some embodiments, all R and R' are methyl or ethyl.

[0014] In some embodiments, the inhibitor reactant is selected from Si(OMet)3Cl, Si(OMet)3Br, Si(OMet)3I,Si(OMet)2Cl2, Si(OMet)2Br2, Si(OMet)2I2, Si(OEt)3Cl, Si(OEt)3Br, Si(OEt)3I, Si(OEt)2Cl2, Si(OEt)2Br2, Si(OEt)2I2, Si(OMet)3(NH2), Si(OMet)2(NH2)2, Si(OEt)3(NH2), Si(OEt)2(NH2)2, Si(OMet)3(NMet2), Si(OMet)2(NMet2)2, Si(OEt)2(NMet2)2, Si(OMet)3(NMetH), Si(OMet)2(NMetH)2, Si(OEt)3(NMetH), Si(OEt)2(NMetH)2, Si(OMet)3(NEt2), Si(OMet)2(NEt2)2, Si(OEt)3(NEt2) and Si(OEt)2(NEt2)2.

[0015] In some embodiments, the depositing of the inhibitor material is performed at a temperature below 400° C. In some embodiments, the inhibitor material is deposited substantially only on the first surface and not on the second surface.

[0016] In one aspect, a method for selectively depositing an organic polymer on a second surface of a substrate relative to a first surface of the substrate is disclosed. The method includes selectively depositing an inhibitor material on the first surface of the substrate according to the present invention, and then selectively depositing the organic polymer on the second surface. In some embodiments, the organic polymer includes a polyimide. In some embodiments, the organic polymer forms a passivation layer on the second surface. In some embodiments, depositing the inhibitor material and depositing the organic polymer are performed in the same reaction chamber.

[0017] In another aspect, a method of selectively depositing a target material on a first surface of a substrate is disclosed. The method includes selectively depositing an inhibitor material according to the present disclosure on the first surface of the substrate before depositing the target material.

[0018] In some embodiments, the method further includes depositing a passivation layer on the second surface of the substrate after selectively depositing the inhibitor material on the first surface, and then depositing the target material on the first surface.

[0019] In some embodiments, the suppressor material is not removed prior to depositing the target material on the first surface.

[0020] In some embodiments, the target material is deposited by a cyclic deposition process. In some embodiments, the target material is deposited by an ALD process.

[0021] In yet another aspect, a semiconductor processing assembly for selectively depositing an inhibitor material on a first surface of a substrate is disclosed. The assembly includes one or more reaction chambers constructed and arranged to hold a substrate; a precursor injector system constructed and arranged to provide an inhibitor reactant in a gas phase into the reaction chamber. The semiconductor processing assembly also includes an inhibitor reactant source container constructed and arranged to contain an inhibitor reactant, the inhibitor reactant including a silicon atom bonded to a first atom and a second atom; wherein the first atom is oxygen and the second atom is selected from nitrogen and a halogen.

[0022] The semiconductor processing assembly is also constructed and arranged to provide the inhibitor reactant into the reaction chamber through the precursor injector system to selectively form the inhibitor material on the first surface of the substrate. In some embodiments, the semiconductor processing assembly according to the present disclosure further includes one or more precursor source containers, wherein the precursor injector system is constructed and arranged to provide one or more precursors from the one or more precursor source containers into the reaction chamber in a vapor phase to deposit the target material on the substrate.

[0023] In another aspect, a method for depositing a silicon-containing material on a substrate is disclosed. The method includes providing a substrate in a reaction chamber, and contacting the substrate with a silicon-containing material having a formula Si(OR) a X b R' cof a gas-phase silicon reactant. In the formula, each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl; each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl; X is selected from NR'2; a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4. The silicon reactant forms a silicon-containing material on the surface. In some embodiments, the silicon-containing material is an inhibitor. An inhibitor according to the present disclosure refers to a substance on the surface of a substrate that reduces or inhibits the deposition of a target material. In some embodiments, the silicon-containing material has a silicon-oxygen ratio of about 1:1 to 1:3. In some embodiments, the silicon-containing material is not subjected to oxidation. In some embodiments, the silicon-containing material is not in contact with an oxygen precursor.

[0024] In yet another aspect, a vapor deposition container is disclosed, comprising a vapor deposition container having the formula Si(OR) a X b R' c In the formula, each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl; each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl; X is selected from NR'2; a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The accompanying drawings, which are included to provide a further understanding of the disclosure and constitute a part of this specification, illustrate exemplary embodiments and together with the description help to explain the principles of the disclosure.

[0026] In the attached picture:

[0027] Figure 1 is a block diagram of an exemplary embodiment of a method of selectively depositing an inhibitor material according to the present disclosure.

[0028] Figure 2 is a block diagram of an exemplary embodiment of a method of selectively depositing an organic polymer according to the present disclosure.

[0029] Figure 3 is a block diagram of an exemplary embodiment of a method of selectively depositing a target material according to the present disclosure.

[0030] Figure 4 a) to e) in FIG. 1 are schematic diagrams of exemplary embodiments of the method according to the present disclosure.

[0031] Figure 5 is a schematic diagram of an embodiment of a semiconductor processing assembly according to the present disclosure.

[0032] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. The illustrations presented herein are not meant to be actual views of any particular layer, structure, device, or processing component, but are merely idealized representations for describing embodiments of the present disclosure. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0033] The descriptions of exemplary embodiments of methods and semiconductor processing assemblies provided below are merely exemplary and are for illustrative purposes only. The following description is not intended to limit the scope of the present disclosure or the claims. In addition, the recitation of multiple embodiments having the features shown is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the features described. For example, various embodiments are set forth as exemplary embodiments and may be recited in dependent claims. Unless otherwise stated, the exemplary embodiments or components thereof may be combined or may be applied separately from each other.

[0034] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed subject matter.

[0035] In one aspect, a method for selectively depositing an inhibitor material on a first surface of a substrate relative to a second surface of the substrate is disclosed. The method includes providing a substrate including a first surface and a second surface in a reaction chamber, and contacting the substrate with a gas-phase inhibitor reactant, the inhibitor reactant comprising a silicon atom bonded to a first atom and a second atom. In the inhibitor reactant, the first atom is oxygen, the second atom is selected from nitrogen and a halogen, and the inhibitor reactant selectively forms the inhibitor material on the first surface.

[0036] As used herein, the terms "layer" and / or "film" may refer to any continuous or non-continuous material, such as a material deposited by the methods disclosed herein. For example, a layer and / or film may include a two-dimensional material, a three-dimensional material, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or clusters of atoms and / or molecules. A film or layer may include a material or layer having pinholes, which may 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.

[0037] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may be composed of a single gas or a gas mixture as appropriate. Reactants and precursors according to the present disclosure may be provided to a reaction chamber in a gas phase. The term "inert gas" may refer to a gas that does not participate in a chemical reaction and / or does not become part of a layer to a perceptible degree. Exemplary inert gases include He and Ar and any combination thereof. In some cases, molecular nitrogen and / or hydrogen may be inert gases. Gases other than process gases, i.e., gases not introduced by a precursor injector system, other gas distribution devices, etc., may be used, for example, to seal a reaction chamber, and may include a sealing gas.

[0038] The term dielectric is used in the description herein to simplify the distinction from metal or metallic surfaces. It will be appreciated by those skilled in the art that not all non-conductive surfaces are dielectric surfaces. For example, a metal or metallic surface may include an oxidized metal surface that is non-conductive or has a very high resistivity. The selective deposition process of the inhibitor material taught herein may be deposited on a dielectric surface, with minimal deposition on such adjacent non-conductive metal or metallic surfaces.

[0039] The terms "precursor" and "reactant" may refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction that produces another compound or element. Precursors typically contain a portion that is at least partially incorporated into the compound or element produced by the chemical reaction. The compound or element thus obtained can be deposited on a substrate. In some cases, the reactant is a precursor. The reactant can also be a molecule that is bound (e.g., chemically adsorbed) on the surface of the substrate without further chemically reacting with additional precursors and / or reactants on the surface. The reactants on the surface of the substrate can be modified, for example, by thermal treatment or plasma treatment.

[0040] In some embodiments, the precursor or reactant is provided in the form of a mixture of two or more compounds. In the mixture, other compounds besides the precursor may be inert compounds or elements. In some embodiments, the precursor or reactant is provided in a composition. The composition may be a solution or a gas under standard conditions.

[0041] As used herein, the term "comprising" means including certain features but does not exclude the presence of other features as long as they do not render the claim unfeasible. In some embodiments, the term "comprising" includes "consisting of."

[0042] As used herein, the term "consisting of" means that, in addition to the features following the phrase, no other features are present in the device / method / product. When the term "consisting of" is used to refer to a compound, substance, or composition of matter, it means that the 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, substrate, or composition of matter. Nevertheless, in some embodiments, in addition to the listed ingredients, the chemical compound, substance, or composition of matter may include other ingredients that are trace elements or impurities.

[0043] In addition, in the present disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any range indicated may include or exclude endpoints. In addition, any values ​​of the variables indicated (regardless of whether they are expressed as "about") may refer to exact values ​​or approximate values, and include equivalents, and may refer to average values, median values, representative values, majority values, etc. In addition, in the present disclosure, the terms "include", "consist of" and "have" independently refer to "usually or broadly include", "comprise", "essentially consist of" or "consist of" in some embodiments. In the present disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some embodiments.

[0044] In the specification, it should be understood that the term "on..." or "above..." can be used to describe a relative positional relationship. Another element, film or layer can be directly on the layer, or another layer (intermediate layer) or element can be inserted therebetween, or a layer can be arranged on the layer but does not completely cover the surface of the layer. Therefore, unless the term "directly" is used alone, the term "on..." or "above..." will be interpreted as a relative concept. Similarly, it should be understood that the term "under...", "below..." or "below..." will be interpreted as a relative concept.

[0045] Substrate

[0046] The deposition method according to the present invention includes providing a substrate in a reaction chamber. The substrate can 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 can include bulk materials, such as silicon (e.g., single crystal silicon), other IV group materials, such as germanium, or other semiconductor materials, such as II-VI group or III-V group semiconductor materials, and can include one or more layers covering or located below the bulk material. In addition, the substrate can include various features, such as depressions, protrusions, etc. formed in or on at least a portion of the substrate layer. For example, the substrate can include a bulk semiconductor material and an insulating or dielectric material layer covering at least a portion of the bulk semiconductor material. The substrate can 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 crystal materials. In some embodiments of the present disclosure, the substrate includes silicon. As described above, in addition to silicon, the substrate can include other materials. Other materials can form layers. Specifically, the substrate can include a partially manufactured semiconductor device.

[0047] The substrate according to the present disclosure includes a first surface and a second surface. The first surface and the second surface have different material properties, allowing the inhibitor material to be selectively deposited on the first surface, and optionally the organic polymer to be selectively deposited 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 the silicon wafer.

[0048] In some embodiments, the substrate may be pretreated or cleaned before or at the start of a 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 a selective deposition process. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some embodiments, before or at the start of a selective deposition process, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species. In some embodiments, before or at the start of a selective deposition process, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species. 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.

[0049] Reaction Chamber

[0050] The method for depositing an inhibitor material 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 can be a single wafer reactor. Alternatively, the reaction chamber can be a batch reactor. The reaction chamber can 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 combination tool in which different processes are performed to form an integrated circuit. The various stages of the method according to the present disclosure, such as a method for depositing an organic polymer or a method for depositing a target material, can be performed in a single reaction chamber, or they can be performed in multiple reaction chambers, such as a reaction chamber of a combination tool, or a deposition station of a multi-station processing chamber.

[0051] In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a showerhead reactor. In some embodiments, the reaction chamber may be a hot wall reactor. In some embodiments, the reaction chamber may be a spatially separated reactor. In some embodiments, the reaction chamber may be a single wafer ALD reactor. In some embodiments, the reaction chamber may be a single wafer ALD reactor for mass production. In some embodiments, the reaction chamber may be a batch reactor for simultaneously producing multiple substrates.

[0052] The reaction chamber of the present disclosure may form part of an atomic layer deposition (ALD) assembly. The reaction chamber may form part of a chemical vapor deposition (CVD) assembly. The processing assembly may be an ALD or CVD processing assembly. In certain parts of the deposition process flow, particularly if an organic polymer is deposited, molecular layer deposition (MLD) may be employed. In some embodiments, the method is performed in a single reaction chamber of a combination tool, but other, preceding or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same combination tool. Optionally, a semiconductor processing assembly including a reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more substrates and / or reactants and / or precursors.

[0053] Cyclic Vapor Deposition

[0054] In some methods according to the present disclosure, in particular in methods for depositing organic polymers and target materials, a cyclic vapor deposition method can be used. Cyclic deposition in the present disclosure refers to a vapor deposition process in which a deposition cycle (usually multiple continuous deposition cycles) is performed in a processing chamber. For the sake of clarity, the deposition of inhibitor materials according to the present disclosure can be a non-cyclic process, in which the inhibitor reactant is continuously provided to the reaction chamber. The inhibitor reactant can be provided to the reaction chamber in pulses.

[0055] 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 a reaction chamber and chemically adsorbed onto a substrate surface (e.g., a substrate surface that may include previously deposited material or other material from a previous deposition cycle). In some embodiments, the precursor on the substrate surface is not easily reacted with an additional precursor (i.e., the deposition of the precursor may be a partially or completely self-limiting reaction). Thereafter, another precursor or reactant may be introduced into the reaction chamber for converting the chemically adsorbed precursor into a desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. During one or more cycles, such as during each step of each cycle, a purge step may be utilized to remove any excess precursor from the processing chamber and / or to remove any excess reactant and / or reaction byproducts from the reaction chamber. Thus, in some embodiments, the cyclic deposition process includes purging the reaction chamber after the precursor is provided into the reaction chamber. Without limiting the present disclosure to any particular theory, ALD and MLD may be similar processes in terms of self-limiting reactions and slower and more controllable layer growth rates compared to CVD. Typically, ALD is used to deposit inorganic materials, such as dielectric materials, metal oxides, metal nitrides, or elemental metals, whereas in MLD the precursors can be completely organic molecules, such as when depositing organic polymers.

[0056] In some embodiments, the process according to the present disclosure may 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. Precursors and reactants may be provided to a reaction chamber or substrate simultaneously, or in partially or completely separated pulses. However, CVD may be performed with a single precursor or two or more precursors that do not react with each other. A single precursor may be decomposed into reactive components deposited on the surface of a substrate. For example, decomposition may be performed by plasma or thermal methods. The substrate and / or reaction chamber may be heated to promote the reaction between gaseous precursors and / or reactants. In some embodiments, precursors and reactants are provided until a layer with a desired thickness is deposited. In some embodiments, a cyclic CVD process may be used to deposit a film with a desired thickness through multiple cycles. In a cyclic CVD process, precursors and / or reactants may be provided to a reaction chamber with pulses that do not overlap or partially or completely overlap. The process may include one or more cyclic stages. In some embodiments, the process may include one or more non-cyclic (i.e., continuous) stages. An example of a continuous phase may be 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 provided continuously in the reaction chamber.

[0057] In some embodiments, the inhibitor material according to the present disclosure is deposited at a pressure of at least 0.01 Torr to at most about 760 Torr, or at least 0.1 Torr to at most 150 Torr, or at least 0.5 Torr to at most 25 Torr, or at least 1 Torr to at most 10 Torr, or at least 2 Torr to at most 5 Torr. For example, the inhibitor material can be deposited at a pressure of about 1 Torr, about 2 Torr, about 3 Torr, about 5 Torr, about 6 Torr, about 8 Torr, about 9 Torr, about 12 Torr, or about 18 Torr. In some embodiments, further processing steps are performed at the same pressure. In some embodiments, further processing steps are performed at a different pressure, which can be lower or higher than the pressure at which the inhibitor material is deposited.

[0058] In some embodiments, the cyclic vapor deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, the temperature increased relative to the ambient temperature promotes chemical reactions. Generally speaking, in the absence of other external energy sources (such as plasma, free radicals or other forms of radiation), the temperature increase provides the energy required to form the target material. However, in some embodiments, the method according to the present disclosure, especially the method of depositing the target material, includes a plasma enhanced deposition method, such as PEALD or PECVD. In some embodiments, inhibitor material deposition can be performed by PEALD or PECVD.

[0059] Selectivity

[0060] The present disclosure relates to selective deposition processes. When a material is selectively formed or deposited on a first surface of a substrate relative to a second surface of the substrate, the selectivity can be given by a percentage calculated as [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). When an organic polymer material is deposited on the second surface, the calculation is accordingly reversed.

[0061] In some embodiments, the selectivity is at least about 30%. In some embodiments, the selectivity is at least about 50%. In some embodiments, the selectivity is at least about 75% or greater than about 85%. In some embodiments, the selectivity is at least about 90% or at least about 93%. In some embodiments, the selectivity is at least about 95% or at least about 98%. In some embodiments, the selectivity is at least about 99% or even at least about 99.5%. In embodiments, the selectivity may vary with the duration or thickness of the deposition.

[0062] Deposition can be measured in any of a variety of ways. In some embodiments, deposition can be given as a measured thickness of deposited material. In some embodiments, deposition can be given as a measured amount of deposited material. Sometimes, selectivity, such as after treating one of at least two surfaces of a substrate with an inhibitor, can be measured as a nucleation delay, which is expressed as the number of deposition cycles before growth of the target material is observed on the different surfaces. In this case, the term "selectivity window" can be used to describe the difference between the number of cycles on the different surfaces before growth of the target material is observed.

[0063] In some embodiments, the inhibitor material is deposited substantially only on the first surface and not on the second surface. Thus, deposition of the inhibitor material occurs only on one surface, such as the first surface, and substantially not on the other surface. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 80% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 50% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 10% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications.

[0064] In some embodiments, selective deposition of the inhibitor material is inherent and does not require prior or additional processing steps that are conveniently performed on the substrate. The selectivity may be inherent to a particular thickness of the deposited material and may be lost if deposition continues beyond a particular process threshold. If thicker layers of material are desired, the contrast between the first surface and the second surface may be enhanced, for example, by intermittent etch-back stages. A plasma, such as a hydrogen plasma, may be used.

[0065] Inhibitor Reactants

[0066] In the method according to the present disclosure, the substrate is contacted with a gas phase inhibitor reactant. Thus, the inhibitor reactant is gaseous when it contacts the substrate. In some applications, such as spin coating, a liquid inhibitor reactant may be used.

[0067] The inhibitor reactant comprises a silicon atom bonded to a first atom and a second atom. In the inhibitor reactant, the first atom is oxygen and the second atom is selected from nitrogen and a halogen. In some embodiments, the inhibitor reactant comprises one silicon atom. In some embodiments, the inhibitor reactant comprises one silicon atom and the silicon atom is bonded to one oxygen atom. In some embodiments, the inhibitor reactant comprises one silicon atom and the silicon atom is bonded to two oxygen atoms. In some embodiments, the inhibitor reactant comprises one silicon atom and the silicon atom is bonded to three oxygen atoms.

[0068] In some embodiments, the first atom in the inhibitor reactant is an oxygen of an alkoxy group. Therefore, in some embodiments, a silicon atom is bonded to at least one alkoxy group. At least one alkoxy group is bonded to a silicon atom through oxygen ("alkoxy oxygen"). In some embodiments, a silicon atom is bonded to two alkoxy groups. In some embodiments, a silicon atom is bonded to three alkoxy groups. Alkoxy groups according to the present disclosure include oxygen atoms bonded to C1 to C6 alkyl or phenyl groups. Therefore, an alkyl group may be aliphatic or aromatic. An alkyl group may be saturated or unsaturated, linear or branched, cyclic or non-cyclic. In some embodiments, an alkyl group is an unsubstituted hydrocarbon, i.e., it contains only carbon and hydrogen. In some embodiments, a silicon atom is bonded to at least two alkoxy oxygen groups.

[0069] The alkoxy group can be a C1 to C6 alkoxy group. In some embodiments, each alkoxy group in the inhibitor reactant is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1,1-dimethylpropoxy, 3-methylbutoxy, 1-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,2-dimethylpropoxy, and 2-methylbutoxy.

[0070] Each alkoxide group bonded to the silicon atom can be independently selected. In some embodiments, the inhibitor reactant comprises two identical alkoxide groups. In some embodiments, the inhibitor reactant comprises two different alkoxide groups. In some embodiments, the inhibitor reactant comprises three identical alkoxide groups. In some embodiments, the inhibitor reactant comprises three different alkoxide groups. In some embodiments, the inhibitor reactant comprises three alkoxide groups, two of which are identical.

[0071] In some embodiments, the inhibitor reactant comprises one methoxy group. In some embodiments, the inhibitor reactant comprises two methoxy groups. In some embodiments, the inhibitor reactant comprises three methoxy groups. In some embodiments, the inhibitor reactant comprises one ethoxy group. In some embodiments, the inhibitor reactant comprises two ethoxy groups. In some embodiments, the inhibitor reactant comprises three ethoxy groups. In some embodiments, the inhibitor reactant comprises one propoxy group. In some embodiments, the inhibitor reactant comprises two propoxy groups. In some embodiments, the inhibitor reactant comprises three propoxy groups.

[0072] In some embodiments, the inhibitor reactant comprises one methoxy group and one ethoxy group. In some embodiments, the inhibitor reactant comprises one methoxy group and two ethoxy groups. In some embodiments, the inhibitor reactant comprises two methoxy groups and one ethoxy group. In some embodiments, the inhibitor reactant comprises one methoxy group and two propoxy groups. In some embodiments, the inhibitor reactant comprises two methoxy groups and one propoxy group. In some embodiments, the inhibitor reactant comprises one propoxy group and two ethoxy groups. In some embodiments, the inhibitor reactant comprises two propoxy groups and one ethoxy group.

[0073] In some embodiments, the second atom in the inhibitor reactant is a nitrogen atom of an amine group. In some embodiments, the amine group is a primary amine (-NH2). In some embodiments, the amine group is a secondary amine (-NRH). In some embodiments, the amine group is a tertiary amine (-NR2). For secondary and tertiary amines, one or two alkyl or aryl groups can be selected from linear, branched and cyclic C1 to C6 alkyl groups and phenyl groups. In tertiary amines, the alkyl groups can be independently selected. Therefore, the alkyl groups attached to the nitrogen atom can be the same or different. In some embodiments, the amine is dimethylamine. In some embodiments, the amine is diethylamine. In some embodiments, the amine is dipropylamine. In some embodiments, the amine is di-n-propylamine. In some embodiments, the amine is diisopropylamine. In some embodiments, the amine is dibutylamine. In some embodiments, the amine is di-n-butylamine. In some embodiments, the amine is di-sec-butylamine. In some embodiments, the amine is di-tert-butylamine. In some embodiments, the amine is diisobutylamine. In some embodiments, the amine is ethylmethylamine. In some embodiments, the amine is methylpropylamine. In some embodiments, the amine is ethylpropylamine.

[0074] In some embodiments, the second atom is a halogen selected from F, Cl, Br, and I. In some embodiments, the second atom is a halogen selected from Cl, Br, and I. In some embodiments, the second atom is a halogen selected from Cl and Br. In some embodiments, the second atom is a halogen selected from Cl and I. In some embodiments, the second atom is F. In some embodiments, the second atom is Cl. In some embodiments, the second atom is Br. In some embodiments, the second atom is I.

[0075] In addition to at least one alkoxy group and at least one nitrogen-containing or halogen group, the inhibitor reactant may include at least one additional atom bonded to the silicon atom. For example, the additional atom may be hydrogen (H) or carbon (C). The carbon atom may be bonded to another carbon atom and / or hydrogen atom. In other words, the silicon atom may be bonded to an alkyl group. For example, the inhibitor reactant may include two alkoxy groups, an amine group and a hydrogen or an alkyl group bonded to the silicon atom. In another example, the inhibitor reactant may include an alkoxy group, two amine groups and a hydrogen or an alkyl group bonded to the silicon atom. In some embodiments, the inhibitor reactant may include an alkoxy group, two halogens and a hydrogen or an alkyl group bonded to the silicon atom. In some embodiments, the inhibitor reactant includes two additional atoms connected to the silicon atom. The additional alkyl group bonded to the silicon atom may be selected from linear and branched C1 to C6 alkyl groups. In some embodiments, the alkyl group is selected from methyl (Met), ethyl (Et), n-propyl (Pr), isopropyl ( i The butyl groups are butyl (Pr), n-butyl (Bu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), n-pentyl (Pe), tert-pentyl (tPe), neopentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), 3-pentyl (2Pe), sec-isopentyl (siPe) and 2-methylbutyl (2-MetBu).

[0076] In some embodiments, the inhibitor reactant is of the formula Si(OR) a X b R' c represents, wherein each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl, each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl, X is selected from halogen or NR'2, a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4.

[0077] In some embodiments, all R and R' are C1 to C4 alkyl. In some embodiments, all R are methyl or ethyl. In some embodiments, all R' are methyl or ethyl. In some embodiments, all R and R' are methyl or ethyl. In some embodiments, all R are methyl. In some embodiments, all R' are methyl. In some embodiments, all R and R' are methyl. In some embodiments, all R are ethyl. In some embodiments, all R and R' are ethyl.

[0078] In some embodiments, the inhibitor reactant comprises a halogen and is selected from: Si(OMet)Met2Cl, Si(OMet)2MetCl, Si(OMet)3Cl, Si(OMet)2HCl, Si(OMet)H2Cl, Si(OMet)Met2Br, Si(OMet)2MetBr, Si(OMet)3Br, Si(OMet)2HBr, Si(OMet)H2Br, Si(OMet)Met2I, Si(OMet)2MetI, Si(OMet)3I, Si(OMet)2HI, Si(OMet)H2I, Si(OMet)MetCl2, Si(OMet)HCl2, Si(OMet)2Cl2, Si(OMet)Cl3, Si(OMet)MetBr2, Si(OMet)HBr2, Si(OMet)2Br2, Si(OMet)Br3, Si(OMet)MetI2, Si(OMet)HI2, Si(OMet)2I2, Si(OMet)I3, Si(OEt)Met2Cl, Si(OEt)2MetCl, Si(OEt)3Cl, Si(OEt)2HCl, Si(OEt)H2Cl, Si(OEt)Met2Br, Si(OEt)2MetBr, Si(OEt)3Br, Si(OEt)2HBr, Si(OEt)H2Br, Si(OEt)Met2I, Si(OEt)2MetI, Si(OEt)3I, Si(OEt)2HI, Si(OEt)H2I, Si(OEt)MetCl2, Si(OEt)HCl2, Si(OEt)2Cl2, Si(OEt)Cl3, Si(OEt)MetBr2, Si(OEt)HBr2, Si(OEt)2Br2, Si(OEt)Br3, Si(OEt)MetI2, Si(OEt)HI2, Si(OEt)2I2, Si(OEt)I3, Si(OMet)Et2Cl, Si(OMet)2EtCl, Si(OMet)Et2Br, Si(OMet)2EtBr, Si(OMet)Et2I, Si(OMet)2EtI, Si(OMet)EtCl2, Si(OMet)EtBr2, Si(OMet)EtI2, Si(OEt)Et2Cl, Si(OEt)2EtCl, Si(OEt)Et2Br, Si(OEt)2EtBr, Si(OEt)Et2I, Si(OEt)2EtI, Si(OEt)EtCl2, Si(OEt)EtBr2Si(OEt)EtI2, Si(OPr)Met2Cl, Si(OPr)2MetCl, Si(OPr)3Cl, Si(OPr)2HCl, Si(OPr)H2Cl, Si(OPr)Met2Br, Si(OPr)2MetBr, Si(OPr)3Br,Si(OPr)2HBr, Si(OPr)H2Br, Si(OPr)Met2I, Si(OPr)2MetI, Si(OPr)3I, Si(OPr)2HI, Si(OPr)H2I, Si(OPr)MetCl2, Si(OPr)HCl2, Si(OPr)2Cl2, Si(OPr)Cl3, Si(OPr)MetBr2,Si(OPr)HBr2, Si(OPr)2Br2, Si(OPr)Br3, Si(OPr)MetI2, Si(OPr)HI2, Si(OPr)2I2, Si(OPr)I3, Si(OPr)Et2Cl, Si(OPr)2EtCl, Si(OPr)Et2Br, Si(OPr)2EtBr, Si(OPr)Et2I,Si(OPr)2EtI, Si(OPr)EtCl2, Si(OPr)EtBr2, Si(OPr)EtI2, Si(OPr)Pr2Cl, Si(OPr)2PrCl, Si(OPr)2EtBr, Si(OPr)Pr2I, Si(OPr)2PrI, Si(OPr)PrCl2, Si(OPr)PrBr2, Si(OPr)PrI2, Si(O, i Pr)Met2Cl, Si(O i Pr)2MetCl, Si(O i Pr)3Cl, Si(O i Pr)2HCl, Si(O i Pr)H2Cl, Si(O i Pr)Met2Br, Si(O i Pr)2MetBr, Si(O i Pr)3Br, Si(O i Pr)2HBr, Si(O i Pr)H2Br, Si(O i Pr)Met2I, Si(O i Pr)2MetI, Si(O i Pr)3I, Si(O i Pr)2HI, Si(O iPr)H2I,Si(O i 2H2O i 2H2O i 2Cl2, Si(O i Cl3, Si(O i )PrMetBr2, Si(O i 2HBr2, Si(O i Pr)2Br2, Si(O i )Br3, Si(O i 2Pr)MetI2, Si(O i 2H2O i Pr)2I2, Si(O i Pr)I3, Si(O i 2Cl2Pr)Et2Cl2Si(O i 2EtCl2Pr i )PrEt2Br, Si(O i 2EtBr, Si(O i Pr)Et2I, Si(O i 2EtI, Si(O i 2H2O i )Pr(O i Pr)EtI2, Si(O i Pr) i Pr2Cl2Si(O i 2 i PrCl2,Si(O i Pr) i Pr2Br, Si(O i 2 i PrBr, Si(O i Pr) i Pr2I, Si(O i 2 i ,PrI,Si(O i Pr) i PrCl2, Si(O i Pr) i PrBr2, Si(O i Pr) i PrI2, Si(O i 2Cl2Si(O i 2PrCl2Si(O i Pr)Pr2Br, Si(Oi Pr)2PrBr, Si(O i Pr)Pr2I, Si(O i Pr)2PrI, Si(O i Pr)PrCl2, Si(O i Pr)PrBr2 and Si(O i Pr)PrI2。

[0079] In some embodiments, the second atom in the inhibitor reactant is the nitrogen of a primary amine group.In some embodiments, the inhibitor reactant containing a primary amine group is selected from the group consisting of: Si(OMet)Met2(NH2), Si(OMet)2Met(NH2), Si(OMet)3(NH2), Si(OMet)2H(NH2), Si(OMet)H2(NH2), Si(OMet)Met(NH2)2, Si(OMet)H(NH2)2, Si(OMet)2(NH2)2, Si(OMet)(NH2)3, Si(OEt)Met2(NH2), Si(OEt)2Met(NH2), Si(OEt)3(NH2),Si(OEt)2H(NH2), Si(OEt)H2(NH2), Si(OEt)Met(NH2)2, Si(OEt)H(NH2)2, Si(OEt)2(NH2)2,Si(OEt)(NH2)3, Si(OMet)Et2(NH2), Si(OMet)2Et(NH2), Si(OMet)Et(NH2)2, Si(OEt)Et2(NH2), Si(OEt)2Et(NH2), Si(OEt)Et(NH2)2, Si(OPr)Met2(NH2), Si(OPr)2Met(NH2), Si(OPr)3(NH2), Si(OPr)2H(NH2), Si(OPr)H2(NH2), Si(OPr)Met(NH2)2, Si(OPr)H(NH2)2,Si(OPr)2(NH2)2, Si(OPr)(NH2)3, Si(OPr)Et2(NH2), Si(OPr)2Et(NH2), Si(OPr)Et(NH2)2,Si(OPr)Pr2(NH2), Si(OPr)2Pr(NH2), Si(OPr)Pr(NH2)2, Si(OiPr)Met2(NH2), Si(OiPr)2Met(NH2), Si(OiPr)3(NH2), Si(OiPr)2H(NH2), Si(OiPr)H2(NH2), Si(OiPr)Met(NH2)2,Si(OiPr)H(NH2)2, Si(OiPr)2(NH2)2, Si(OiPr)(NH2)3, Si(OiPr)Et2(NH2), Si(OiPr)2Et(NH2), Si(OiPr)Et(NH2)2, Si(OiPr)iPr2(NH2), Si(OiPr)2iPr(NH2), Si(OiPr)iPr(NH2)2, Si(OiPr)Pr2(NH2), Si(OiPr)2Pr(NH2) and Si(OiPr)Pr(NH2)2.

[0080] In some embodiments, the second atom is the nitrogen of an alkylamine group, ie, the nitrogen atom of a secondary amine. In some embodiments, the inhibitor reactant is selected from: Si(OMet)Met2(NMetH), Si(OMet)2Met(NMetH), Si(OMet)3(NMetH), Si(OMet)2H(NMetH), Si(OMet)H2(NMetH), Si(OMet)Met(NMetH)2, Si(OMet)H(NMetH)2, Si(OMet)2(NMetH)2, Si(OMet)(NMetH)3, Si(OEt)Met2(NMetH), Si(OEt)2Met(NMetH), Si(OEt)3(NMetH), Si(OEt)2H(NMetH), Si(OEt)H2(NMetH), Si(OEt)Met(NMetH)2, Si(OEt)H(NMetH)2, Si(OEt)2(NMetH)2, Si(OEt)(NMetH)3, Si(OMet)Et2(NMetH), Si(OMet)2Et(NMetH), Si(OMet)Et(NMetH)2, Si(OEt)Et2(NMetH), Si(OEt)2Et(NMetH), Si(OEt)Et(NMetH)2, Si(OPr)Met2(NMetH), Si(OPr)2Met(NMetH), Si(OPr)3(NMetH), Si(OPr)2H(NMetH), Si(OPr)H2(NMetH), Si(OPr)Met(NMetH)2, Si(OPr)H(NMetH)2, Si(OPr)2(NMetH)2, Si(OPr)(NMetH)3, Si(OPr)Et2(NMetH), Si(OPr)2Et(NMetH), Si(OPr)Et(NMetH)2, Si(OPr)Pr2(NMetH), Si(OPr)2Pr(NMetH), Si(OPr)Pr(NMetH)2, Si(O i Pr)Met2(NMetH), Si(O i Pr)2Met(NMetH), Si(O i Pr)3(NMetH), Si(O i Pr)2H(NMetH), Si(O i Pr)H2(NMetH), Si(O iPr)Met(NMetH)2, Si(O i Pr)H(NMetH)2, Si(O i Pr)2(NMetH)2, Si(O i Pr)(NMetH)3, Si(O i Pr)Et2(NMetH), Si(O i Pr)2Et(NMetH), Si(O i Pr)Et(NMetH)2, Si(O i Pr) i Pr2(NMetH), Si(O i 2 i Pr(NMetH), Si(O i Pr) i Pr(NMetH)2, Si(O i Pr)Pr2(NMetH), Si(O i Pr)2Pr(NMetH), Si(O iPr)Pr(NMetH)2, Si(OMet)Met2(NEtH), Si(OMet)2Met(NEtH), Si(OMet)3(NEtH), Si(OMet)2H(NEtH), Si(OMet)H2(NEtH), Si(OMet)Met(NEtH)2, Si(OMet)H(NEtH)2, Si(OMet)2(NEtH)2, Si(OMet)(NEtH)3, Si(OEt)Met2(NEtH), Si(OEt)2Met(NEtH), Si(OEt)3(NEtH), Si(OEt)2H(NEtH), Si(OEt)H2(NEtH), Si(OEt)Met(NEtH)2, Si(OEt)H(NEtH)2, Si(OEt)2(NEtH)2, Si(OEt)(NEtH)3, Si(OMet)Et2(NEtH), Si(OMet)2Et(NEtH), Si(OMet)Et(NEtH)2, Si(OEt)Et2(NEtH), Si(OEt)2Et(NEtH), (OEt)H2(NEtH), Si(OEt)Et(NEtH)2, Si(OPr)Met2(NEtH), Si(OPr)2Met(NEtH), Si(OPr)3(NEtH), Si(OPr)2H(NEtH), Si(OPr)H2(NEtH), Si(OPr)Met(NEtH)2,Si(OPr)H(NEtH)2, Si(OPr)2(NEtH)2, Si(OPr)(NEtH)3, Si(OPr)Et2(NEtH), Si(OPr)2Et(NEtH), Si(OPr)Et(NEtH)2, Si(OPr)Pr2(NEtH), Si(OPr)2Pr(NEtH), Si(OPr)Pr(NEtH)2, Si(O i Pr)Met2(NEtH), Si(O i Pr)2Met(NEtH), Si(O i Pr)3(NEtH), Si(O i Pr)2H(NEtH), Si(O i Pr)H2(NEtH), Si(O i Pr)Met(NEtH)2, Si(O i Pr)H(NEtH)2, Si(O i Pr)2(NEtH)2, Si(O iPr)(NEtH)3, Si(O i Pr)Et2(NEtH), Si(O i Pr)2Et(NEtH), Si(O i Pr)Et(NEtH)2, Si(O i Pr) i Pr2(NEtH), Si(O i 2 i Pr(NEtH), Si(O i Pr) i Pr(NEtH)2, Si(O i Pr)Pr2(NEtH), Si(O i Pr)2Pr(NEtH), Si(O iPr)Pr(NEtH)2, Si(OMet)Met2(NPrH), Si(OMet)2Met(NPrH), Si(OMet)3(NPrH), Si(OMet)2H(NPrH), Si(OMet)H2(NPrH), Si(OMet)Met(NPrH)2, Si(OMet)H(NPrH)2, Si(OMet)2(NPrH)2, Si(OMet)(NPrH)3, Si(OEt)Met2(NPrH), Si(OEt)2Met(NPrH), Si(OEt)3(NPrH), Si(OEt)2H(NPrH), Si(OEt)H2(NPrH),Si(OEt)Met(NPrH)2, Si(OEt)H(NPrH)2, Si(OEt)2(NPrH)2, Si(OEt)(NPrH)3, Si(OMet)Et2(NPrH), Si(OMet)2Et(NPrH), Si(OMet)Et(NPrH)2, Si(OEt)Et2(NPrH), Si(OEt)2Et(NPrH), Si(OEt)Et(NPrH)2, Si(OPr)Met2(NPrH), Si(OPr)2Met(NPrH), Si(OPr)3(NPrH), Si(OPr)2H(NPrH), Si(OPr)H2(NPrH), Si(OPr)Met(NPrH)2, Si(OPr)H(NPrH)2,Si(OPr)2(NPrH)2, Si(OPr)(NPrH)3, Si(OPr)Et2(NPrH), Si(OPr)2Et(NPrH), Si(OPr)Et(NPrH)2, Si(OPr)Pr2(NPrH), Si(OPr)2Pr(NPrH), S i (OPr)Pr(NPrH)2, Si(O i )Met2(NPrH), Si(O i Pr)2Met(NPrH), Si(O i Pr)3(NPrH), Si(O i Pr)2H(NPrH), Si(O i Pr)H2(NPrH),Si(O i Pr)Met(NPrH)2, Si(O i Pr)H(NPrH)2, Si(O i Pr)2(NPrH)2, Si(O i Pr)(NPrH)3, Si(Oi Pr)Et2(NPrH), Si(O i Pr)2Et(NPrH), Si(O i Pr)Et(NPrH)2, Si(O i Pr) i Pr2(NPrH), Si(O i Pr)2 i Pr(NPrH), Si(O i Pr) i Pr(NPrH)2, Si(O i Pr)Pr2(NPrH), Si(O i Pr)2Pr(NPrH), Si(O i Pr)Pr(NPrH)2, Si(OMet)Met2(N i PrH), Si(OMet)2Met(N i PrH), Si(OMet)3(N i PrH), Si(OMet)2H(N i PrH), Si(OMet)H2(N i PrH), Si(OMet)Met(N i PrH)2, Si(OMet)H(N i PrH)2, Si(OMet)2(N i PrH)2, Si(OMet)(N i PrH)3, Si(OEt)Met2(N i PrH), Si(OEt)2Met(N i PrH), Si(OEt)3(N i PrH), Si(OEt)2H(N i PrH), Si(OEt)H2(N i PrH), Si(OEt)Met(N i PrH)2, Si(OEt)H(N i PrH)2, Si(OEt)2(N i PrH)2, Si(OEt)(N i PrH)3, Si(OMet)Et2(N i PrH), Si(OMet)2Et(N i PrH), (OMet)Et(NiPrH)2, Si(OEt)Et2(N i PrH), Si(OEt)2Et(Ni PrH), Si(OEt)Et(N i 2PrH)2, Si(OPr)Met2(N i PrH), Si(OPr)2Met(N i PrH), Si(OPr)3(N i PrH), Si(OPr)2H(N i PrH), Si(OPr)H2(N i PrH), Si(OPr)Met(N i PrH)2, Si(OPr)H(N i 2PrH)2, 2PrH)2 i 2PrH)2, Si(OPr)(N i PrH)3, Si(OPr)Et2(N i PrH), Si(OPr)2Et(N i PrH), Si(OPr)Et(N i PrH)2, Si(OPr)Pr2(N i PrH), Si(OPr)2Pr(N i PrH), Si(OPr)Pr(N i PrH)2, Si(O i )Met2(N i PrH), Si(O i Pr)2Met(N i PrH), Si(O i Pr)3(N i PrH), Si(O i 2H(N) i PrH), Si(O i )H2(N i PrH), Si(O i )Met(N i PrH)2, Si(O i (N)H(Pr) i PrH)2, Si(O i Pr)2(N i PrH)2, Si(O i Pr)(N i PrH)3, Si(O i )Et2(N i PrH), Si(O i Pr)2Et(N i PrH), Si(Oi Pr)Et(N i PrH)2, Si(O i Pr) i Pr2(N i PrH), Si(O i 2 i Pr(N i PrH), Si(O i Pr) i Pr(N i PrH)2, Si(O i Pr)Pr2(N i PrH), Si(O i Pr)2Pr(N i PrH)Si(O i Pr(N)Pr(N) i PrH)2.

[0081] In some embodiments, the second atom is the nitrogen of a dialkylamine group, ie, a nitrogen atom of a tertiary amine. In some embodiments, the inhibitor reactant is selected from the group consisting of: Si(OMet)Met2(NMet2), Si(OMet)2Met(NMet2), Si(OMet)3(NMet2), Si(OMet)2H(NMet2), Si(OMet)H2(NMet2), Si(OMet)Met(NMet2)2, Si(OMet)H(NMet2)2, Si(OMet)2(NMet2)2, Si(OMet)(NMet2)3, Si(OEt)Met2(NMet2), Si(OEt)2Met(NMet2), Si(OEt)3(NMet2), Si(OEt)2H(NMet2), Si(OEt)H2(NMet2), Si(OEt)Met(NMet2)2, Si(OEt)H(NMet2)2, Si(OEt)2(NMet2)2, Si(OEt)(NMet2)3, Si(OMet)Et2(NMet2), Si(OMet)2Et(NMet2), Si(OMet)Et(NMet2)2, Si(OEt)Et2(NMet2), Si(OEt)2Et(NMet2), Si(OEt)Et(NMet2)2, Si(OPr)Met2(NMet2), Si(OPr)2Met(NMet2), Si(OPr)3(NMet2), Si(OPr)2H(NMet2), Si(OPr)H2(NMet2), Si(OPr)Met(NMet2)2, Si(OPr)H(NMet2)2, Si(OPr)2(NMet2)2, Si(OPr)(NMet2)3, Si(OPr)Et2(NMet2), Si(OPr)2Et(NMet2), Si(OPr)Et(NMet2)2, Si(OPr)Pr2(NMet2), Si(OPr)2Pr(NMet2), Si(OPr)Pr(NMet2)2, S i (O i Pr)Met2(NMet2), Si(O i Pr)2Met(NMet2), Si(O i Pr)3(NMet2), Si(O i Pr)2H(NMet2), Si(O i Pr)H2(NMet2), Si(O i Pr)Met(NMet2)2, Si(Oi Pr)H(NMet2)2, Si(O i Pr)2(NMet2)2, Si(O i Pr)(NMet2)3, Si(O i Pr)Et2(NMet2), Si(O i Pr)2Et(NMet2), Si(O i Pr)Et(NMet2)2, Si(O i Pr) i Pr2(NMet2), Si(O i Pr) 2 i Pr(NMet2), Si(O i Pr) i Pr(NMet2)2, Si(O i Pr)Pr2(NMet2), Si(O i Pr)2Pr(NMet2), Si(O i<h2 style=";text-align:left;direction:ltr">Pr)Pr(NMet2)2, Si(OMet)Met2(NEt2), Si(OMet)2Met(NEt2), Si(OMet)3(NEt2), Si(OMet)2H(NEt2), Si(OMet)H2(NEt2), Si(OMet)Met(NEt2)2, Si(OMet)H(NEt2)2, Si(OMet)2(NEt2)2, Si(OMet)(NEt2)3, Si(OEt)Met2(NEt2), Si(OEt)2Met(NEt2), Si(OEt)3(NEt2), Si(OEt)2H(NEt2), Si(OEt)H2(NEt2), Si(OEt)Met(NEt2)2, Si(OEt)H(NEt2)2, Si(OEt)(NEt2)3, Si(OMet)Et2(NEt2), Si(OMet)2Et(NEt2),Si(OMet)Et(NEt2)2, Si(OEt)Et2(NEt2), Si(OEt)2Et(NEt2), Si(OEt)Et(NEt2)2, Si(OPr)Met2(NEt2), Si(OPr)2Met(NEt2), Si(OPr)3(NEt2), Si(OPr)2H(NEt2), Si(OPr)H2(NEt2),Si(OPr)Met(NEt2)2, Si(OPr)H(NEt2)2, Si(OPr)2(NEt2)2, Si(OPr)(NEt2)3, Si(OPr)Et2(NEt2), Si(OPr)2Et(NEt2), Si(OPr)Et(NEt2)2, Si(OPr)Pr2(NEt2), Si(OPr)2Pr(NEt2),Si(OPr)Pr(NEt2)2, Si(O)<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)Met2(NEt2), Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)2Met(NEt2), Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)3(NEt2), Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)2H(NEt2), Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)H2(NEt2), Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)Met(NEt2)2, Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)H(NEt2)2, Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)2(NEt2)2, Si(O<h2 style=";text-align:left;direction:ltr"> i <h2 style=";text-align:left;direction:ltr"> Pr)(NEt2)3, Si(O<h2 style=";text-align:left;direction:ltr"> iPr)Et2(NEt2), Si(O i Pr)2Et(NEt2), Si(O i Pr)Et(NEt2)2,Si(O i Pr)iPr2(NEt2), Si(O i Pr)2 i Pr(NEt2), Si(O i (Ex) i Pr(NEt2)2, Si(O i Pr)Pr2(NEt2), Si(O i Pr)2Pr(NEt2), Si(O i Pr)Pr(NEt2)2, Si(OMet)Met2(NPr2), Si(OMet)2Met(NPr2), Si(OMet)3(NPr2), Si(OMet)2H(NPr2), Si(OMet)H2(NPr2), Si(OMet)Met(NPr2)2, Si(OMet)H(NPr2)2, Si(OMet)2(NPr2)2, Si(OMet)(NPr2)3, Si(OEt)Met2(NPr2), Si(OEt)2Met(NPr2),Si(OEt)3(NPr2), Si(OEt)2H(NPr2), Si(OEt)H2(NPr2), Si(OEt)Met(NPr2)2, Si(OEt)H(NPr2)2, Si(OEt)2(NPr2)2, Si(OEt)(NPr2)3, Si(OMet)Et2(NPr2), Si(OMet)2Et(NPr2),Si(OMet)Et(NPr2)2, Si(OEt)Et2(NPr2), Si(OEt)2Et(NPr2), Si(OEt)Et(NPr2)2, Si(OPr)Met2(NPr2), Si(OPr)2Met(NPr2), Si(OPr)3(NPr2), Si(OPr)2H(NPr2), Si(OPr)H2(NPr2),Si(OPr)Met(NPr2)2, Si(OPr)H(NPr2)2, Si(OPr)2(NPr2)2, Si(OPr)(NPr2)3, Si(OPr)Et2(NPr2), Si(OPr)2Et(NPr2), Si(OPr)Et(NPr2)2, Si(OPr)Pr2(NPr2), Si(OPr)2Pr(NPr2),Si(OPr)Pr(NPr2)2, Si(O iPr)Met2(NPr2), Si(O i Pr)2Met(NPr2), Si(O i Pr)3(NPr2), Si(O i Pr)2H(NPr2), Si(O i Pr)H2(NPr2), Si(O i Pr)Met(NPr2)2, Si(O i Pr)H(NPr2)2, Si(O i Pr)2(NPr2)2, Si(O i Pr)(NPr2)3, Si(O i Pr)Et2(NPr2), Si(O i Pr)2Et(NPr2), Si(O i Pr)Et(NPr2)2,Si(O i Pr) i Pr2(NPr2), Si(O i Pr) 2 i Pr(NPr2), Si(O i Pr) i Pr(NPr2)2, Si(O i Pr)Pr2(NPr2), Si(O i Pr)2Pr(NPr2), Si(O i Pr)Pr(NPr2)2, Si(OMet)Met2(N i Pr2), Si(OMet)2Met(N i Pr2), Si(OMet)3(N i Pr2), Si(OMet)2H(NiPr2), Si(OMet)H2(N i Pr2), Si(OMet)Met(N i Pr2)2, Si(OMet)H(N i Pr2)2, Si(OMet)2(N i Pr2)2, Si(OMet)(N i Pr2)3, Si(OEt)Met2(N i Pr2), Si(OEt)2Met(N i Pr2), Si(OEt)3(N i Pr2), Si(OEt)2H(N i Pr2), Si(OEt)H2(N iPr2), Si(OEt)Met(N i Pr2)2, Si(OEt)H(N i Pr2)2, Si(OEt)2(N i Pr2)2, Si(OEt)(N i Pr2)3, Si(OMet)Et2(N i Pr2),Si(OMet)2Et(N i Pr2), Si(OMet)Et(N i Pr2)2, Si(OEt)Et2(N i Pr2), Si(OEt)2Et(N i Pr2), Si(OEt)Et(N i Pr2)2, Si(OPr)Met2(N i Pr2), Si(OPr)2Met(N i Pr2), Si(OPr)3(N i Pr2), Si(OPr)2H(N i Pr2), Si(OPr)H2(N i Pr2), Si(OPr)Met(N i Pr2)2, Si(OPr)H(N i Pr2)2, Si(OPr)2(N i Pr2)2, Si(OPr)(N i Pr2)3, Si(OPr)Et2(N i Pr2), Si(OPr)2Et(N i Pr2), Si(OPr)Et(N i Pr2)2, Si(OPr)Pr2(N i Pr2), Si(OPr)2Pr(N i Pr2), Si(OPr)Pr(N i Pr2)2, Si(O i Pr)Met2(N i Pr2), Si(O i Pr)2Met(N i Pr2), Si(O i Pr)3(N i Pr2), Si(O i Pr)2H(N i Pr2), Si(O i Pr)H2(N i Pr2), Si(Oi Pr)Met(NiPr2)2, Si(O i Pr)H(N i Pr2)2, Si(O i Pr)2(N i Pr2)2, Si(O i Pr)(N i Pr2)3, Si(O i Pr)Et2(N i Pr2), S i (O i Pr)2Et(N i Pr2), Si(O i Pr)Et(N i Pr2)2, Si(O i Pr) i Pr2(N i Pr2), Si(O i Pr)2 i Pr(N i Pr2), Si(O i Pr) i Pr(N i Pr2)2, Si(O i Pr)Pr2(N i Pr2), Si(O i Pr)2Pr(N i Pr2) and Si(O i Pr)Pr(N i Pr2)2.

[0082] In general, the above inhibitor reactants having nitrogen as the second atom can be described as follows, using R to represent H, Met, Et, Pr, iPr, Bu, sBu or tBu. Each R can be independently selected, so they can be the same or different. Si(OMet)Met2(NR2), Si(OMet)2Met(NR2), Si(OMet)3(NR2), Si(OMet)2H(NR2), Si(OMet)H2(NR2), Si(OMet)Met(NR2)2, Si(OMet)H(NR2)2, Si(OMet)2(NR2)2, Si(OMet)(NR2)3, Si(OEt)Met2(NR2), Si(OEt)2Met(NR2), Si(OEt)3(NR2), Si(OEt)2H(NR2), Si(OEt)H2(NR2), Si(OEt)Met(NR2)2, Si(OEt)H(NR2)2, Si(OEt)2(NR2)2, Si(OEt)(NR2)3, Si(OMet)Et2(NR2), Si(OMet)2Et(NR2), Si(OMet)Et(NR2)2, Si(OEt)Et2(NR2), Si(OEt)2Et(NR2), Si(OEt)Et(NR2)2, Si(OPr)Met2(NR2), Si(OPr)2Met(NR2), Si(OPr)3(NR2), Si(OPr)2H(NR2), Si(OPr)H2(NR2), Si(OPr)Met(NR2)2, Si(OPr)H(NR2)2, Si(OPr)2(NR2)2, Si(OPr)(NR2)3, Si(OPr)Et2(NR2), Si(OPr)2Et(NR2), Si(OPr)Et(NR2)2, Si(OPr)Pr2(NR2), Si(OPr)2Pr(NR2), Si(OPr)Pr(NR2)2, Si(O i Pr)Met2(NR2), Si(O i Pr)2Met(NR2), Si(O i Pr)3(NR2), Si(O i Pr)2H(NR2), Si(O i Pr)H2(NR2), Si(O i Pr)Met(NR2)2, Si(O i Pr)H(NR2)2, Si(O i Pr)2(NR2)2, Si(O i Pr)(NR2)3, Si(O i Pr)Et2(NR2), Si(Oi Pr)2Et(NR2), Si(O i Pr)Et(NR2)2, Si(O i Pr) i Pr2(NR2), Si(O i 2 i Pr(NR2), Si(O i Pr) i Pr(NR2)2, Si(O i Pr)Pr2(NR2), Si(O i Pr)2Pr(NR2), Si(O i Pr)Pr(NR2)2, Si(OMet)Met2(NRH), Si(OMet)2Met(NRH), Si(OMet)3(NRH), Si(OMet)2H(NRH), Si(OMet)H2(NRH), Si(OMet)Met(NRH)2, Si(OMet)H(NRH)2,Si(OMet)2(NRH)2, Si(OMet)(NRH)3, Si(OEt)Met2(NRH), Si(OEt)2Met(NRH), Si(OEt)3(NRH), Si(OEt)2H(NRH), Si(OEt)H2(NRH), Si(OEt)Met(NRH)2, Si(OEt)H(NRH)2, Si(OEt)2(NRH)2, Si(OEt)(NRH)3, Si(OMet)Et2(NRH), Si(OMet)2Et(NRH), Si(OMet)Et(NRH)2, Si(OEt)Et2(NRH), Si(OEt)2Et(NRH), Si(OEt)Et(NRH)2, Si(OPr)Met2(NRH), Si(OPr)2Met(NRH), Si(OPr)3(NRH), Si(OPr)2H(NRH), Si(OPr)H2(NRH), Si(OPr)Met(NRH)2, Si(OPr)H(NRH)2, Si(OPr)2(NRH)2, Si(OPr)(NRH)3, Si(OPr)Et2(NRH), Si(OPr)2Et(NRH), Si(OPr)Et(NRH)2, Si(OPr)Pr2(NRH), Si(OPr)2Pr(NRH), Si(OPr)Pr(NRH)2, Si(OiPr)Met2(NRH), Si(O i Pr)2Met(NRH), Si(O iPr)3(NRH), Si(O i Pr)2H(NRH),Si(O i Pr)H2(NRH), Si(O i Pr)Met(NRH)2, Si(O i Pr)H(NRH)2, Si(O i Pr)2(NRH)2, Si(O i Pr)(NRH)3, Si(O i Pr)Et2(NRH), Si(O i Pr)2Et(NRH), Si(O i Pr)Et(NRH)2, Si(O i (Pr) i Pr2(NRH),Si(O i Pr)2 i Pr(NRH), Si(O i (Pr) i Pr(NRH)2, Si(OiPr)Pr2(NRH), Si(O i Pr)2Pr(NRH) and Si(O i Pr)Pr(NRH)2.

[0083] In some examples, the inhibitor reacts with: Si(OMet)3Cl, Si(OMet)3Br, Si(OMet)3I,Si(OMet)2Cl2, Si(OMet)2Br2, Si(OMet)2I2, Si(OEt)3Cl, Si(OEt)3Br, Si(OEt)3I, Si(OEt)2Cl2, Si(OEt)2Br2, Si(OEt)2I2, Si(OMet)3(NH2), Si(OMet)2(NH2)2, Si(OEt)3(NH2), Si(OEt)2(NH2)2, Si(OMet)3(NMet2), Si(OMet)2(NMet2)2, Si(OEt)3(NMet2), Si(OEt)2(NMet2)2 Si(OMet)3(NMetH), Si(OMet)2(NMetH)2, Si(OEt)3(NMetH), Si(OEt)2(NMetH)2, Si(OMet)3(NEt2), Si(OMet)2(NEt2)2, Si(OEt)3(NEt2) and Si(OEt)2(NEt2)2.

[0084] In the method according to the present invention, the inhibitor reactant selectively forms an inhibitor material on the first surface. Without limiting the present disclosure to any particular theory, the inhibitor reactant may have a higher affinity for dielectric or non-conductive surfaces, particularly surfaces containing silicon oxide, through specific components. As a result, the dielectric surface may become silylated, which, together with additional treatment of the substrate, may prevent further deposition on the first surface. For example, the inhibitor material may reduce or substantially prevent the deposition of an organic polymer on the first surface. An organic polymer such as an organic polymer containing polyimide may be used as an intermediate passivation of the second surface, and after the organic polymer is deposited on the second surface, deposition of a target material on the first surface may be achieved on the first surface. The inhibitor material may be removed before depositing the target material, but this may not be necessary. In some embodiments, the inhibitor material is partially removed from the first surface before the target material is deposited on the first surface.

[0085] According to some exemplary embodiments, structures are formed using the methods described herein. The exemplary structures may also include one or more layers, such as a metal, metallic or conductive layer covering a dielectric, or other layers deposited using methods of selectively depositing inhibitor materials and / or organic polymers. The structure may be or form part of a CMOS structure, such as one or more PMOS and NMOS structures, or other device structures.

[0086] According to further embodiments of the present disclosure, the methods and / or structures described herein may be used to form a device or a portion thereof. The device may be, for example, a CMOS device or form a portion thereof.

[0087] The present disclosure also relates to a method of depositing a silicon-containing material on a substrate. The silicon-containing material may be an inhibitor material, and the silicon reactant used to deposit the silicon-containing material may be the same compound as the inhibitor reactant disclosed herein. However, the use of the silicon reactant may be different from the inhibitor reactant because its purpose is not to inhibit the deposition of another material, but the silicon-containing material may play a role in the final semiconductor device produced by the method disclosed herein. The method of depositing the silicon-containing material includes providing a substrate in a reaction chamber and contacting the substrate with a material having the formula Si(OR) a X b R' cof a gas-phase silicon reactant. In the formula, each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl, each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl, X is selected from halogen or NR'2, a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4. The silicon reactant forms a silicon-containing material on the surface. In some embodiments, the silicon-containing material is an inhibitor. An inhibitor according to the present disclosure refers to a substance on the surface of a substrate that reduces or inhibits the deposition of a target material. In some embodiments, the silicon-containing material has a silicon-oxygen ratio of about 1:1 to 1:3. In some embodiments, the silicon-containing material is not subjected to oxidation. In some embodiments, the silicon-containing material is not in contact with an oxygen precursor.

[0088] In one aspect, a method is disclosed for selectively depositing a metal-containing material on a dielectric surface of a substrate relative to a metal-containing surface of the same substrate. The metal-containing surface can be an elemental metal surface, such as a copper surface, a cobalt surface, a molybdenum surface, or a tungsten surface, or a combination thereof. In some embodiments, the dielectric surface comprises silicon oxide or consists essentially of silicon oxide. In some embodiments, the dielectric surface forms at least a portion of a feature sidewall, and the metal-containing surface forms at least a portion of a feature bottom. In some embodiments, the deposited metal-containing material is a metal nitride. In some embodiments, the deposited metal-containing material is a metal oxide. In some embodiments, the deposited metal-containing material is selected from yttrium oxide, aluminum oxide, titanium nitride, and tantalum nitride. In some embodiments, the deposited metal-containing material is an elemental metal. In some embodiments, the metal-containing surface comprises a passivation layer comprising polyimide, and the dielectric surface comprises an inhibitor material according to the present disclosure.

[0089] In yet another aspect, a vapor deposition container is disclosed, comprising a vapor deposition container having the formula Si(OR) a X b R' c of inhibitor reactants. In the formula, each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl, each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl, X is selected from NR'2, a is 1, 2 or 3; b is 1 or 2; c is 0, 1 or 2; and a + b + c = 4. The vapor deposition container configuration and arrangement according to the present disclosure is used for vapor deposition. It may include features necessary for use in a vapor deposition assembly, such as valves, outlets, housings or other structural features.

[0090] The present disclosure is further explained by the following exemplary embodiments depicted in the accompanying drawings. The illustrations given herein are not meant to be actual views of any particular material, structure, or assembly, but are merely schematic representations of embodiments of the present disclosure. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the sizes of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. Specifically, the relative etching rates of different materials shown in the drawings may deviate from experimental results, and the details may vary depending on process conditions. The layers, structures, devices, and processing components depicted in the drawings may contain additional elements and details, which may be omitted for clarity.

[0091] For the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the methods, layers, structures, devices, and processing components described herein may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between the various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems, and / or may not exist in some embodiments.

[0092] Figure 1 1 is a block diagram of an exemplary embodiment of a method 100 according to the present disclosure. First, in stage 102, a substrate is provided in a reaction chamber. As described in the present disclosure, the substrate includes a first surface and a second surface. For example, the first surface may be a dielectric surface, and the second surface may be a metal or metallic surface. In some embodiments, the first surface is a silicon-containing dielectric surface, such as a silicon oxide surface or a low-k surface, such as a SiOC surface. The first surface and the second surface may be adjacent surfaces. They may be located on the same vertical plane and have the same orientation. However, the first surface and the second surface may alternatively be two surfaces of a feature, such as a gap, a via, a fin, etc. In some embodiments, the first surface is a sidewall of the feature. In some embodiments, the first surface is an outer sidewall of the feature. In some embodiments, the first surface is an inner sidewall of the feature. In some embodiments, the second surface is the bottom of the feature. In some embodiments, the second surface is the top surface of the feature. In some embodiments, the feature includes a first metal surface located at the bottom of the feature. The bottom may be substantially coplanar with the substrate surface. In some embodiments, the feature includes a second dielectric substantially perpendicular to the bottom of the feature, such as a silicon oxide surface.

[0093] In some embodiments, the first surface includes a material selected from SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe and combinations thereof. In some embodiments, the first surface is a dielectric surface. In some embodiments, the first surface is a low-k surface. Here, the low-k surface refers to a surface with a k value at most similar to that of silicon oxide. In some embodiments, the first surface includes an oxide. In some embodiments, the first surface includes a nitride. In some embodiments, the first surface includes silicon. In some embodiments, the first surface includes a silicon-based dielectric material. Examples of silicon-containing dielectric materials include silicon oxide-based materials, including grown or deposited silicon dioxide, doped and / or porous oxides, and native oxides on silicon. In some embodiments, the first surface includes silicon oxide. In some embodiments, the first surface is a silicon oxide surface, such as a native oxide surface, a thermal oxide surface, or a chemical oxide surface. In some embodiments, the first surface includes carbon. In some embodiments, the first surface includes SiN. In some embodiments, the first surface includes SiOC. In some embodiments, the first surface is an etch stop layer. The etch stop layer may include, for example, a nitride.

[0094] In some embodiments, the second surface is a conductive surface. In some embodiments, the second surface comprises a material selected from a metal, amorphous carbon, a metal oxide, and a metal nitride. In some embodiments, the second surface comprises a transition metal. In some embodiments, the second surface comprises an elemental metal. In some embodiments, the second surface is an elemental metal.

[0095] In some embodiments, the second surface comprises the element molybdenum. In some embodiments, the second surface is the element molybdenum. In some embodiments, the second surface comprises the element tungsten. In some embodiments, the second surface is the element tungsten. In some embodiments, the second surface comprises the element cobalt. In some embodiments, the second surface is the element cobalt. In some embodiments, the second surface comprises the element copper. In some embodiments, the second surface is the element copper. In some embodiments, the second surface comprises titanium nitride. In some embodiments, the second surface is titanium nitride. In some embodiments, the second surface comprises tantalum nitride. In some embodiments, the second surface is tantalum nitride. In some embodiments, the second surface comprises aluminum nitride. In some embodiments, the second surface is aluminum nitride.

[0096] For an embodiment in which a surface of a substrate comprises a metal, the surface is referred to as a metallic surface. In certain embodiments, the metallic surface is composed of or substantially composed of one or more metals. The metallic surface can be a metallic surface or a metallic surface. In certain embodiments, the metal or metallic surface can comprise a metal, a metal oxide and / or a mixture thereof. In certain embodiments, the metal or metallic surface can comprise surface oxidation. In certain embodiments, the metal or metallic material of the metal or metallic surface is conductive with or without surface oxidation. In certain embodiments, the metal or metallic surface comprises one or more transition metals. In certain embodiments, the metal or metallic surface comprises one or more transition metals of the 4th to 11th groups of the periodic table of elements.

[0097] In some embodiments, the second surface comprises a metal selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ru and Al. Thus, in some embodiments, the second surface comprises titanium. In some embodiments, the second surface comprises vanadium. In some embodiments, the second surface comprises niobium. In some embodiments, the second surface comprises tantalum. In some embodiments, the second surface comprises chromium. In some embodiments, the second surface comprises molybdenum. In some embodiments, the second surface comprises tungsten. In some embodiments, the second surface comprises manganese. In some embodiments, the second surface comprises iron. In some embodiments, the second surface comprises cobalt. In some embodiments, the second surface comprises nickel. In some embodiments, the second surface comprises copper. In some embodiments, the second surface comprises zinc. In some embodiments, the second surface comprises ruthenium. In some embodiments, the second surface comprises aluminum.

[0098] In some embodiments, the second surface comprises the element titanium. In some embodiments, the second surface comprises the element vanadium. In some embodiments, the second surface comprises the element niobium. In some embodiments, the second surface comprises the element tantalum. In some embodiments, the second surface comprises the element chromium. In some embodiments, the second surface comprises the element molybdenum. In some embodiments, the second surface comprises the element tungsten. In some embodiments, the second surface comprises the element manganese. In some embodiments, the second surface comprises the element iron. In some embodiments, the second surface comprises the element cobalt. In some embodiments, the second surface comprises the element nickel. In some embodiments, the second surface comprises the element copper. In some embodiments, the second surface comprises the element zinc. In some embodiments, the second surface comprises the element ruthenium. In some embodiments, the second surface comprises the element aluminum. In some embodiments, the second surface comprises an alloy of two or more metals.

[0099] In some embodiments, the metallic surface includes titanium nitride. In some embodiments, the metal or metallic surface includes one or more noble metals, such as Ru. In some embodiments, the metal or metallic surface includes conductive metal oxide. In some embodiments, the metal or metallic surface includes conductive metal nitride. In some embodiments, the metal or metallic surface includes conductive metal carbide. In some embodiments, the metal or metallic surface includes conductive metal boride. In some embodiments, the metal or metallic surface includes a combined conductive material. For example, the metal or metallic surface may include one or more of ruthenium oxide (RuOx), niobium carbide (NbCx), niobium boride (NbBx), nickel oxide (NiOx), cobalt oxide (CoOx), niobium oxide (NbOx), tungsten carbonitride (WNCx), tantalum nitride (TaN) or titanium nitride (TiN).

[0100] In some embodiments, the substrate includes a first dielectric surface and a second metal or metallic surface. In some embodiments, the substrate includes a second metal nitride surface. In some embodiments, the substrate includes a second conductive metal nitride surface. In some embodiments, the second surface may include an H termination. In some embodiments, the first surface may be a SiO2-based surface. In some embodiments, the first surface may include Si-O bonds. In some embodiments, the first surface may include a low-k material based on SiO2. In some embodiments, the first surface may contain greater than about 30% or greater than about 50% SiO2. In certain embodiments, the first surface may include or consist of a silicon dioxide surface.

[0101] In some embodiments, the first surface is a SiO2 surface and the second surface is a metal surface. In some embodiments, the first surface is a SiN surface and the second surface is a metal surface, such as an elemental metal surface. In some embodiments, the first surface is a SiOC surface and the second surface is a metal surface. In some embodiments, the first surface is a SiON surface and the second surface is a metal surface. In some embodiments, the first surface is a SiOCN surface and the second surface is a metal surface. The second metal surface can be, for example, a copper surface, a ruthenium surface, a tungsten surface, a cobalt surface or a molybdenum surface. In some embodiments, the second surface includes a metal oxide. In some embodiments, the second surface includes aluminum oxide. In some embodiments, the metal oxide surface is an oxidized surface of a metallic material. In some embodiments, a metal oxide surface is produced by oxidizing at least the surface of a metallic material using an oxygen compound, such as a compound containing O3, H2O, H2O2, O2, oxygen atoms, plasma or free radicals or a mixture thereof. In some embodiments, the metal oxide surface is a natural oxide formed on a metallic material.

[0102] In some embodiments, the metal oxide layer is selectively deposited on a first dielectric surface of the substrate relative to a second conductive (e.g., metal or metallic) surface of the substrate. In some embodiments, the first surface comprises hydroxyl (—OH) terminals. In some embodiments, the second surface comprises hydrogen (—H) terminals.

[0103] In some embodiments, an inhibitor material (e.g., an inhibitor layer) is selectively deposited on a first silicon-containing surface relative to a second metal oxide surface of the substrate. In some embodiments, the metal oxide is selected from aluminum oxide, hafnium oxide, and zirconium oxide. In some embodiments, the second surface comprises a high-k material. In some embodiments, the high-k material is selected from hafnium oxide, zirconium oxide, and combinations thereof. In some embodiments, the second surface is a hafnium oxide surface. In some embodiments, the second surface is a zirconium oxide surface. In some embodiments, the second surface is a hafnium zirconium oxide surface. In some embodiments, the second surface is a hafnium oxide surface and the first surface is a silicon-containing surface, such as a surface containing silicon and oxygen. In some embodiments, the second surface is a zirconium oxide surface and the first surface is a silicon-containing surface. In some embodiments, the second surface is a hafnium zirconium oxide surface and the first surface is a silicon-containing surface.

[0104] Prior to providing the vapor phase inhibitor reactant into the reaction chamber, the substrate may be heated at stage 102 .

[0105] At stage 104, the substrate is contacted with a gas phase inhibitor reactant. In an exemplary embodiment, the inhibitor reactant may include a trialkoxydialkylaminosilane. The contacting of the substrate with the inhibitor reactant may be performed at a temperature below 400°C, such as at a temperature of about 100°C to about 400°C, such as at a temperature of about 200°C, or about 250°C, or about 300°C, or about 320°C, or about 350°C.

[0106] At stage 106, an inhibitor material is formed on the first surface. Forming the inhibitor material in 106 may not be a discrete step, but rather it may occur when the substrate is contacted with the gas-phase inhibitor reactant. Depending on the deposition conditions, formation of the inhibitor material may occur substantially instantaneously when the inhibitor reactant contacts the first surface of the substrate. In some embodiments, formation of the inhibitor material may be delayed, or the inhibitor reactant on the substrate surface may be treated to induce formation of the inhibitor material on the first surface.

[0107] The contact of substrate and inhibitor reactant is carried out by providing the inhibitor reactant into the reaction chamber. The contact of substrate and inhibitor reactant can be carried out for a long enough time to accumulate an appropriate amount of inhibitor material on the first surface of substrate. For example, the inhibitor reactant can contact with substrate for at least about 10 seconds, for example, about 10 seconds to about 400 seconds, for example, about 30 seconds to about 300 seconds, or about 30 seconds to about 240 seconds, or about 30 seconds to about 200 seconds, or about 60 seconds to about 300 seconds, or about 100 seconds to about 300 seconds, or about 100 seconds to about 200 seconds, or about 200 seconds to about 300 seconds. The length of inhibitor treatment depends on treatment conditions, such as temperature, pressure, the partial pressure of inhibitor reactant and the reactivity of inhibitor reactant to the first surface material. The inhibitor reactant can contact with substrate by pulse alone. The reaction chamber can be purged between the pulses of the inhibitor reactant. For example, a pulse length from about 0.5 second to about 10 seconds can be used. In some tests, a pulse length of 5 seconds was used. In some embodiments, the inhibitor reactant is provided to the reaction chamber in about 15 to about 30 cycles, such as in about 20 or about 25 cycles. The inhibitor reactant may be pulsed into the reaction chamber to contact the substrate, and the reaction chamber may be optionally purged ( Figure 1 The cycle 108 in the above embodiment. For example, the purge length between two consecutive pulses can vary between 0.5 seconds and 5 seconds. The deposition of the organic polymer can be performed before repeatedly contacting the substrate with the gas phase inhibitor reactant at 104. The frequency of depositing the inhibitor material on the substrate may depend on whether the inhibitor material is consumed or loses its inhibitory properties during the deposition of the organic polymer. The appropriate frequency of depositing the inhibitor material can be determined experimentally.

[0108] In some embodiments, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition process of the inhibitor material. In some embodiments, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition process. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some embodiments, before or at the beginning of the selective deposition process, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species. In some embodiments, before or at the beginning of the selective deposition process, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species. 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.

[0109] Figure 2 is a block diagram of another exemplary embodiment of a method according to the present disclosure. Figure 2In method 200, blocks 202, 204, 206, and 208 are as for Figure 1 The corresponding blocks 102, 104, 106 and 108 in the embodiment of FIG. Figure 2 In an embodiment, the method includes depositing 210 an organic polymer.

[0110] Ring 208 corresponds to Figure 1 The optional ring 214 indicates that the deposition of the inhibitor material may be repeated after initially passivating the first surface to prevent the deposition of the organic polymer. However, the optional ring 214 indicates that the deposition of the inhibitor material may be repeated during the selective deposition of the organic polymer 210.

[0111] The deposition of the organic polymer according to the present disclosure 210 is carried out by a cyclic vapor deposition process. For example, the deposition of the organic polymer can be an MLD process. The deposition of the organic polymer includes providing a first gas phase organic precursor into a reaction chamber 210a, and providing a second gas phase organic precursor into a reaction chamber 210b. Providing the first gas phase organic precursor 210a and providing the second gas phase organic precursor 210b can define a deposition cycle. The deposition cycle (loop 212) can be repeated until an organic polymer of a suitable thickness has been deposited on the second surface of the substrate. The first and second gas phase organic precursors selectively form an organic polymer on the second surface. In some embodiments, the organic polymer includes polyimide. In some embodiments, the organic polymer includes polyamide. In some embodiments, the organic polymer forms a passivation layer on the second surface.

[0112] According to the process 210 described herein, various reactants can be used to deposit organic polymers. For example, in some embodiments, the first organic precursor is a diamine. In some embodiments, the first reactant can be, for example, 1,6-diaminohexane, 1,3-diaminopentane, a triamine, such as tris(2-aminoethyl)amine, or a cyclic compound comprising at least two primary amine groups, such as 1,4-diaminocyclohexane or p-phenylenediamine. In some embodiments, the substrate is contacted with the first organic precursor before contacting with the second organic precursor. Therefore, in some embodiments, the substrate can be contacted with the diamine before contacting with the second organic precursor.

[0113] In some embodiments, the second organic precursor is capable of reacting with the adsorbed species of the first reactant under deposition conditions. For example, in some embodiments, the second organic precursor is an anhydride, such as furan-2,5-dione (maleic anhydride). The anhydride can be a dianhydride, such as pyromellitic dianhydride (PMDA). In some embodiments, the second reactant can be any other monomer having two reactive groups that will react with the first reactant.

[0114] In some embodiments, the organic precursor does not contain metal atoms. In some embodiments, the organic precursor does not contain semimetal atoms. In some embodiments, one of the organic precursors includes metal or semimetal atoms. In some embodiments, the organic precursor includes carbon and hydrogen and one or more of the following elements: N, O, S, P or a halide, such as Cl or F.

[0115] In some embodiments, the organic precursor for selective deposition of the organic polymer 210 may be an aliphatic compound containing 1-6 carbon atoms, 2-5 carbon atoms, 2-4 carbon atoms, 5 or less carbon atoms, 4 or less carbon atoms, 3 or less carbon atoms, or 2 carbon atoms. In some embodiments, the bond between carbon atoms in the reactant or precursor may be a single bond, a double bond, a triple bond, or some combination thereof. Therefore, in some embodiments, the first organic precursor may contain two amino groups. In some embodiments, the amino group of the first organic precursor may occupy one or both terminal positions on the aliphatic carbon chain. However, in some embodiments, the amino group of the first organic precursor may not occupy any terminal position on the aliphatic carbon chain. In some embodiments, the first organic precursor may include a diamine. In some embodiments, the first organic precursor may include an organic precursor selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopropane, 2,3-butylene diamine, 2,2-dimethyl-1,3-propylene diamine.

[0116] In some embodiments, the first organic precursor provided to the reaction chamber at 210a is a liquid precursor under standard conditions. In some embodiments, the evaporated first organic precursor includes diamines, such as 1,6-diaminohexane, 1,3-diaminopentane, triamines, such as tris(2-aminoethyl)amine, or cyclic compounds including at least two primary amine groups, such as 1,4-diaminocyclohexane or p-phenylenediamine. The substrate is then exposed to the first organic precursor vapor 210a. The substrate is also exposed to a second gas phase precursor 210b, such as an organic precursor, such as a dianhydride. The dianhydride can be, for example, pyromellitic dianhydride (PMDA). The cyclic exposure of the substrate to the first and second organic precursors results in the deposition of an organic polymer. The method may include additional steps and may be repeated, but does not need to be performed in the order shown, nor in the same order in each repetition, and it can be easily extended to more complex vapor deposition techniques.

[0117] The first organic precursor according to the present disclosure may include at least two carbon atoms, such as 1,2-diaminoethane. In some embodiments, the first organic precursor includes three carbon atoms. In some embodiments, the first organic precursor includes four carbon atoms. For example, the first organic precursor may be selected from 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane and 2,4-diaminobutane. Therefore, in some embodiments, at least one amino group is connected to a carbon atom bonded to two other carbon atoms. In other words, at least one amino group may be located at the end of a carbon chain. In some embodiments, a diamine according to the present disclosure includes five carbon atoms. In some embodiments, a diamine according to the present disclosure includes six carbon atoms.

[0118] In some embodiments, the carbon chain of the first organic precursor is branched. Thus, there is at least one carbon atom bonded to three or four other carbon atoms. In some embodiments, there is one such branching position in the first organic precursor. In some embodiments, there are two such branching positions in the first organic precursor. In some embodiments, there are three or more branching points. In some embodiments, the side chain of the longer carbon chain is a methyl group. In some embodiments, the side chain of the longer carbon chain is an ethyl group. In some embodiments, the side chain of the longer carbon chain is a propyl group. In some embodiments, the side chain of the longer carbon chain is an isopropyl group. In some embodiments, the side chain of the longer carbon chain is a butyl group. In some embodiments, the side chain of the longer carbon chain is a tert-butyl group. In some embodiments, the side chain of the first organic precursor is a straight chain alkyl chain. In some embodiments, the side chain of the first organic precursor is a branched chain alkyl chain. In some embodiments, the side chain of the first organic precursor is a cyclic alkyl chain.

[0119] In some embodiments, the first organic precursor is a C2 to C11 compound. The number of carbon atoms in the first organic precursor generally affects the volatility of the compound, so that higher weight compounds may not be as volatile as smaller compounds. However, it is found that medium-sized first organic precursors containing, for example, four, five or six carbon atoms may have suitable properties for use as first organic precursors in selective deposition processes according to the present disclosure. For example, 1,3-diaminopentane is a liquid at room temperature, has a boiling point of 164°C at atmospheric pressure, has a vapor pressure of about 2.22 Torr at 25°C, and reaches a vapor pressure of 1 Torr at a temperature below 20°C. Therefore, when 1,3-diaminopentane is used as a precursor for organic polymer deposition according to the present invention, the precursor container does not need to be heated. This is beneficial for the tool life of the precursor because it is not easily degraded during continuous use. In addition, liquid precursors have the advantage that the precursor container is cheaper to load than solid precursors. In some embodiments, the first organic precursor includes 1,3-diaminopentane.

[0120] In some embodiments of the present disclosure, the amine group is connected to non-adjacent carbon atoms. This may be conducive to the availability of the amine group to react with the second precursor. In some embodiments, there is a carbon atom between the carbon atoms in conjunction with the amino group. In some embodiments, there is at least one carbon atom between the carbon atoms in conjunction with the amino group. In some embodiments, there are two carbon atoms between the carbon atoms in conjunction with the amino group. In some embodiments, there are at least two carbon atoms between the carbon atoms in conjunction with the amino group. In some embodiments, there are three carbon atoms between the carbon atoms in conjunction with the amino group. In some embodiments, there are at least three carbon atoms between the carbon atoms in conjunction with the amino group. In some embodiments, there are four carbon atoms between the carbon atoms in conjunction with the amino group. In some embodiments, there are at least four carbon atoms between the carbon atoms in conjunction with the amino group.

[0121] In some embodiments, the first organic precursor includes 1,5-diamino-2-methylpentane. Although 1,5-diamino-2-methylpentane has a lower vapor pressure than 1,3-diaminopentane, it is also a liquid at ambient temperature, requiring a modest temperature of about 40°C to reach a vapor pressure of 1 Torr.

[0122] In some embodiments, the carbon atom bonded to the amine nitrogen in the first organic precursor is bonded to at least two carbon atoms. Thus, in some embodiments in which the first organic precursor comprises five or more carbons, at least one amino group may be located away from the end of the carbon chain. The structure of the first organic precursor affects its properties during the vapor deposition process. The branching of the first organic precursor, including the number of branches and the relative position of the amino group to the branches, may result in the deposited organic polymer having different properties. Without limiting the present disclosure to any particular theory, steric factors, for example, may result in certain reactions being preferred because this may provide the possibility of designing a deposition process for a given purpose by using different first organic precursors, taking into account, for example, thermal budgets, organic polymer growth rate requirements, and the necessary degree of selectivity.

[0123] In some embodiments, the first organic precursor is a cyclic diamine. In some embodiments, the first organic precursor includes cyclopentanedialkylamine, cyclohexanedialkylamine, cyclopentadienyldialkylamine, benzenedialkylamine, cyclopentanetrialkylamine, cyclohexanetrialkylamine, cyclopentadienyltrialkylamine, and benzenetrialkylamine.

[0124] In some embodiments, the first organic precursor is an aromatic diamine. In some embodiments, the aromatic diamine is a diaminobenzene, such as 1,2-diaminobenzene, 1,3-diaminobenzene, or 1,4-diaminobenzene. In some embodiments, the aromatic diamine comprises an alkylamino group at at least one position. For example, the alkylamino group can be a C1-C3 alkylamino group, such as -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2, or -CH2CH(CH3)NH2.

[0125] In some embodiments, the first organic precursor is selected from 1,3-diaminopentane, 1,4-diaminopentane, 2,4-diaminopentane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diaminobutane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,4-diamino-4-methylpentane, 1,3-diaminobutane, 1,5-diaminohexane In some embodiments, the first organic precursor includes 1,3-diaminohexane, 2,5-diaminohexane, 1,3-diamino-5-methylhexane, 4,4,4-trifluoro-1,3-diamino-3-methylbutane, 2,4-diamino-2-methylpentane, 4-(1-methylethyl)-1,5-diaminohexane, 3-aminobutyramide, 1,3-diamino-2-ethylhexane, 2,7-diamino-2,7-dimethyloctane, 1,3-diaminobenzene and 1,4-diaminobenzene. In some embodiments, the first organic precursor includes a halogen.

[0126] In some embodiments, according to the present invention, triamines can be used for the deposition of organic polymers. Providing such molecules can advantageously affect the availability of polymerization sites of the second gas phase organic precursor. The availability of three amine groups in a single molecule can lead to a denser polymer network, which in turn can reduce the migration of metals through organic polymers. In embodiments utilizing organic polymers according to the present disclosure as passivation layers, this property may be advantageous. Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (with amines on carbons 1, 2 and 3 or on carbons 1, 2 and 4), triaminopentane (especially with amines on carbons 1 and 5, plus amines on any one of carbons 2, 3 or 4). Similarly, triaminohexane can contain amine groups on carbons 1 and 6, and on any one of positions 2, 3, 4 or 5; triaminoheptane can contain amine groups on carbons 1 and 7 and any one of positions 2, 3, 4, 5 or 6; and triaminooctane can contain amine groups on carbons 1 and 8 and any one of positions 2, 3, 4, 5, 6 or 7. In addition, branched carbon chains, in particular 2-aminomethyl-1,3-diaminopropane, 2-aminomethyl-1,4-diaminobutane (or an alternative with two amino groups elsewhere in the butane chain), 2-aminomethyl-1,5-diaminopentane (or an alternative with two amino groups elsewhere in the pentane chain), 3-aminomethyl-1,5-diaminopentane (or an alternative with two amino groups elsewhere in the pentane chain), 2-aminomethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain), 3-aminomethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain), 3-aminoethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain). In addition, aromatic triamines such as 1,3,5-triaminobenzene can be alternatives for certain embodiments.

[0127] In some embodiments, the second vapor-phase organic precursor includes pyromellitic dianhydride (PMDA).

[0128] In some embodiments, the deposited polymer comprises polyimide. Thus, in some embodiments, the organic polymer comprises polyimide. In some embodiments, the organic polymer consists essentially only of polyimide. In some embodiments, the organic polymer comprises polyamic acid. In some embodiments, the organic polymer consists essentially only of polyamic acid and polyimide. In some embodiments, the organic polymer is deposited at a temperature below 190°C and subsequently heat treated (annealed) at a temperature of about 190°C or higher (e.g., from about 200°C to about 500°C) to increase the ratio of the organic polymer from polyamic acid to polyimide. Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, other polymeric forms, or mixtures of the above materials.

[0129] In some embodiments, the substrate is thermally annealed for about 1 to about 15 minutes. In some embodiments, the substrate is thermally annealed at a temperature of about 200° C. to about 500° C. In some embodiments, the thermal annealing step includes two or more steps, wherein the substrate is thermally annealed at a first temperature for a first time period and then thermally annealed at a second temperature for a second time period.

[0130] In some embodiments, the deposited organic polymer is exposed to active substances generated by plasma. In embodiments where the organic polymer is used as a passivation material, this can improve the passivation properties of the organic polymer. For example, active substances generated by plasma containing hydrogen and argon can be used. The organic polymer can be exposed to plasma for about 1 second to about 1 minute, for example, about 1 second to about 30 seconds, or about 5 seconds to about 30 seconds, or about 1 second to about 15 seconds, or about 3 seconds to about 20 seconds, for example, about 5 seconds, about 10 seconds, about 20 seconds or about 30 seconds. At least about 20W, or at least about 50W, for example, about 20W to about 100W, for example, a plasma power of 30W, 50W or 70W can be used. Suitable plasma power and the duration of plasma exposure can be determined by experiment.

[0131] In some embodiments, as an alternative or supplement to a plasma treatment intended to change the properties of an organic polymer, a plasma treatment may be used to at least partially remove an inhibitor material from a first surface. In such embodiments, a higher plasma energy is typically used, which may negatively affect the passivation properties of the organic polymer, for example by removing the organic polymer from a second surface. The inhibitor reactants according to the present disclosure may have the advantage of requiring less removal than alternative inhibitor reactants. This may be beneficial because damage to the organic polymer—and possibly damage to other surfaces exposed to the plasma—may be reduced. This may improve the selectivity of subsequent deposition steps. In addition, compared to conventional inhibitor reactants and inhibitor materials deposited using them, the inhibitor reactants according to the present disclosure may allow the target material to grow after a shorter plasma exposure.

[0132] Before, after, or between the processing steps described herein, additional treatments, such as thermal or chemical treatments, may be performed. For example, the treatment may modify the surface or remove portions of the material on the substrate surface exposed at various stages of the process. In some embodiments, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition of the organic polymer. In some embodiments, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition of the organic polymer. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some embodiments, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species before or at the beginning of the selective deposition of the organic polymer. In some embodiments, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species before or at the beginning of the selective deposition of the organic polymer. In some embodiments, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition of the organic polymer 210, however, in some embodiments, the pretreatment or cleaning process may be performed in a separate reaction chamber. In addition, the deposition of the inhibitor materials 204, 206 and the deposition of the organic polymer 210 may be performed in the same reaction chamber, or in separate reaction chambers of the same combination tool. The deposition of the inhibitor materials 204, 206 and the deposition of the organic polymer 210 may be performed in the same deposition station, or in separate deposition stations of a multi-station chamber.

[0133] Figure 3 is a block diagram of another exemplary embodiment of a method 300 according to the present disclosure.

[0134] exist Figure 3 In method 300, blocks 302, 304, 306, and 308 are as for Figure 1 The corresponding blocks 102, 104, 106 and 108 of the embodiment of Figure 2 Blocks 202, 204, 206, and 208 of the embodiment of the present invention are performed as described.

[0135] Loop 308 corresponds to Figure 1 and Figure 2 108 and 208, and represents that after initially passivating the first surface to prevent deposition of the organic polymer, deposition of the inhibiting material may be repeatedly inhibited. Similarly, optional loop 314 corresponds to Figure 2 214, and indicates that the deposition of the inhibitor material may be renewed during the selective deposition of the organic polymer 310. In embodiments where the target material is deposited on the first surface 318, the deposition of the inhibitor material 304, 306 may be resumed after some deposition of the passivation layer including the organic polymer, optionally the cycle 314.

[0136] Figure 3 The embodiment depicted in FIG. 1 corresponds to depositing a target material 318 on a first surface. The deposition of the target material on the first surface includes depositing a passivation layer 310 on a second surface. The passivation layer may be, for example, Figure 2 The organic polymer layer explained. Optionally, depositing the target material on the first surface may include at least partially removing the inhibitor material 316 from the first surface before depositing the target material 318 on the first surface.

[0137] The selective deposition process of the target material 318 according to the present disclosure may be a cyclic deposition process, such as an ALD process. For example, the target material deposited at stage 318 may be aluminum oxide, silicon oxide, aluminum-doped silicon oxide, yttrium oxide, or a metal nitride, such as TiN or TaN.

[0138] For example, deposition 318 can be performed by, for example, providing a metal (Al, Mo, Ti, Ta, Y) or semi-metal (e.g., Si) precursor into a reaction chamber and providing a second precursor alternately and sequentially into the reaction chamber. For example, the second precursor can be an oxygen precursor, or a nitrogen precursor, or a reducing agent. After one or both precursors, the reaction chamber can be optionally purged. Various cycle options, including main cycle alternatives, are known in the art, and additional metals or other precursors can be used in the process to adjust the composition of the target material. The deposition cycle (including the metal or semi-metal precursor pulse and the second precursor pulse) can be performed 1 to about 1000 times, such as 2 to about 800 times, or about 5 to about 500 times, or about 10 to about 500 times, or about 20 to about 500 times, or about 50 to about 500 times, or about 100 to about 500 times, or about 250 to about 500 times, or about 2 to about 250 times, or about 2 to about 150 times, or about 2 to about 100 times, or about 2 to about 75 times, or about 2 to about 50 times, or about 2 to about 30 times, or about 2 to about 10 times. The number of deposition cycles can be determined experimentally depending on the desired thickness and other characteristics of the target material.

[0139] An example of a target material that can be deposited according to the method disclosed herein is aluminum oxide. It can be selectively deposited using dimethyl aluminum isopropoxide as an aluminum precursor and water as an oxygen precursor. Aluminum oxide deposition is selective to surfaces containing an organic passivation layer (e.g., a passivation layer containing polyimide). Relative to metal surfaces, aluminum oxide can be deposited on silicon oxide-based materials. In various tests conducted, it was observed that the growth delay of aluminum oxide was significantly reduced compared to the inhibitor reactants of the prior art using the inhibitor material according to the present invention. Therefore, metal-containing materials can be grown on the first surface without removing the inhibitor material. In addition, after the organic passivation material is deposited on the second surface, a hydrogen-containing plasma is used to clean the substrate. It has also been observed that the use of the inhibitor reactants disclosed herein can significantly reduce the duration of plasma treatment, possibly leading to improved process performance and / or efficiency.

[0140] Figure 4 is a schematic diagram of an exemplary embodiment of a method according to the present disclosure. Figure 4 A) to e) in FIG. 1 schematically illustrate an embodiment of the method according to the present disclosure. Figure 4 In a), a substrate 400 is depicted that includes a first surface 402 and a second surface 404. Figure 4 In b), an inhibitor material 406 according to the present disclosure is deposited on the first surface 402 relative to the second surface 404. Figure 4 In c), the second surface 404 is selectively passivated by the organic passivation layer 408 relative to the first surface 402 including the inhibitor layer 406. Figure 4 In d), a target material, such as a metal-containing material layer 410, is selectively deposited on the first surface 402 relative to the passivated second surface 404.

[0141] More specifically, Figure 4 4 shows a substrate 400 having two surfaces 402, 404, which have different material properties. The first surface may include, consist of, or consist essentially of a silicon oxide-based material or another dielectric material, such as the silicon-based material described in the present disclosure. The second surface 402 may include, consist essentially of, or consist of a metal such as Cu, W, or Mo, or a metallic material such as TiN disclosed herein.

[0142] Figure 4 b) shows the first surface 402 after the inhibition layer is deposited. Figure 4 a) of the substrate 400. Although Figure 4 Although depicted as a layer in FIG. 4 , the inhibitor material at first surface 402 may be very thin. Figure 4 c) shows that after selectively depositing an organic passivation layer 408 on the second surface 404, for example by forming a layer comprising polyimide, Figure 4 b) of the substrate 400.

[0143] Figure 4 d) shows that according to the method disclosed herein, after selectively depositing a target material layer 410 (eg, a metal oxide layer or a metal nitride layer) on the first surface 402 relative to the passivated second surface 404, Figure 4 c) of the substrate 400. Any target material 410 deposited on the second surface 404 (e.g., on the passivation layer 408) can be removed by processing (e.g., an etch-back process). However, this may be challenging for some materials because they have high etching resistance. Therefore, in many embodiments, etch-back is not performed, but the selectivity of the process is high enough without it. In other embodiments, the target material on the second surface 404 can be removed during the subsequent removal of the passivation layer 408. In some embodiments, etching is used as a post-deposition process to clean the final surface, and / or remove the passivation.

[0144] Inhibitor material 406 Figure 4 However, in some embodiments, the inhibitor material 406 may be removed prior to depositing the target material 410 on the first surface 402. This may be desirable, for example, in embodiments where the first surface 402 and the second surface 404 are in the same orientation, as is the case in the example shown. However, Figure 4 is an illustrative embodiment in which the first surface and the second surface may be in different orientations, such as at an angle relative to each other, such as perpendicular. In such embodiments, effective plasma cleaning of surfaces positioned in the direction of plasma flow may be challenging, and the present method may be advantageous. In further embodiments, the inhibitor material may be partially removed by plasma cleaning. The choice of process flow depends on factors such as the application in question, the deposited materials, and the requirements of the material stack, and may be adjusted based on these considerations.

[0145] Figure 4 e) shows Figure 4The substrate of d) in the post-deposition treatment, for example, removes the passivation layer 408 from the second surface 404 by an etching process. In some embodiments, the etching process may include exposing the substrate 400 to a plasma. In some embodiments, the plasma may include oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof. In some embodiments, the plasma may include hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. In some embodiments, the plasma may include a rare gas species, such as Ar or He species. In some embodiments, the plasma may be mainly composed of rare gas species. In some embodiments, the plasma may include other species, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or a combination thereof. In some embodiments, the etching process may include exposing the substrate to an etchant containing oxygen, such as O3. In some embodiments, the substrate may be exposed to an etchant having a temperature between about 30°C and about 500°C, or between about 100°C and about 400°C, or between about 100°C and about 300°C. In some embodiments, the etchant may be supplied in one continuous pulse, or may be supplied in multiple pulses. Removal of the passivation layer 408 may be used to strip any remaining target material from the second surface, or to completely remove the passivation layer 108 or partially remove the passivation layer 508 in a cyclic selective deposition and removal.

[0146] Figure 5 is a schematic diagram of an embodiment of a semiconductor processing assembly 500 according to the present disclosure.

[0147] In yet another aspect, a semiconductor processing assembly 500 for selectively depositing an inhibitor material on a first surface of a substrate is disclosed. The semiconductor processing assembly 500 includes one or more reaction chambers 520, which are constructed and arranged to hold a substrate, a precursor injector system 501, which is constructed and arranged to provide an inhibitor reactant in a gas phase into the reaction chamber 520. The semiconductor processing assembly 500 also includes an inhibitor reactant source container 502, which is constructed and arranged to contain the inhibitor reactant. The semiconductor processing assembly 500 is constructed and arranged to provide the inhibitor reactant into the reaction chamber 520 via the precursor injector system 501 for selectively forming an inhibitor material on the first surface of the substrate.

[0148] In some embodiments, the semiconductor processing assembly 500 further includes one or more precursor source containers 503, 504, and the precursor injector system 501 is constructed and arranged to provide one or more precursors in a gas phase into the reaction chamber 520. The precursor may be an organic precursor for depositing a passivation layer on the second surface of the substrate. Alternatively or in addition, the precursor may be a metal precursor, a semi-metal precursor, an oxygen precursor, a nitrogen precursor, or other precursor for depositing a target material on the first surface of the substrate.

[0149] The processing assembly 500 may include optional additional source containers that are constructed and arranged to contain additional reactants used in substrate processing. For example, the additional source container (not shown) may be constructed and arranged to contain an etchant.

[0150] Processing assembly 500 can be used to perform the methods described herein. In the example shown, processing assembly 500 includes one or more reaction chambers 520, precursor injector system 501, source containers 502, 503, 504, optional and additional source containers, exhaust source 522, and controller 530. Processing assembly 500 may 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. Reaction chamber 520 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber described herein.

[0151] Inhibitor reactant source container 502 may include a container and an inhibitor reactant as described herein-alone or mixed with one or more carrier gases (e.g., inert gases). Therefore, although three source containers 502-504 are shown, processing assembly 500 may include any suitable number of source containers. Source containers 502-504 may be coupled to reaction chamber 520 via pipelines 512-514, which may each include a flow controller, a valve, a heater, etc. In some embodiments, each of source containers 502-504 may be independently heated or maintained at ambient temperature. In some embodiments, the source container is heated so that the precursor or reactant reaches a temperature suitable for evaporation.

[0152] Exhaust source 522 may include one or more vacuum pumps.

[0153] Controller 530 includes electronic circuits and software to selectively operate valves, manifolds, heaters, pumps, and other components included in processing assembly 500. Such circuits and components are used to introduce precursors, reactants, and other gases from corresponding sources. Controller 530 can control the timing of gas pulse sequences, the temperature of substrates and / or reaction chamber 520, the pressure within reaction chamber 520, and various other operations to provide proper operation of processing assembly 500. Controller 530 can include control software to electrically or pneumatically control valves to control the flow of precursors, reactants, and other gases into and out of reaction chamber 520. Controller 530 can include modules, such as software or hardware components, that perform specific tasks.

[0154] Other configurations of the processing assembly 500 are also possible, including different numbers and types of precursors and source containers. For example, the reaction chamber 520 may include more than one, for example two or four deposition stations. If, for example, inhibition, passivation, deposition and / or etching are performed in the same reaction chamber, this multi-station configuration may have advantages. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and reactant sources that can be used to achieve the goal of selectively and in a coordinated manner supplying gases to the reaction chamber 520. In addition, as a schematic representation of the processing assembly 500, many components have been omitted for simplicity of description, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0155] During operation of the processing assembly 500, substrates such as semiconductor wafers (not shown) are transferred from, for example, a substrate handling system to the reaction chamber 520. Once the substrates are transferred to the reaction chamber 520 (i.e., they are provided in the reaction chamber 520), one or more gases from a gas source, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into the reaction chamber 520.

[0156] The exemplary embodiments of the present disclosure described above do not limit the scope of the present disclosure, as these embodiments are merely examples of embodiments of methods, structures, devices, and processing components, which are defined by the appended claims and their legal equivalents. Any equivalent embodiments are within the scope of the present disclosure. Various modifications of the present disclosure, such as alternative useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

[0157] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

[0158] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various methods and components, and other features, functions, acts, and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method of selectively depositing an inhibitor material on a first surface of a substrate relative to a second surface of the substrate, the method comprising: providing a substrate including a first surface and a second surface in a reaction chamber; contacting the substrate with a vapor phase inhibitor reactant, the inhibitor reactant comprising silicon atoms bonded to first atoms and second atoms; wherein the first atom is oxygen and the second atom is selected from nitrogen and a halogen; and The inhibitor reactant selectively forms an inhibitor material on the first surface.

2. The method according to claim 1, wherein: The first surface includes a dielectric material.

3. A method according to any one of the preceding claims, wherein: The first surface includes a material selected from the group consisting of SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, and combinations thereof.

4. The method according to claim 1 or 2, wherein: The dielectric material includes metal oxide or metal nitride.

5. The method according to claim 4, wherein: The dielectric material is selected from the group consisting of aluminum oxide, hafnium oxide, zirconium oxide, aluminum nitride, tantalum nitride, and combinations thereof.

6. A method according to any one of the preceding claims, wherein: The second surface includes a material selected from the group consisting of metal, amorphous carbon, metal oxide, and metal nitride.

7. A method according to any one of the preceding claims, wherein: The second surface comprises a metal selected from the group consisting of Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ru and Al.

8. A method according to any one of the preceding claims, wherein: The second surface comprises elemental metal.

9. A method according to any one of the preceding claims, wherein: The first atom is the oxygen of an alkoxy group.

10. The method according to claim 9, wherein: The silicon atom is bonded to at least two oxygen atoms, and each oxygen atom is an oxygen of an alkoxy group.

11. A method according to any one of the preceding claims, wherein: The second atom is the nitrogen atom of the amine group.

12. The method according to claim 11, wherein: The amine group is a tertiary amine.

13. The method according to any one of claims 1 to 10, wherein: The second atom is a halogen selected from F, Cl, Br and I.

14. A method according to any one of the preceding claims, wherein: The inhibitor reactant is of the formula Si(OR) a X b R' c It indicates that, Each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl; Each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl; X is selected from halogen or NR'2; a is 1, 2, or 3; b is 1 or 2; c is 0, 1, or 2; and a + b + c = 4.

15. The method according to claim 14, wherein: All R and R' are C1 to C4 alkyl.

16. A method according to any one of the preceding claims, wherein: The inhibitor reactant is selected from Si(OMet)3Cl, Si(OMet)3Br, Si(OMet)3I, Si(OMet)2Cl2, Si(OMet)2Br2, Si(OMet)2I2, Si(OEt)3Cl, Si(OEt)3Br, Si(OEt)3I, Si(OEt)2Cl2, Si(OEt)2Br2, Si(OEt)2I2, Si(OMet)3(NH2),Si(OMet)2(NH2)2, Si(OEt)3(NH2), Si(OEt)2(NH2)2, Si(OMet)3(NMet2), Si(OMet)2(NMet2)2, Si(OEt)3(NMet2), Si(OEt)2(NMet2)2, Si(OMet)3(NMetH), Si(OMet)2(NMetH)2, Si(OEt)3(NMetH), Si(OEt)2(NMetH)2, Si(OMet)3(NEt2), Si(OMet)2(NEt2)2, Si(OEt)3(NEt2) and Si(OEt)2(NEt2)2.

17. A method according to any one of the preceding claims, wherein: The deposition is carried out at a temperature below 400°C.

18. A method according to any one of the preceding claims, wherein: The inhibitor material is deposited substantially only on the first surface and not on the second surface.

19. A method of selectively depositing a target material on a first surface of a substrate, the method comprising selectively depositing an inhibitor material on the first surface of the substrate according to any one of claims 1 to 18 before depositing the target material.

20. The method according to claim 19, wherein: The method also includes depositing a passivation layer on a second surface of the substrate after selectively depositing an inhibitor material on the first surface, and then depositing the target material on the first surface.

21. The method according to claim 20, wherein: The inhibitor material is not removed prior to depositing the target material on the first surface.

22. A method for depositing a silicon-containing material on a substrate, the method comprising: providing a substrate in a reaction chamber; The substrate is connected with a Si(OR) a X b R' c The vapor phase silicon reactant is contacted with Each R is independently selected from linear, branched and cyclic C1 to C6 alkyl and phenyl; Each R' is independently selected from H, linear, branched and cyclic C1 to C6 alkyl and phenyl; X is selected from NR'2; a is 1, 2, or 3; b is 1 or 2; c is 0, 1, or 2; and a + b + c = 4; Therein, the silicon reactant forms a silicon-containing material on the surface.

23. The method according to claim 22, wherein: The silicon-containing material has a silicon-to-oxygen ratio of about 1:1 to 1:3.

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