Improved polymer inhibitors for regioselective deposition

Abstract

Methods and apparatus for forming a passivation layer on a substrate are disclosed, comprising: providing a substrate in a reaction chamber, the substrate comprising a first surface and a second surface; contacting the substrate with a first precursor comprising an amine compound, the amine compound comprising at least two amine groups; and contacting the substrate with a second precursor comprising at least one thioanhydride, where contacting the substrate with the first and second precursors selectively forms a film on the first surface relative to the second surface.

Description

Technical Field

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

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

[0003] Semiconductor manufacturers are increasingly interested in selective deposition, which can reduce the steps required for conventional patterning, thereby reducing processing costs. Selective deposition can also enhance scaling in 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. More efficient and reliable techniques are needed to improve selectivity and reduce defectivity in selective deposition.

[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 at the time of conceiving the subject matter of the present disclosure, or constitutes prior art. Summary of the invention

[0005] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to necessarily identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] Disclosed are a method and apparatus for forming a passivation layer on a substrate, comprising: providing a substrate in a reaction chamber, the substrate comprising a first surface and a second surface, contacting the substrate with a first precursor comprising an amine compound containing at least two amine groups, and contacting the substrate with a second precursor comprising at least one thioanhydride, wherein contacting the substrate with the first and second precursors selectively forms a film on the first surface relative to the second surface.

[0007] In some examples, the passivation layer includes a polyimide film. In some examples, the passivation layer includes a polyimide film pyromellitic dithioanhydride.

[0008] In some examples, the contacting operation includes a deposition cycle, and the process includes one or more deposition cycles.

[0009] In some examples, the contacting operation further includes repeating the contacting operation until a passivation layer of a desired thickness has been formed.

[0010] In various examples, the first surface is a metal carbide, a metal oxide, a metal nitride, a metal boride, an elemental metal, a metallic surface, amorphous carbon, or a combination thereof.

[0011] In some examples, the first surface includes a metal including aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V) or a combination thereof.

[0012] In various examples, the first surface is a dielectric surface comprising SiCOx, SiOx, silicon, SiO2, zirconium oxide (ZrO2), hafnium oxide (HfO2), aluminum oxide (Al2O3), titanium nitride (TiN) and titanium oxide (TiO2) or aluminum nitride (AlN) or a combination thereof.

[0013] In some examples, the first surface includes RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN, or TiN, or a combination thereof.

[0014] In various examples, the second surface includes a passivation barrier layer formed thereon.

[0015] In some examples, the second surface includes a metal including aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V) or a combination thereof.

[0016] In various examples, the second surface is a dielectric surface comprising SiCOx, SiOx, silicon, SiO2, zirconium oxide (ZrO2), hafnium oxide (HfO2), aluminum oxide (Al2O3), titanium nitride (TiN) and titanium oxide (TiO2) or aluminum nitride (AlN) or a combination thereof.

[0017] In some examples, the second surface includes RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN, or TiN, or a combination thereof.

[0018] In certain examples, the passivating barrier layer includes a self-assembled monolayer (SAM) or an alkylsilane having at least one alkoxy group bonded to a silicon atom.

[0019] In various examples, the first precursor includes a diamine, a triamine, a tetraamine, a cyclic compound including at least two primary amines, or a combination thereof.

[0020] In some examples, the second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by formula (1):

[0021] (1)

[0022] Wherein, R and R' independently comprise hydrocarbon groups. In various examples, at least one of the hydrocarbon groups independently comprises one or more of the following: O, N or S or a combination thereof.

[0023] In certain examples, the second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by formula (2):

[0024] (2)

[0025] Wherein, R comprises a hydrocarbon group. In various examples, the hydrocarbon group comprises one or more of the following: O, N or S or a combination thereof.

[0026] In some examples, the second precursor includes a compound including a thioanhydride group and an acid anhydride group, the compound including a structure represented by formula (3):

[0027] (3)

[0028] Wherein, R and R' independently comprise hydrocarbon groups. In various examples, wherein at least one of the hydrocarbon groups independently comprises one or more of the following: O, N or S or a combination thereof.

[0029] In various examples, the second precursor includes a compound including one thioanhydride group and one anhydride group, the compound including a structure represented by general formula (4):

[0030] (4)

[0031] Wherein, R comprises a hydrocarbon group. In various examples, the hydrocarbon group comprises one or more of the following: O, N or S or a combination thereof.

[0032] In various examples, the second precursor includes a compound including at least one thioanhydride group, the compound including a structure represented by formula (5):

[0033] (5)

[0034] wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of the following: O, N or S or a combination thereof; and wherein X is selected from S or O.

[0035] In some examples, the second precursor includes a compound including two or more anhydride groups, the compound including a structure represented by formula (6):

[0036] (6)

[0037] wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of the following: O, N or S or a combination thereof; and wherein X' and X" are independently selected from S, Se, Te, NH, NR" or O, wherein R" is a C1 to C6 compound.

[0038] In some examples, the second precursor includes a compound represented by formula (7):

[0039] (7)

[0040] wherein R1, R2 and R3 independently comprise hydrocarbon groups, which optionally include one or more of the following: O, N or S or a combination thereof; and wherein Y is selected from S, Se, Te, NH, NR" or O, wherein R" is a C1 to C6 compound.

[0041] In some examples, the process also includes depositing a material selectively on the second surface of the substrate relative to the passivation layer.

[0042] In various examples, the material is a first dielectric and the second surface is a second dielectric.

[0043] In some examples, the material is a dielectric and the second surface is a metal.

[0044] In some examples, the material is a metal and the second surface is a dielectric.

[0045] In various examples, the material is a metal and the second surface is a metal including a conductive metal nitride.

[0046] In order to summarize the present disclosure and the advantages achieved relative to the prior art, certain objects and advantages of the present disclosure have been described above. Of course, it should be understood that all of these objects or advantages may not be achieved according to any specific embodiment or example of the present disclosure. Thus, for example, those skilled in the art will recognize that the examples disclosed herein can be implemented in a manner that achieves or optimizes one advantage or a group of advantages taught or suggested herein, without necessarily achieving other objects or advantages taught or suggested herein.

[0047] All of these examples are within the scope of the present disclosure.These and other embodiments will become apparent to those skilled in the art through the following detailed description of certain examples with reference to the accompanying drawings, the present disclosure not being limited to any particular examples discussed. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] To easily identify the discussion of any particular element or act, the most significant digit(s) in a reference number refers to the figure number in which the element is first introduced.

[0049] Figure 1 is a flow chart generally illustrating an atomic layer deposition (ALD) process for selectively depositing organic films.

[0050] Figure 2 is a flow chart generally illustrating an atomic layer deposition (ALD) process for selectively depositing organic films.

[0051] Figure 3 is a schematic diagram of an apparatus configured for selectively depositing a polymer layer.

[0052] Figure 4 is a flow chart generally illustrating an atomic layer deposition (ALD) process for selectively depositing organic films.

[0053] Figure 5 is a flow chart generally illustrating an atomic layer deposition (ALD) process for selectively depositing organic films. DETAILED DESCRIPTION

[0054] The descriptions of exemplary embodiments of methods, layers, structures, devices, 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. 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.

[0055] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed subject matter.

[0056] 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 including an alkylsilane having at least one alkoxy group bonded to a silicon atom, wherein the inhibitor reactant selectively forms the inhibitor material on the first surface.

[0057] 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 a cluster 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.

[0058] 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 the 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 the reaction chamber, and may include sealing gases.

[0059] The term dielectric is used in the description herein to simplify the distinction from metal or metallic surfaces. Those skilled in the art will appreciate 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 method 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.

[0060] 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 at the surface. The reactants on the substrate surface can be modified by, for example, thermal treatment or plasma treatment.

[0061] In some embodiments, the precursor or reactant is provided as a mixture of two or more compounds. In the mixture, the 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.

[0062] 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".

[0063] As used herein, the term "consisting of" means that, in addition to the features following the wording, no other features are present in the device / method / product. When the term "consisting of" is used to refer to a chemical compound, substance, or composition of matter, it means that the chemical compound, substance, or composition of matter contains only the listed components. Similarly, when the term "essentially consisting of" is used to refer to a chemical compound, substance, or composition of matter, it means that the chemical compound, substance, or composition of matter contains the listed components, but may also contain trace elements and / or impurities that do not significantly affect the characteristics of the chemical compound, substance, or composition of matter. Nevertheless, in some embodiments, in addition to the listed ingredients, the chemical compound, substance, or composition of matter may include other ingredients that are trace elements or impurities.

[0064] 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 "including", "consisting of" and "having" independently refer to "usually or broadly including", "comprising", "essentially consisting of" or "consisting 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.

[0065] 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.

[0066] Substrate

[0067] 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 the bulk material or located below it. 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.

[0068] 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.

[0069] 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.

[0070] Reaction Chamber

[0071] 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 may be a single wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a vapor 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 dielectric material, may be performed in a single reaction chamber, or they may 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.

[0072] 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.

[0073] 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, 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 of the substrate and / or reactants and / or precursors.

[0074] Cyclic Vapor Deposition

[0075] In some methods according to the present disclosure, particularly methods for depositing organic polymers and dielectric materials, a cyclic vapor deposition method may be used. Cyclic deposition in the present disclosure refers to a vapor deposition process in which a deposition cycle (usually multiple consecutive deposition cycles) is performed in a process chamber. For clarity, the deposition of inhibitor materials according to the present disclosure may be a non-cyclic process in which the inhibitor reactant is.

[0076] 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 the desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. During one or more cycles, 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, whereas in MLD the precursors can be entirely organic molecules, such as when depositing organic polymers.

[0077] 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, the 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 use multiple cycles to deposit a film with a desired thickness. In a cyclic CVD process, precursors and / or reactants may be provided to a reaction chamber in the form of non-overlapping or partially or completely overlapping pulses. 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 stage 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.

[0078] According to some aspects of the present disclosure, selective deposition can be used to deposit material on a first surface relative to a second surface. The two surfaces can have different material properties.

[0079] In some examples, an organic material such as polyamide or polyimide is selectively deposited on a first conductive (e.g., metal or metallic) surface of a substrate relative to a second dielectric surface of the substrate. In some examples, the second surface includes -OH groups, such as a silicon oxide-based surface. In some examples, the second surface may additionally include -H terminations, such as HF-immersed Si or HF-immersed Ge surfaces. In such examples, the surface of interest will be considered to include -H terminations and materials below the -H terminations. In some examples, an organic material such as polyamide or polyimide is selectively deposited on a first dielectric surface of a substrate relative to different second dielectric surfaces. In some such examples, the dielectric has different compositions (e.g., silicon, silicon nitride, carbon, silicon oxide, silicon oxynitride, germanium oxide). In other such examples, the dielectric may have the same basic composition (e.g., silicon oxide-based), but has different material properties due to the formation method (e.g., thermal oxide, native oxide, deposited oxide). In some examples, a vapor deposition method is used. In some examples, a cyclic vapor deposition is used, such as a cyclic CVD or atomic layer deposition (ALD) process. After the selective deposition of the organic material is complete, further processing may be performed to form the desired structure.

[0080] For example, one of the surfaces includes metal, and the other surface does not include metal, unless otherwise specified, if the surface is referred to as a metal surface in this article, it can be a metal surface or a metallic surface. In some examples, the metal or metallic surface can include metal, metal oxide and / or its mixture. In some examples, the metal or metallic surface can include surface oxidation. In some examples, the metal or metallic material of the metal or metallic surface is conductive with or without surface oxidation. In some examples, the metal or metallic surface includes one or more transition metals. In some examples, the metal or metallic surface includes aluminum. In some examples, the metal or metallic surface includes one or more of the following: aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V) or a combination thereof. In some examples, the metallic surface includes titanium nitride. In some examples, the metal or metallic surface includes one or more noble metals, such as Ru. In some examples, the metal or metallic surface includes a conductive metal oxide, nitride, carbide, boride, or a combination thereof. For example, the metal or metallic surface may include one or more of the following: RuOx , NbC x , NbB x , NiO x , CoO x ,NbO x , WNCx, TaN, MoNx, WNx, AlOx and / or TiN.

[0081] In some examples, the metal or metallic surface can include Zn, Fe, Mn, or Mo. In some examples, the metal or metallic surface can be any surface capable of accepting or cooperating with the first or second precursor used in the selective deposition process as described herein.

[0082] In some examples, the organic material is selectively deposited on the metal oxide surface relative to other surfaces. The metal oxide surface can be, for example, WO x , HfO x , TiO x , AlO x or ZrO x In some examples, the metal oxide surface is an oxidized surface of a metallic material. In some examples, the 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 examples, the metal oxide surface is a native oxide formed on a metallic material.

[0083] In some examples, the first surface can include a passivated metal surface, such as a passivated Cu surface. That is, in some examples, the first surface can include a metal surface including a passivation layer, such as an organic passivation layer, such as a benzotriazole (BTA) layer.

[0084] In some examples, the organic material is selectively deposited on the first dielectric surface relative to the second SiO2 surface. In some examples, the organic material is selectively deposited on the first dielectric surface relative to the second Si or Ge surface, such as the HF-immersed Si or HF-immersed Ge surface.

[0085] In some examples, the organic material is selectively deposited on the first metal or metallic surface of the substrate relative to the second dielectric surface of the substrate. In some examples, the organic material of selective deposition is polyamide, polyimide or other polymeric materials. The term dielectric is used in the description of this article to simplify the distinction from other surfaces (i.e., 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, the metal or metallic surface can include a non-conductive or oxidized metal surface with very high resistivity. The selective deposition process taught herein can be deposited on such non-conductive metallic surfaces, and the deposition on the adjacent dielectric surface is minimal.

[0086] In some examples, the organic material is selectively deposited on the first metal oxide surface of the substrate relative to the second SiO2 surface. In some examples, the first metal oxide surface can be, for example, WO x , HfO x , TiO x , AlO x or ZrO x In some examples, the organic material is deposited on the first dielectric surface relative to the second SiO2 surface. In some examples, the second SiO2 surface can be, for example, a native oxide, a thermal oxide, or a chemical oxide. In some examples, the organic material is selectively deposited on the first metal oxide surface relative to a second Si or Ge surface, such as an HF-immersed Si or HF-immersed Ge surface.

[0087] In some examples, a substrate comprising a first metal or metallic surface and a second dielectric surface is provided. In some examples, a substrate comprising a first metal oxide surface is provided. In some examples, the second surface may include -OH groups. In some examples, the second surface may be a SiO2-based surface. In some examples, the second surface may include Si-O bonds. In some examples, the second surface may include SiO2-based low-k materials. In some examples, the second surface may include greater than about 30% or greater than about 50% SiO2. In some examples, the second surface may include GeO2. In some examples, the second surface may include Ge-O bonds. In some examples, an organic material is selectively deposited on a first metal or metallic surface relative to a second Si or Ge surface, such as a Si immersed in HF or a Ge immersed in HF surface.

[0088] In some examples, the first surface may include a silicon dioxide surface and the second dielectric surface may include a different second silicon dioxide surface. For example, in some examples, the first surface may include a natural or chemically grown silicon dioxide surface. In some examples, the second surface may include a thermally grown silicon dioxide surface. In other examples, the first or second surface may be replaced with a deposited silicon oxide layer. Thus, in some examples, an organic material may be selectively deposited on a first silicon dioxide surface of a substrate relative to a second silicon dioxide surface formed by a different technique and therefore having different material properties.

[0089] In some examples, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition process. In some examples, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition process. In some examples, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some examples, 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 process. In some examples, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species before or at the beginning of the selective deposition process. In some examples, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition process, however, in some examples, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0090] The term "about" is used herein to mean within standard measurement accuracy.

[0091] Selective deposition using the methods described herein can be advantageously achieved by treating the second dielectric surface to prevent deposition thereon and / or treating the first surface (whether metallic or a different dielectric surface) to catalyze deposition. Thus, in some examples, the second dielectric surface can include a passivating barrier or inhibitor layer, such as a self-assembled monolayer (SAM), which can prevent the top surface of the second dielectric surface from being exposed to the chemicals of the deposition process described herein. Thus, in some examples, selectivity is achieved by using a capping agent or catalyst, where one of the first or second surfaces is not directly exposed to the deposition reactants.

[0092] Vapor deposition techniques can be applied to organic films and polymers, such as polyimide films, polyamide films, polyurea films, polyurethane films, polythiophene films, etc. Compared with the application of liquid precursors, CVD of polymer films can produce greater thickness control, mechanical flexibility, conformal coverage and biocompatibility. Sequential deposition processing of polymers can produce high growth rates in small research-scale reactors. Similar to CVD, sequential deposition processes can produce greater thickness control, mechanical flexibility and conformality. The terms "sequential deposition" and "cyclic deposition" are used in this article to refer to processes in which a substrate is exposed to different precursors alternately or sequentially, regardless of whether the reaction mechanism is similar to ALD, CVD, MLD or a mixture thereof.

[0093] In some examples, the processes described herein may be batch processes, that is, the processes may be performed on two or more substrates simultaneously. In some examples, the processes described herein may be performed on two or more, five or more, 10 or more, 25 or more, 50 or more, or 100 or more substrates simultaneously. In some examples, the substrate may include a wafer, such as a semiconductor or silicon wafer. In some examples, the substrate may have a diameter of 100 mm or more, 200 mm or more, or 300 mm or more. In some cases, a substrate having a diameter of 450 mm or more may be ideal.

[0094] Selectivity

[0095] Selectivity can be given as a percentage calculated by [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured by any of a variety of methods. In some examples, deposition can be given as a measured thickness of deposited material. In some examples, deposition can be given as a measured amount of deposited material.

[0096] In some examples, the selectivity is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%. In the examples described herein, the selectivity can vary with the duration or thickness of the deposition. Surprisingly, for the vapor phase polymer film deposition described herein, it has been found that the selectivity increases with the increase in the duration of the deposition. In contrast, typical selective deposition based on differential nucleation on different surfaces tends to decrease in selectivity with the increase in the duration or thickness of the deposition.

[0097] In some examples, deposition occurs only on the first surface and not on the second surface. In some examples, 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 examples, 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 examples, 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.

[0098] In some examples, the thickness of the organic film deposited on the first surface of the substrate can be less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm, or less than about 1 nm, and the ratio of material deposited on the first surface of the substrate relative to the second surface of the substrate can be greater than or equal to about 2:1, greater than or equal to about 20:1, greater than or equal to about 15:1, greater than or equal to about 10:1, greater than or equal to about 5:1, greater than or equal to about 3:1, or greater than or equal to about 2:1.

[0099] In some examples, the selectivity of the selective deposition processes described herein may depend on the materials comprising the first and / or second surface of the substrate. For example, in some examples where the first surface comprises a BTA-passivated Cu surface and the second surface comprises a natural or chemical silicon dioxide surface, the selectivity may be greater than about 8:1 or greater than about 15:1. In some examples where the first surface comprises a metal or metal oxide and the second surface comprises a natural or chemical silicon dioxide surface, the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples where the first surface comprises a chemical or natural silicon dioxide surface and the second surface comprises a thermal silicon dioxide surface, the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples where the first surface comprises natural or chemical silicon dioxide and the second surface comprises a Si-H termination (e.g., a HF-impregnated Si surface), the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples where the first surface comprises a Si-H termination (e.g., a HF-impregnated Si surface) and the second surface comprises thermal silicon dioxide, the selectivity may be greater than about 5:1 or greater than about 10:1.

[0100] Selective deposition

[0101] The deposition processes taught herein can achieve high growth rates and throughputs, and can produce high quality organic thin films.

[0102] In some examples, a substrate including a first surface and a second surface is provided. The first and second surfaces may have different material properties. In some examples, the first surface may be a metallic surface and the second surface may be a dielectric surface. In some examples, a first precursor is evaporated to form a first precursor vapor. Under standard temperature and pressure conditions (room temperature and atmospheric pressure), the evaporated reactant may be a liquid or a solid. In some examples, the evaporated reactant includes an organic precursor, such as an amine, such as a diamine, such as 1,6-diamantane (DAH), or another organic precursor, such as a dianhydride, such as pyromellitic dianhydride (PMDA) and / or pyromellitic dithioanhydride (PMDTA). The substrate is then exposed to the first precursor vapor and an organic film is deposited. The method may include additional steps and may be repeated, but does not need to be performed in the order shown, and if repeated, does not need to be performed in the same order in each repetition, and can be easily extended to more complex vapor deposition techniques.

[0103] In some examples, the organic film includes a polymer. In some examples, the deposited polymer is a polyimide. In some examples, the deposited polymer is a polyamide. Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, other polymeric forms, or mixtures of the above materials. The techniques taught herein can be applied to vapor deposition techniques, including CVD, VPD, ALD, and MLD in various reactor configurations.

[0104] Selective deposition

[0105] Figure 1 An example process 100 for selectively passivating a substrate 128 having a first surface 104 relative to a second surface 106 (or inhibitor surface 112) followed by selective deposition on the second surface 106 relative to the passivated first surface 104 is schematically illustrated. The following description of the process 100 refers to Figure 2 and 3 .

[0106] In one example, process 100 begins at operation 120, where a substrate 128 having a first surface 104 and a second surface 106 is supported in a reaction chamber 302 (see Figure 3 In the illustrated example, the first surface 104 includes a first material 110. The first material 110 may be any of a variety of materials.

[0107] In some examples, the first material 110 may be metallic and / or include a metal. Thus, the first material 110 may include a metal oxide, a metal nitride, a metal boride, an elemental metal, a metallic surface, an amorphous carbon, or a combination thereof. In some examples, the first material 110 may include aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V), etc. or a combination thereof. In some examples, the first material 110 may include RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN or TiN.

[0108] In some examples, the first material 110 may be a dielectric. Therefore, the first material 110 may include SiCOx, SiOx, Si, a high-k material or a low-k material, etc. or a combination thereof. In some examples, the first material 110 may include zirconium oxide (ZrOx), hafnium oxide (HfOx), aluminum oxide (Al2O3), titanium nitride (TiN), titanium oxide (TiOx), aluminum nitride (AlN), etc. or a combination thereof.

[0109] In the illustrated example, the second surface 106 includes a second material 114. The second material 114 may include any of a variety of materials.

[0110] In some examples, the second material 114 may include a dielectric. Thus, the second material 114 may include SiCOx, SiOx, Si, a high-k material, a low-k material, or the like, or a combination thereof. In some examples, the second material 114 may include a dielectric, such as zirconium oxide (ZrOx), hafnium oxide (HfOx), aluminum oxide (Al2O3), titanium nitride (TiN), titanium oxide (TiOx), aluminum nitride (AlN), or the like, or a combination thereof.

[0111] In some examples, the second material 114 may be metallic and / or include a metal. In some examples, the second material 114 may include a metal oxide, a metal nitride, a metal boride, an elemental metal, a metallic surface, an amorphous carbon, or a combination thereof. In some examples, the second material 114 may include aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V), etc. or a combination thereof. In some examples, the second material 114 may include RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN or TiN or a combination thereof.

[0112] Process 100 may continue to operation 122 where selective deposition of a passivation layer 108 on the first surface 104 may be performed.

[0113] In some examples, the first material 110 and the second material 114 of the substrate 128 can be different in material, and thus the exposed first surface 104 and the second surface 106 can be different in material. For example, the first material 110 can be metallic and / or include a metal, and the second material 114 can include a dielectric, such as a low-k layer (typically a silicon oxide-based layer) or a silicon surface with a native oxide (also in the form of silicon oxide) formed thereon. Thus, the first surface 104 can be metallic and / or include a metal, and the second surface 106 can include a dielectric, such as a low-k layer (typically a silicon oxide-based layer) or a silicon surface with a native oxide (also in the form of silicon oxide) formed thereon.

[0114] At operation 122, selective deposition of a passivation layer 108 on the first surface 104 may be performed. The passivation layer 108 may be a polymer layer selectively deposited on the metallic surface of the first surface 104. An example method for selectively depositing a polymer layer by vapor deposition techniques is disclosed in U.S. Pat. No. 10,373,820, issued on August 6, 2019, the entire disclosure of which is incorporated herein by reference. Further information and examples of selective deposition of a polymer layer used as a passivation layer are provided below.

[0115] In some examples, the polymer selectively deposited is a polyimide. In some examples, the polymer deposited is a polyamide. Other examples of deposited polymers include dimers, trimers, polyurea layers, polythiophene polyurethanes, polythioureas, polyesters, polyimines, other polymeric forms, or mixtures of the above materials. The vapor-deposited organic material includes polyamic acid, which can be a precursor for polymer formation. The selectively deposited layer can be a mixture including a polymer and a polyamic acid, which, for the purposes of this disclosure, will be considered a polymer.

[0116] In an example, the organic material deposited on the second surface 106 can be removed by an etch-back process. In some examples, an etching process after the selective deposition of the organic layer can remove the deposited organic material from the first surface 104 and the second surface 106 of the substrate. In some examples, the etching process can be isotropic.

[0117] In one example, the etching process can remove the same amount or thickness of material from the first and second surfaces. That is, in some examples, the etching rate of the organic material deposited on the first surface 104 can be substantially similar to the etching rate of the organic material deposited on the second surface 106. Due to the selectivity of the deposition process described herein, the amount of organic material deposited on the second surface 106 of the substrate 128 is significantly less than the amount of material deposited on the first surface 104 of the substrate 128. Therefore, the etching process can completely or almost completely remove the deposited organic material from the second surface 106 of the substrate, while the deposited organic material can remain on the first surface 104 of the substrate 128.

[0118] In operation 124, selective deposition of a material layer 116 on a second surface 106 (in this example, an inorganic dielectric surface) relative to a passivation layer 108 on a first surface 104 may be performed. In one example, the first surface 104 may be a conductive metal or metallic surface. In one example, the material layer 116 may be a dielectric material, particularly a metal oxide, such as zirconium oxide, hafnium oxide, and / or titanium oxide. U.S. Patent No. 11,081,342, issued on August 3, 2021, discloses an example method for selectively depositing such a metal oxide layer by vapor deposition techniques, which employs a hydrophobic precursor to aid selectivity relative to an organic passivation layer, the entire disclosure of which is incorporated herein by reference. Further information and examples of selective deposition of metal oxides and other layers of interest are provided below.

[0119] In one example, material layer 116 material deposited on passivation layer 108 may be removed by an etch-back process. Because material layer 116 is selectively deposited on second surface 106, any material layer 116 material remaining on passivation layer 108 will be thinner than material layer 116 formed on second surface 106. Thus, the etch-back process may be controlled to remove all material on passivation layer 108 without removing all material layer 116 from dielectric second surface 106. Repeatedly selectively depositing and etching back in this manner may result in an increase in the thickness of material including material layer 116 on second surface 106 with each cycle of deposition and etching. Repeatedly selectively depositing and etching back in this manner may also result in an increase in the overall selectivity of material on dielectric because each cycle of deposition and etching leaves a clean passivation layer 108 and material deposited by selective deposition of layer of interest 110 is less likely to nucleate on passivation layer 108.

[0120] Alternatively, any material layer 116 material may be removed during the subsequent removal of the passivation layer in a stripping process. As is known in the art, the stripping process removes material above by undercutting to remove the underlying material. Any material layer 116 material formed on the passivation layer 110 during a short selective deposition process tends to be discontinuous, thereby allowing the etchant to contact the underlying material to be removed. The stripping etch does not require complete removal of the passivation layer 110 in order to remove all unwanted material layer 116 material from the surface of the passivation layer 110, so that a direct etch or stripping method can be used to remove material layer 116 material from the surface of the passivation layer 110 in a cyclic selective deposition and removal.

[0121] At operation 126, a substrate 128 is shown after the passivation layer 110 is removed from the first surface 104. In some examples, the etching process may include exposing the substrate to a plasma. In some examples, the plasma may include oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof. In some examples, the plasma may include hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. In some examples, the plasma may also include a rare gas species, such as an Ar or He species. In some examples, the plasma may be mainly composed of a rare gas species. In some cases, the plasma may include other species, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or a combination thereof. In some examples, the etching process may include exposing the substrate to an etchant containing oxygen, such as O3. In some examples, the substrate may be exposed to an etchant having a temperature between about 30°C and about 500°C, preferably between about 100°C and about 400°C. In some examples, the etchant may be supplied in one continuous pulse, or may be supplied in multiple shorter pulses. The passivation layer 110 removal may be used to strip any remaining layer of interest 10 material from the passivation layer, or to completely remove the passivation layer or partially remove the passivation layer in a cyclic selective deposition and removal.

[0122] As described above, in some examples, O3 (e.g., O3 / N2) can be used in the etching process to remove the organic passivation layer. In some examples, the etching process can be performed at a substrate temperature of about 20°C to about 500°C. In some examples, the etching process can be performed at a substrate temperature of about 50°C to about 300°C. In some examples, the etching process can be performed at a substrate temperature of about 125°C to about 200°C. In some examples, the etching process can be performed at a rate of about 0.05nm / minute to about 50.0nm / minute. In some examples, the etching process can be performed at a rate of about 0.1nm / minute to about 5.0nm / minute. In some examples, the etching process can be performed at a rate of about 0.2nm / minute to about 2.5nm / minute. In some examples for single wafer or small batch (e.g., 5 wafers or less) processing, a low O3 concentration etching process can be used, wherein the low O3 concentration etching process is performed at 0.01 torr to 200 torr, more specifically about 0.1 torr to 100 torr (e.g., 2 torr). The etchant pulse can be between 0.01 seconds and 20 seconds, particularly between 0.05 seconds and 10 seconds, and even more particularly between 0.1 seconds and 2 seconds (e.g., 0.5 second pulse / 0.5 second purge of O3). The O3 flow rate can range from 0.01slm to 1slm, more particularly from 0.01slm to 0.250slm. The inert (e.g., N2) carrier gas flow rate can range from 0.1slm to 20slm, more particularly from 0.5slm to 5slm (e.g., 1.2slm). In some examples, a high O3 concentration etching process can be used, wherein the high O3 concentration etching process is performed at 1-100 Torr, more particularly 5-20 Torr (e.g., 9 Torr), with each cycle having a longer exposure time. For example, the O3 exposure time can be between 0.1 seconds and 20 seconds, more particularly between 0.5 seconds and 5 seconds (e.g., 1 second pulse / 1 second purge of O3). The O3 flow rate for such high O3 concentration process may be between 0.1slm and 2.0slm, more particularly between 0.5slm and 1.5slm (e.g. 750sccm), with an inert (e.g. N2) dilution flow rate of 0.1slm to 20slm, more particularly 0.5slm to 5slm (e.g. 1.2slm).

[0123] Additional treatments, such as heat treatment or chemical treatments, may be performed before, after, or between the aforementioned processes. For example, the treatment may modify the surface or remove portions of metal, silicon oxide, polymer passivation, and metal oxide surfaces exposed at various stages of the process. In some examples, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition process. In some examples, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition process. In some examples, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some examples, 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 process. In some examples, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species before or at the beginning of the selective deposition process. In some examples, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition process, whereas in some examples, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0124] In some examples, the material difference between the two surfaces allows the vapor deposition method to selectively deposit an organic passivation layer on the first surface relative to the second surface. In some embodiments, cyclic vapor deposition is used, such as using a cyclic CVD or atomic layer deposition (ALD) process. In some embodiments, the selectivity of the organic passivation layer can be achieved without a passivation / sealing agent on the surface to receive fewer organic layers; and / or without a catalyst on the surface to receive more organic layers. For example, in an embodiment where the first surface is metallic and the second surface is a dielectric, the polymer can be selectively deposited directly on the metallic surface relative to the inorganic dielectric surface. In other embodiments where the first surface is a dielectric and the second surface is metallic, the second surface can be treated first to inhibit polymer deposition thereon. For example, an inhibitor, such as a passivation barrier self-assembled monolayer (SAM) and / or an alkyl silane or other inhibitory substance (described in further detail below) can be first formed on a metallic (or other suitable material) surface to promote the selective deposition of a polymer passivation layer on a dielectric surface (e.g., an inorganic dielectric surface) relative to a second metallic surface covered with a SAM or other inhibitor. An example method for selectively depositing a SAM for use as a passivation barrier ("inhibitor") is disclosed in U.S. Patent Application No. 17 / 388,773, filed on July 29, 2021, the entire disclosure of which is incorporated herein by reference. Further information and examples of selectively depositing a SAM for use as a passivation barrier are provided below. An example method for selectively depositing an alkylsilane passivation barrier ("inhibitor") is disclosed in U.S. Provisional Patent Application No. 63 / 583,732, filed on September 19, 2023, the entire disclosure of which is incorporated herein by reference. Further information and examples of selective deposition of alkylsilanes used as passivation barriers are provided below.

[0125] After the selective deposition of the organic passivation is complete, a further selective deposition of a material of interest, such as a metal oxide or metal layer, may be performed on the unpassivated second surface relative to the passivated first surface.

[0126] Figure 2 A second embodiment of a selective passivation process 200 of a first surface 204 relative to a second surface 206 is schematically illustrated, followed by a selective deposition on the second surface 206 relative to the passivated first surface 204. In the illustrated embodiment, the first material 210 and the first surface 204 comprise an inorganic dielectric material; the second material 210 is metallic, the second surface 206 comprises a metallic surface; and the material of interest 216 deposited on the second surface comprises a dielectric material or a metal. The following description of the process 100 refers to Figure 2 and 3 .

[0127] Figure 2 Shows something like Figure 1 The substrate has substantially different surfaces. However, for this embodiment, the surface is described in opposite terms. In particular, the second surface 206 may include or be defined by a metallic material, a metal oxide, a metal nitride, a metal boride, an elemental metal, a metallic surface, an amorphous carbon or a combination thereof. In some examples, the second surface 206 may be aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V) or the like or a combination thereof. In other examples, the second surface 206 may be RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN or TiN or a combination thereof.

[0128] In one example, the first material 210 and / or the first surface 204 may include an inorganic dielectric, such as a low-k layer (usually a silicon oxide-based layer) or a silicon surface on which a native oxide (also in the form of silicon oxide) is formed, for example, the first material 210 and / or the first surface 204 may include SiCOx, SiOx, SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, Si, a high-k material, a low-k material, etc. or a combination thereof. In some examples, the first material 210 and / or the first surface 204 may include zirconium oxide (ZrOx), hafnium oxide (HfOx), aluminum oxide (Al2O3), titanium nitride (TiN), titanium oxide (TiOx), aluminum nitride (AlN), etc. or a combination thereof.

[0129] The following description of process 200 refers to Figure 2 and 3 In one example, process 200 begins at operation 220, where a substrate 228 having a first surface 204 and a second surface 206 is supported in reaction chamber 302 (see Figure 3 ).

[0130] The process 200 may continue to operation 222, where a selective deposition of a "passivation barrier layer" (interchangeably referred to herein as an "inhibitor") 209 on the second surface 206 may be performed. The passivation barrier layer is formed on the second surface. Note that the term "blocking" does not mean that the subsequent selective deposition of the passivation layer is completely blocked by the passivation barrier layer. Rather, the passivation barrier layer on the second surface only needs to inhibit the deposition of the passivation layer to have a lower growth rate relative to the growth rate on the first surface.

[0131] In one embodiment, the passivation barrier or inhibitor 209 may include a self-assembled monolayer (SAM). Preferably, the SAM may be selectively formed on the second (metallic) surface 206 and not on the first (dielectric) surface 204. In some examples, sulfur-containing SAMs have been found to be particularly effective in minimizing the deposition of passivation layers thereon. An example sulfur-containing SAM using vapor-delivered 1-dodecyl mercaptan (CH3(CH2)11SH) may be used in operation 222.

[0132] In some examples, inhibitor 209 may include an alkylsilane, such as bis(tert-amyloxy)methylsilanol, tri(tert-amyloxy)silanol, tri(tert-butoxy)silanol (TBS), tri(isopropoxy)silanol (TIS), or tri(tert-amyloxy)silanol (TPS), bis(tert-amyloxy)methylsilanol, bis(tert-butoxy)methylsilanol, or bis(tert-amyloxy)ethylsilanol. Contacting substrate 228 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.

[0133] In another example, the inhibitor 209 can be represented by formula (1):

[0134] SiaRx(OH)y(OR')z

[0135] wherein: a is 1, 2 or 3, x is 1, 2 or 3, y is 0, 1 or 2, z is 1, 2 or 3, provided that x + y + z = a + 2, and each R and R' is independently selected from linear and branched C1 to C8 alkyl groups.

[0136] In one example, R' of Formula 1 is selected from isopropyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-methylbutyl, 3-methylbutyl, 3-pentyl, 1,2-dimethylpropyl and 2-methylbutyl. In one example, R is methyl or ethyl.

[0137] In one example, Formula 1 is selected from Si(OH)CH3(OCH(CH3)2)2, Si(OH)2CH3(OCH(CH3)2), Si(OH)(CH3)2(OCH(CH3)2), Si(OH)CH3(OC(CH3)3)2, Si(OH)2CH3(OC(CH3)3), Si(OH)(CH3)2(OC(CH3)3), Si(OH)CH2CH3(OC(CH3)3)2, Si(OH)(CH2CH3)2(OC(CH3)3), Si(OH)CH3(OC[(CH3)2(CH2CH3)])2, Si(OH)2CH3[(CH3)2(CH2CH3)], Si(OH)(CH3)2[(CH3)2(CH2CH3)], SiCH3(OCH(CH3)2)3, Si(CH3)2(OCH(CH3)2)2, Si(CH3)3(OCH(CH3)2),SiCH3(OC(CH3)3)3, Si(CH3)2(OC(CH3)3)2, Si(CH3)3(OC(CH3)3), Si(CH2CH3)(OC(CH3)3)3, Si(CH2CH3)2(OC(CH3)3)2, Si(CH2CH3)3(OC(CH3)3), SiCH3(OC[(CH3)2(CH2CH3)])3, Si(CH3)2[(CH3)2(CH2CH3)]2 and Si(CH3)3[(CH3)2(CH2CH3).

[0138] In one example, Formula 1 is selected from Si(OH)2R(OR'), Si(OH)R2(OR'), Si(OH)R(OR')2, R(OR')(OH)Si-Si(OH)R(OR'), Si2(OH)2R2(OR')2, Si2(OH)R2(OR')2, SiR(OR')3, SiR2(OR')2, SiR3(OR'), R2(OR')Si-SiR2(OR'), R(OR')2Si-SiR(OR')2.

[0139] In some embodiments, the first surface 204 is a high-k surface, and the second surface 206 is a silicon-containing dielectric surface, such as a silicon oxide surface or a low-k surface, such as a SiOC surface.

[0140] At operation 224, a passivation layer 208, in this case an inorganic dielectric layer, is formed on the first surface 204 relative to the passivation barrier layer 209 on the second surface 206. As described in U.S. Patent No. 10,373,820, issued on August 6, 2019, the entire disclosure of which is incorporated herein by reference, the deposition process described therein is capable of depositing polymers on inorganic dielectrics, and can even be selectively deposited on different types of silicon oxides (i.e., at different deposition rates). In this embodiment, the SAM, alkyl silane or other suitable inhibitor prevents the polymer from being deposited thereon, so that the polymer can be selectively formed on the first surface and can serve as a passivation layer to prevent subsequent deposition. In addition, the passivation layer 208 may include any of the passivating materials described above or below herein, such as any polyimide or polyamide formed from anhydrides, including thioanhydrides (e.g., pyromellitic dithioanhydride).

[0141] At operation 226, the inhibitor 209 is removed from the second surface 206 of the substrate 228. For example, the SAM material can be removed by heat treatment at a temperature lower than the temperature for removing a polymer layer such as polyimide. Thus, the passivation layer is selectively left on the first surface 204, while the second surface 206 is exposed.

[0142] At operation 228, a material layer 216 is deposited on the second surface 206 relative to the passivation layer 208 on the first surface 204. As described in the first embodiment and in U.S. Pat. No. US11,081,342 issued on August 3, 2021, the entire disclosure of which is incorporated herein by reference, metal oxides can be selectively deposited on many different surfaces using vapor deposition techniques and hydrophobic precursors to facilitate selectivity relative to organic passivation layers. Further information and examples of selective deposition of metal oxides and other layers of interest are provided below.

[0143] Alternatively, the material layer 216 may be a metal layer. U.S. Patent No. 8,956,971 issued on February 17, 2015 and U.S. Patent No. 9,112,003 issued on August 18, 2015 teach a process for selectively depositing metal materials on metallic surfaces relative to other material surfaces including organic surfaces, and their entire disclosures are incorporated herein by reference.

[0144] Alternatively, material layer 216 may be a dielectric layer. U.S. Provisional Patent Application US63 / 583,732 filed on September 19, 2023 (the entire disclosure of which is incorporated herein by reference) teaches a process for selectively depositing dielectric materials on metallic surfaces relative to other material surfaces (including organic surfaces). Material layer 216 may be any other suitable material known to those skilled in the art.

[0145] At operation 230, passivation layer 208 may be removed from surface 204 of substrate 228, leaving a selectively formed dielectric, metal, metal oxide or other suitable material layer 216 on the metal. Passivation layer 208 may be removed as described above with respect to the first embodiment, such as by an O3 etch.

[0146] Figure 3 A deposition assembly 300 according to the present disclosure is shown in schematic form. The deposition assembly 300 can be used to perform the methods described herein and / or selectively deposit organic materials described herein. In yet another aspect, the semiconductor processing assembly 300 can be configured to selectively deposit an inhibitor material on a first surface of a substrate.

[0147] In the illustrated example, the deposition assembly 300 includes one or more reaction chambers 302, a precursor injector system 301, a first precursor container 304, a second precursor container 306, a third precursor container 307, an exhaust source 344, and a controller 345. The deposition assembly 300 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. The reaction chamber 302 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber described herein.

[0148] The first precursor container 304 may include a container and one or more first precursors described herein, either alone or mixed with one or more carrier gases (e.g., inert gases). The second precursor container 306 may include a container and one or more second precursors described herein, either alone or mixed with one or more carrier gases. The third precursor container 307 may include a container and one or more inhibitors described herein, either alone or mixed with one or more carrier gases. Although three source containers 304, 306, and 307 are shown, the deposition assembly 300 may include any suitable number of source containers. The source containers 304, 306, and 307 may be coupled to the reaction chamber 302 via respective lines 314, 316, and 318, which may each include a flow controller, a valve, a heater, and the like. In some examples, the first precursor 310 in the first precursor container 304, the second precursor 312 in the second precursor container 306, and the inhibitor 315 in the third precursor container 307 may be heated.

[0149] The exhaust source 344 may include one or more vacuum pumps. The controller 345 includes electronic circuits and software to selectively operate valves, manifolds, heaters, pumps and other components included in the deposition assembly 300. Such circuits and components are used to introduce precursors, reactants and purge gases from corresponding sources. The controller 345 can control the timing of the gas pulse sequence, the temperature of the substrate and / or the reaction chamber 302, the pressure in the reaction chamber 302, and various other operations to provide the correct operation of the deposition assembly 300. The controller 345 may include control software to control the flow of precursors, reactants and purge gases into and out of the reaction chamber 302 by electrically or pneumatically controlling the valve. The controller 345 may include modules that perform specific tasks, such as software or hardware components. The module may be configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0150] Other configurations of the deposition assembly 300 are possible, including different numbers and types of precursor and reactant sources. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and auxiliary reactant sources that can be used to achieve the goal of selectively and in a coordinated manner supplying gases into the reaction chamber 302. In addition, as a schematic representation of the deposition assembly, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0151] During operation of deposition assembly 300, a substrate such as a semiconductor wafer (e.g., optional substrate 128 or 228) is transferred from, for example, a substrate handling system to reaction chamber 302. Once the substrate is transferred to reaction chamber 302, one or more gases from a gas source, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into reaction chamber 302.

[0152] In one example, the first precursor 310 may include a diamine, a triamine, a tetraamine, and / or a cyclic compound comprising at least two primary amine groups, as described in more detail herein. In one example, the second precursor 312 may include an anhydride, such as furan-2,5-dione (maleic anhydride), a dianhydride (e.g., pyromellitic anhydride (PMDA)), and / or a dianhydride comprising at least one thioanhydride group (e.g., 1,2,4,5-tetrathio-cyclo-1,2:4,5-bis(dehydrosulfide)1,2,4,5-benzenetetracarboxylic acid (pyromellitic dithioanhydride (PMDTA)), as described in more detail herein.

[0153] Figure 4An example process 400 for selective passivation of a substrate including a first surface and a second surface is shown. In one example, at block 11, a substrate is provided. The first and second surfaces may have different material properties. In some examples, the first surface may be a conductive surface, such as a metal or metallic surface, and the second surface may be a dielectric surface. In some embodiments, the first surface may be a dielectric surface and the second surface may be a different second dielectric surface. In some embodiments, the first and second surfaces may have the same basic composition but may have different material properties due to different formation methods (e.g., thermal oxide, deposited oxide, native oxide).

[0154] In some embodiments, the first precursor may be evaporated at a first temperature to form a first vapor precursor. In some embodiments, the first precursor vapor is transported to the substrate through a gas line at a second temperature. In some embodiments, the second transport temperature is higher than the first evaporation temperature. In some embodiments, at block 12, the substrate is contacted with the first vapor precursor or reactant for a first exposure time. In some embodiments, the substrate may be contacted with the first vapor precursor at a third temperature higher than the first temperature.

[0155] In some embodiments, the first precursor exposure time is from about 0.01 second to about 60 seconds, from about 0.05 second to about 30 seconds, from about 0.1 second to about 10 seconds, or from about 0.2 second to about 5 seconds. Those skilled in the art can easily determine the optimal exposure time according to the specific circumstances. In some embodiments in which a batch reactor can be used, an exposure time greater than 60 seconds can be used.

[0156] In some embodiments, at block 13, the substrate is contacted with a second vapor precursor or reactant for a second exposure time. In some embodiments, the second precursor may evaporate at a fourth temperature to form a second vapor precursor. In some embodiments, the second precursor vapor is transported to the substrate via a gas line at a second temperature. In some embodiments, a fifth transport temperature is higher than the first evaporation temperature. In some embodiments, the substrate may be contacted with the second vapor precursor at a sixth temperature higher than the fourth temperature. In some embodiments, the sixth temperature may be substantially the same as the third temperature at which the first vapor precursor contacts the substrate.

[0157] In some embodiments, the second precursor exposure time is from about 0.01 second to about 60 seconds, from about 0.05 second to about 30 seconds, from about 0.1 second to about 10 seconds, or from about 0.2 second to about 5 seconds. Those skilled in the art can easily determine the optimal exposure time according to the specific circumstances. In some embodiments in which a batch reactor can be used, an exposure time greater than 60 seconds can be used.

[0158] In box 14, the organic film is selectively deposited on the first surface relative to the second surface. Those skilled in the art will understand that the selective deposition of the organic film is the result of the above-mentioned contact actions 12-13, rather than a separate action. In some embodiments, the above-mentioned contact actions (boxes 12-13) can be considered as a deposition cycle. In some embodiments, the deposition cycle can be repeated until an organic film of a desired thickness is selectively deposited. This selective deposition cycle can be repeated until a film of sufficient thickness remains on the substrate (decision box 15) and the deposition is completed (box 16). The selective deposition cycle can include additional actions that do not need to be performed in the same order or identically in each repetition, and can be easily extended to more complex vapor deposition techniques. For example, the selective deposition cycle can include additional reactant supply processes, such as supplying and removing (relative to the substrate) additional reactants in each cycle or selected cycles. Although not shown, the process may additionally include the use of an inhibitor (e.g., as described above with respect to Figure 2 as described above), treating the deposited film to form a polymer (eg, UV treatment, annealing, etc.).

[0159] Figure 5 An example process 500 for selective passivation of a substrate comprising a first surface and a second surface is shown. In one example, at box 21, a substrate comprising a first surface and a second surface is provided. The first and second surfaces can have different material properties. In some embodiments, the first surface can be a conductive surface, such as a metal or metallic surface, and the second surface can be a dielectric surface. In some embodiments, the first surface can be a dielectric surface and the second surface can be a different second dielectric surface. In some embodiments, the first surface can be a dielectric surface and the second surface can include a different second dielectric surface. In some examples, the first surface can be a dielectric (or other material) surface and the second surface can include a passivation barrier or inhibitor layer, such as a self-assembled monolayer (SAM) or an alkyl silane or other inhibitory substance (e.g., as described with respect to Figure 2 In some embodiments, the first and second surfaces may have the same basic composition, but may have different material properties due to different formation methods (eg, thermal oxide, deposited oxide, native oxide).

[0160] In some embodiments, a sequential deposition method for selective vapor deposition of an organic film includes evaporating a first precursor at a first temperature at frame 22 to form a first precursor vapor. In some embodiments, the first precursor vapor is transported to the substrate through a gas pipeline at a second temperature. In some embodiments, the second transport temperature is higher than the first evaporation temperature. In some embodiments, at frame 23, the substrate is contacted with the gas phase first precursor for a first exposure period. In some embodiments, the first precursor or a substance thereof is chemically adsorbed on the substrate in a self-saturating or self-limiting manner. The gas pipeline can be any conduit that transports the first precursor vapor from a source to the substrate. In some embodiments, the substrate can be exposed to the first precursor vapor at a third temperature higher than the first temperature.

[0161] In some embodiments, the first precursor exposure time is from about 0.01 second to about 60 seconds, from about 0.05 second to about 30 seconds, from about 0.1 second to about 10 seconds, or from about 0.2 second to about 5 seconds. Those skilled in the art can easily determine the optimal exposure time according to the specific circumstances. In some embodiments in which a batch reactor can be used, an exposure time greater than 60 seconds can be used.

[0162] In frame 24, the first precursor vapor (and any volatile reaction byproducts) of excess can then be removed from contact with the substrate. This removal can be achieved by, for example, purging, evacuating, removing the substrate from a chamber or region exposed to the first precursor, or a combination thereof. In some embodiments, the first precursor removal time, for example, the purge time, is about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 30 seconds, about 0.1 seconds to about 10 seconds, or about 0.2 seconds to about 5 seconds. Those skilled in the art can easily determine the best removal time according to the circumstances. In some embodiments where a batch reactor can be used, a removal time greater than 60 seconds can be used.

[0163] In some embodiments, at block 25, the second precursor may be evaporated at a fourth temperature to form a second vapor-phase precursor. In some embodiments, the second precursor vapor is transported to the substrate via a gas line at a second temperature. In some embodiments, a fifth transport temperature is higher than the first evaporation temperature. In some embodiments, the substrate may be contacted with the second vapor-phase precursor at a sixth temperature higher than the fourth temperature. In some embodiments, the sixth temperature may be substantially the same as the third temperature at which the first vapor-phase precursor contacts the substrate. In some embodiments, at block 26, the substrate may be exposed to the second precursor vapor for a second exposure time. In some embodiments, the second precursor may react with an adsorbed species of the first precursor on the substrate.

[0164] In some embodiments, the first precursor exposure time is from about 0.01 second to about 60 seconds, from about 0.05 second to about 30 seconds, from about 0.1 second to about 10 seconds, or from about 0.2 second to about 5 seconds. Those skilled in the art can easily determine the optimal exposure time according to the specific circumstances. In some embodiments in which a batch reactor can be used, an exposure time greater than 60 seconds can be used.

[0165] In some embodiments, in frame 27, excess second precursor vapor (and any volatile reaction byproducts) is removed from contact with the substrate so that the first precursor vapor and the second precursor vapor do not mix. In some embodiments, the vapor deposition process of the organic film does not use plasma and / or free radicals, and can be considered as a thermal vapor deposition process. In some embodiments, the second precursor removal time, such as the purge time, is about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 30 seconds, about 0.1 seconds to about 10 seconds, or about 0.2 seconds to about 5 seconds. Those skilled in the art can easily determine the best removal time according to the specific circumstances. In some embodiments where a batch reactor can be used, a removal time greater than 60 seconds can be used.

[0166] In frame 28, the organic film is selectively deposited on the first surface relative to the second surface. Those skilled in the art will understand that the selective deposition of the organic film is the result of the above-mentioned contact action rather than a separate action. The organic film may include various films, including but not limited to polymers, such as polyimide films, polyamide films, polyurea films, polyurethane films, polythiophene films, etc. In some embodiments, the above-mentioned contact and removal (and / or stop supply) actions (frames 23-27) may be considered as a deposition cycle. In some embodiments, the deposition cycle may be repeated until an organic film of a desired thickness is selectively deposited. This selective deposition cycle (frame 29) may be repeated until a film of sufficient thickness is left on the substrate and the deposition ends (frame 30). The selective deposition cycle may include additional actions that do not need to be performed in the same order or in the same manner in each repetition, and may be easily extended to more complex vapor deposition techniques. For example, the selective deposition cycle may include additional reactant supply processes, such as supplying and removing additional reactants in each cycle or selected cycle. Although not shown, the process may also include treating the deposited film to form a polymer (e.g., UV treatment, annealing, etc.).

[0167] Various reactants can be used in the above process. For example, the first precursor or reactant is an organic reactant, such as a diamine (e.g., 1,6-diamantane (DAH)), a triamine (e.g., tris(aminoethyl)methylsilane), a tetraamine (e.g., 2,2-bis(aminomethyl)-1,3-propylenediamine), and / or a cyclic compound comprising at least two primary amine groups. In some examples, the second precursor or precursor is also an organic reactant capable of reacting with the adsorbed material of the first precursor under deposition conditions. For example, the second precursor can be an anhydride, such as furan-2,5-dione (maleic anhydride), a dianhydride (e.g., pyromellitic dianhydride (PMDA) and / or pyromellitic dithioanhydride (PMDTA)), or any other substance having two reactive groups that will react with the first precursor.

[0168] In some examples, the substrate is contacted with the first precursor prior to contacting with the second precursor. However, in some examples, the substrate may be contacted with the second precursor prior to contacting with the first precursor.

[0169] Although the above process begins with contacting the substrate with a first vapor precursor, in other examples, the process may begin with contacting the substrate with a second vapor precursor. Those skilled in the art will appreciate that in the processes described herein, contacting the substrate with the first precursor and the second precursor is interchangeable.

[0170] In some examples, different reactants can be used to tune film properties. For example, 4,4′-oxydiphenylamine or 1,4-diaminobenzene can be used instead of 1,6-diaminohexane to deposit polyimide films to obtain a more rigid structure with more aromaticity and increased dry etch resistance.

[0171] In some examples, the reactants do not include metal atoms. In some examples, the reactants do not include semi-metal atoms. In some examples, one of the reactants includes metal or semi-metal atoms. In some examples, the reactants include carbon and hydrogen and one or more of the following elements: N, O, S, P or halides, such as Cl or F. In some examples, the first precursor can include, for example, adipoyl chloride (AC).

[0172] The deposition conditions may vary depending on the selected reactants and may be optimized according to the selection. In some examples, the reaction temperature may be selected from a range of about 80°C to about 250°C. In some examples, such as when the selectively deposited organic film comprises polyimide, the reaction temperature may be selected from a range of about 170°C to about 210°C. In some examples, such as when the selectively deposited organic film comprises polyamide, the reaction temperature may be selected from a range of about 80°C to about 150°C. In some examples where the selectively deposited organic film comprises polyimide, the reaction temperature may be greater than about 160°C, 180°C, 190°C, 200°C, or 210°C. In some examples where the selectively deposited organic film comprises polyamide, the reaction temperature may be greater than about 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C.

[0173] In some examples, the reaction chamber pressure can be from about 1 mTorr to about 1000 Torr.

[0174] For example, for sequential deposition of polyimide using PMDTA and DAH in a single wafer deposition tool, the substrate temperature can be selected from a range of about 150°C to about 250°C, or from a range of about 170°C to about 225°C, and the pressure can be selected from a range of about 1 mTorr to about 760 Torr, more specifically between about 100 mTorr to about 100 Torr.

[0175] In some examples, the selectively deposited or formed organic film does not contain metal atoms. In some examples, the selectively deposited or formed organic film does not contain semi-metal atoms. In some examples, the selectively deposited or formed organic film contains metal or semi-metal atoms. In some examples, the selectively deposited or formed organic film contains carbon and hydrogen and one or more of the following elements: N, O, S or P.

[0176] Examples of suitable reactors that can be used for the selective deposition process described herein include ALD equipment available from ASM America, Inc. in Phoenix, Arizona, and ASM Europe BV in Almere, the Netherlands, such as the F-120® reactor, Pulsar® reactors, such as the Pulsar 3000® or Pulsar 2000®, and the Advance® 400 series reactors. In addition to these ALD reactors, many other types of reactors capable of growing organic thin films can be used, including CVD reactors, VDP reactors, and MLD reactors.

[0177] In some examples, a suitable reactor may be a batch reactor and may include two or more substrates. In some examples, the substrate may include, for example, a wafer. In some examples, a suitable reactor may be a batch reactor, which may include two or more, five or more, 10 or more, 25 or more, 50 or more, or 100 or more substrates. In some examples, the substrate may include a wafer, such as a semiconductor or silicon wafer. In some examples, the substrate may have a diameter of 100 mm or more, 200 mm or more, or 300 mm or more. In some cases, a substrate with a diameter of 450 mm or more may be ideal.

[0178] In some examples, the first surface (e.g., metallic surface) of the substrate onto which the organic film is selectively deposited may include a structure on a semiconductor substrate or an integrated circuit workpiece. In some examples, the first surface of the substrate may include one or more metal lines or points. For example, the first surface of the substrate may include W, Co, or Cu lines, and the second surface may include a silicon oxide-based material. That is, in some examples, the substrate may include at least a first portion of a first metallic surface and a second portion of the first metallic surface, wherein the first and second portions of the first metallic surface are separated by a second dielectric surface on the substrate.

[0179] In some examples, the selectivity of the selective deposition process described herein can be varied based on the size or spacing of the portion of the first surface on which the organic film is selectively deposited. In some examples, the selectivity of the selective deposition process described herein can increase as the spacing of the features comprising the first surface increases. Increased spacing is used herein as a convention in the semiconductor industry, meaning a greater number of features in a given size, or greater density and closer spacing between features.

[0180] In some examples, the selective deposition process can achieve a desired selectivity on a substrate, wherein the periodicity of the features including the first surface is less than about 1 micron, less than about 500 nm, less than about 250 nm, or less than about 100 nm. In some examples, the periodicity of the features including the first surface is less than 40 nm, or even less than 20 nm. As used herein, periodicity refers to the distance between the two nearest repeating structures, materials, or surfaces on a substrate. In some examples, the selectivity of the selective deposition process may depend on the distance between a first portion of the substrate including the first surface and a second portion of the substrate including the first surface, such as the periodicity described above for repeating a pattern on a substrate. In some examples, the selectivity of the selective deposition process described herein may increase as the distance between portions of the first material decreases.

[0181] In some examples, the selective deposition process can achieve a desired selectivity on a substrate including a first portion of a first surface and a second portion of the first surface separated by a distance. In some examples, the desired selectivity can be achieved when the distance between the first and second portions of the first surface is less than about 1 micron, less than about 500 nm, less than about 250 nm, or less than about 100 nm.

[0182] In some examples, the selectivity of a selective deposition process may be related to the number of growth or deposition cycles performed in the selective deposition process. In some examples, the selectivity of a selective deposition process may increase with the number of deposition cycles. For example, the selectivity of a selective deposition process including 250 deposition cycles may be less than the selectivity of a selective deposition process including 1000 deposition cycles, where the conditions of the deposition cycles in each process are substantially the same. This is surprising because typical selective vapor deposition processes tend to lose selectivity with greater thickness or deposition duration.

[0183] In some examples, an increase in the number of deposition cycles in a selective deposition process can result in a corresponding increase in the selectivity of the process. For example, in some examples, doubling the number of deposition cycles can result in a selective deposition process that is twice as selective.

[0184] Although typically the deposition or reaction temperature for the selective deposition processes described herein is greater than or equal to the vaporization temperature of the first and second precursors, in some other examples, the reaction temperature may be less than one or both of the vaporization temperatures of the reactants.

[0185] According to the process described herein, various reactants can be used to deposit polyamide or polyimide films. For example, in some examples, the first precursor or reactant is an amine, such as a diamine. In some examples, the first precursor can be a diamine (e.g., 1,6-diamantane (DAH)), a triamine (e.g., tris(aminoethyl)methylsilane), a tetramine (e.g., 2,2-bis(aminomethyl)-1,3-propylenediamine) and / or a cyclic compound comprising at least two primary amine groups. In some examples, the substrate is contacted with the first precursor before contacting with the second precursor. Therefore, in some examples, the substrate can be contacted with an amine such as a diamine before contacting with the second precursor.

[0186] In some examples, the second precursor or precursor is also an organic reactant capable of reacting with the adsorbed species of the first precursor under the deposition conditions. For example, in some examples, the second precursor or reactant is an organic reactant such as an anhydride, such as furan-2,5-dione (maleic anhydride), a dianhydride such as pyromellitic dianhydride (PMDA) and / or pyromellitic dithioanhydride (PMDTA), or any other substance having two reactive groups that will react with the first precursor.

[0187] In some examples, the reactants do not include metal atoms. In some examples, the reactants do not include semi-metal atoms. In some examples, one of the reactants includes metal or semi-metal atoms. In some examples, the reactants include carbon and hydrogen and one or more of the following elements: N, O, S, P or halides, such as Cl or F. In some examples, the first precursor can include, for example, adipoyl chloride (AC).

[0188] The first precursor

[0189] In some examples, a first precursor for the selective deposition process described herein may have the general formula: R 1 (NH2)2(1)

[0190] Wherein, R1 can be an aliphatic carbon chain containing 1-5 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 examples, the bond between carbon atoms in the reactant or precursor can be a single bond, a double bond, a triple bond or some combination thereof. Therefore, in some examples, the reactant can contain two amino groups. In some examples, the amino group of the reactant can occupy one or both terminal positions on the aliphatic carbon chain. However, in some examples, the amino group of the reactant may not occupy any terminal position on the aliphatic carbon chain. In some examples, the reactant can include a diamine. In some examples, the reactant can include an organic precursor selected from 1,2-diaminoethane (1), 1,3-diaminopropane (1), 1,4-diaminobutane (1), 1,5-diaminopentane (1), 1,2-diaminopropane (1), 2,3-butylene diamine, 2,2-dimethyl-1,3-propylene diamine (1).

[0191] In some examples, the evaporated reactant may also be a diamine, such as 1,4-diaminobenzene, decane-1,10-diamine, 4-nitrobenzene-1,3-diamine, 4,4′-oxydiphenylamine, or ethylenediamine. In some examples, the first precursor is evaporated to form a first precursor vapor. The evaporated precursor may be a liquid or a solid under standard temperature and pressure conditions (room temperature and atmospheric pressure). The substrate is then exposed to the first precursor vapor. The substrate is also exposed to a second gas phase precursor, such as an organic precursor, such as a dianhydride. For example, the dianhydride may be pyromellitic dianhydride (PMDA) and / or dithioanhydride, such as pyromellitic dithioanhydride (PMDTA). The cyclic exposure of the substrate to the two precursors results in the deposition of an organic material. 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 may be easily extended to more complex vapor deposition techniques.

[0192] In various examples, the first precursor can include an amine, such as a diamine, a triamine, and / or a tetraamine (eg, 1,3-diaminopentane (1,3-DAP), cyclohexane-1,3,5-triamine, or 2,2-bis(aminomethyl)-1,3-propylenediamine).

[0193] Diamine

[0194] In one example, the diamine compound of the first precursor according to the present disclosure may include at least three carbon atoms. In some embodiments, the diamine is a C2 to C15 compound. In some embodiments, the diamine includes a halogen. In some embodiments, the two amine groups are attached to different carbon atoms, and the two carbon atoms are not adjacent.

[0195] For example, the diamine compound of the first precursor according to the present disclosure may contain four carbons and be selected from 1,2-diaminobutane; 1,3-diaminobutane and 2,4-diaminobutane. Thus, in the four-carbon example, at least one amino group is attached to a carbon atom that is bound to two other carbon atoms. In other words, at least one amino group is not at the end of the carbon chain.

[0196] The first precursor may include a molecule containing at least two amine groups. In some embodiments, the molecule containing at least two amine groups includes at least one primary amine. In some embodiments, the molecule containing at least two amine groups may include two primary amines, three primary amines, or four primary amines.

[0197] In some examples, the first precursor comprising at least two amine groups can be selected from: 4,4'-oxydiphenylamine; 1,4-diaminobenzene, 2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; 1,2-diaminopropane; 2,3-butanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-diaminopentane; 1,4-diaminopentane; 2,4-diaminopentane; 2,4-diamino-2,4-dimethylpentane; 1,5-diamino-2-methylpentane; 1,3-diamino-3-methylbutane; 2,5-diamino-2,5-dimethylhexane; 1,4-diamino-4-methylpentane; 1,3 -diaminobutane; 1,5-diaminohexane; 1,3-diaminohexane; 1,6-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, 1,4-diaminobenzene; 1,6-diaminohexane; decane-1,10-diamine; and / or 4-nitrobenzene-1,3-diamine or its cis or trans stereoisomers.

[0198] In some examples, the two amine groups of the diamine can be bonded to a cyclic carbon backbone, or a carbon backbone including a carbon-carbon double bond and / or a carbon-carbon triple bond. As used herein, the term "carbon backbone" refers to a main continuous chain or carbon atoms present in a cyclic structure containing three or more carbon atoms. Such diamines may include, for example, one or more of the following: trans-1,4-diaminocyclohexane; 2,4-diamino-2,4-dimethylpentane; 1,5-diamino-2-methylpentane; 1,3-diamino-3-methylbutane; 2,5-diamino-2,5-dimethylhexane; 1,2-diaminocyclopropane; 1,3-diaminocyclobutane; 1,3-diaminocyclohexane; 1,3-diaminocyclopentane; 1,4-diaminocyclohexane; 1,3-diaminocycloheptane; 1,4-diaminocycloheptane; 2,7-diamino-2,7-dimethyloctane; diaminocyclohexane; 1,3-diaminobenzene and 1,4-diaminobenzene or their cis or trans stereoisomers.

[0199] In some examples, the first precursor may include a diamine containing a branched carbon chain. Therefore, at least one carbon atom is bonded to three or four other carbon atoms. In some examples, there is one such branching position in the diamine compound. In some examples, there are two such branching positions in the diamine compound. In some examples, there are three or more branching points. In some examples, the side chain from the longer carbon chain is one of the following: methyl, ethyl, propyl, isopropyl, butyl or tert-butyl or a combination thereof. In some examples, the side chain of the diamine compound of the first precursor is a linear alkyl chain. In some examples, the side chain of the diamine compound of the first precursor is a branched alkyl chain. In some examples, the side chain of the diamine compound of the first precursor is a cyclic alkyl chain.

[0200] In some examples, the diamine compound of the first precursor is a C3 to C11 compound. The number of carbon atoms in the diamine compound generally affects the volatility of the compound, so that higher molecular weight compounds may not be as volatile as smaller compounds. In some examples, a medium-sized diamine compound containing at least five carbon atoms may have suitable properties for use as a diamine precursor in a selective deposition process according to the present invention. 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 (1,3-DAP) can be used as a precursor for organic material deposition according to the present disclosure, the precursor container does not need to be heated. This may be advantageous 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 precursor includes 1,3-DAP.

[0201] In some examples of the present disclosure, the amine group is attached to non-adjacent carbon atoms. This may be advantageous for the availability of the amine group to react with the second precursor. In some examples, there is one carbon atom between the carbon atoms that are bound to the amino group. In some examples, there is at least one carbon atom between the carbon atoms that are bound to the amino group. In some examples, there are two carbon atoms between the carbon atoms that are bound to the amino group. In some examples, there are at least two carbon atoms between the carbon atoms that are bound to the amino group. In some examples, there are three carbon atoms between the carbon atoms that are bound to the amino group. In some examples, there are at least three carbon atoms between the carbon atoms that are bound to the amino group. In some examples, there are four carbon atoms between the carbon atoms that are bound to the amino group. In some examples, there are at least four carbon atoms between the carbon atoms that are bound to the amino group.

[0202] In some examples, the first 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 moderate temperature of about 40°C to reach a vapor pressure of 1 Torr.

[0203] In some examples, the carbon atom bonded to the amine nitrogen in the diamine compound is bonded to at least two carbon atoms. Thus, in some examples where the diamine contains three or more carbons, at least one amino group is not located at the end of the carbon chain. The structure of the diamine compound affects its properties during vapor deposition. The branches of the diamine compound, including the number of branches and the relative position of the amino group to the branches, may result in deposited organic materials having different properties. Without limiting the invention to any particular theory, for example, steric factors may result in certain reactions being preferred. This may provide the possibility of designing a deposition process for a given purpose by using different diamine compounds, taking into account, for example, thermal budgets, organic material growth rate requirements, and the necessary degree of selectivity.

[0204] In some examples, the diamine compound of the first precursor is an aromatic diamine. In some examples, the aromatic diamine is a diaminobenzene, such as 1,2-diaminobenzene, 1,3-diaminobenzene; 1,4-diaminobenzene; or a cis or trans stereoisomer thereof. In some examples, the aromatic diamine comprises an alkylamino group at at least one position. For example, the alkylamino group can be a C1 to C3 alkylamino group, such as -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2 or -CH2CH(CH3)NH2.

[0205] In some examples, the diamine compound of the first precursor is selected from the group consisting of: trans-1,4-diaminocyclohexane; 1,2-diaminocyclopropane; 1,3-diaminocyclobutane; 1,3-diaminocyclohexane; 1,3-diaminocyclopentane; 1,3-diaminocycloheptane; 1,4-diaminocycloheptane; 4,4'-oxydiphenylamine; 1,4-diaminobenzene; 2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; 1,2-diaminopropane; 2,3-butylene diamine; 2,2-dimethyl-1,3-propanediamine; 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-methyl 1,3-Diaminobutane; 1,5-Diaminohexane; 1,3-Diaminohexane; 1,6-Diaminohexane; 2,5-Diaminohexane; 1,3-Diamino-5-methylhexane; 4,4,4-Trifluoro-1,3-Diamino-3-methylbutane; 2,4-Diamino-2-methylpentane pentane; 4-(1-methylethyl)-1,5-diaminohexane; 3-aminobutyramide; 1,3-diamino-2-ethylhexane; 2,7-diamino-2,7-dimethyloctane; 1,4-diaminocyclohexane; diaminocyclohexane; 1,3-diaminobenzene; decane-1,10-diamine; 4-nitrobenzene-1,3-diamine and 1,4-diaminobenzene and their trans and cis stereoisomers. In some examples, the diamine compound contains a halogen.

[0206] Triamine

[0207] In some examples, the first precursor can include a triamine compound (e.g., any branched aliphatic or aromatic compound containing three primary amine functional groups), which can be combined with a second precursor disclosed herein (e.g., PMDTA) to form a passivation layer (e.g., to prevent film formation on non-growth surfaces during area-selective deposition).

[0208] In one example, the triamine may include the following structure:

[0209]

[0210] wherein X is CR, Si-R, Sn-R, N, P or As, and n1, n2 and n3 are positive integers.

[0211] Providing such a molecule can advantageously affect the availability of polymerization sites for the second gas phase reactant. The availability of three amine groups in a single molecule can result in a denser polymer network, which can reduce metal migration through the organic material. In examples utilizing organic materials according to the present disclosure as passivation layers, this property may be advantageous.

[0212] Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (with amines on carbons 1, 2 and 3 or carbons 1, 2 and 4), triaminopentane (particularly with amines on carbons 1 and 5, plus an amine on either carbon 2 or 3). Similarly, triaminohexane can contain amine groups on carbons 1 and 6, and at either position 2 or 3; triaminoheptane can contain amine groups on carbons 1 and 7 and at either position 2, 3 or 4; and triaminooctane can contain amine groups on carbons 1 and 8 and at either position 2, position 3 or position 4. Furthermore, branched carbon chains, in particular tris(aminoethyl)phosphine; tris(aminoethyl)arsine; bis(aminoethyl)aminomethylamine; tris(aminoethyl)silane; tris(aminoethyl)stannane; tris(aminoethyl)methylsilane; 2-toluene-1,3,5-triamine; pentane-1,2,4-triamine; cyclohexane-1,3,5-triamine; pentane-1,3,5-triamine; tris(2-aminoethyl)amine; 2-aminomethyl-1,3-diaminopropane; 2-(aminomethyl)propane-1,3-diamine; propane-1,2,3-triamine; 2-(aminomethyl)butane-1,4-diamine; 2-aminomethyl-1,4-diaminobutane (or alternatives with two amino groups elsewhere in the butane chain) ; tris(2-aminoethyl)phosphine; 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) or its cis or trans stereoisomers may be alternatives for some examples. In addition, aromatic triamines, such as 2-methylbenzene-1,3,5-triamine and / or 1,3,5-triaminobenzene or its cis or trans stereoisomers, may be alternatives for some examples.

[0213] In some examples, the organic film includes a polymer. In some examples, the deposited polymer is a polyimide. In some examples, the deposited polymer is a polyamide. In some examples, the deposited polymer is a polyamic acid. Therefore, in some examples, the organic material includes a polyimide. In some examples, the organic material is substantially composed only of polyimide. In some examples, the organic material includes polyamic acid. In some examples, the organic material is substantially composed only of amide and polyimide. In some examples, the organic material is deposited at a temperature below 190°C and then heat treated at a temperature of about 190°C or higher (e.g., 200°C or 210°C) to increase the ratio of the organic material 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.

[0214] Tetramine

[0215] The first precursor may include a tetramine, which may be combined with a second precursor disclosed herein (e.g., PMDTA) to form a passivation layer (e.g., to prevent film formation on non-growth surfaces during area selective deposition). The use of a tetramine may produce a cross-linked form of the polyimide, which may improve selectivity relative to a form without cross-linking.

[0216] Tetramines are defined as molecules containing four -NH2 groups attached to a hydrocarbon group containing 1 to 12 carbon atoms. In some examples, the hydrocarbon group may contain other elements such as O, N, or S that link the hydrocarbon subunits together.

[0217] In some embodiments, the hydrocarbon group includes an alkyl chain that can be branched or unbranched. In some embodiments, the hydrocarbon group includes aromatic hydrocarbons. In some embodiments, the hydrocarbon group includes an alkyl group and an aryl group. In some embodiments, two or more -NH2 groups are attached to the same carbon atom. In some embodiments, two or more -NH2 groups are attached to adjacent carbon atoms. In some embodiments, two or more -NH2 groups are attached to non-adjacent carbon atoms. In some embodiments, one or more -NH2 groups are substituted by -NHR groups, wherein R is a hydrocarbon group containing 1 to 6 carbon atoms. In some embodiments, one or more -NH2 groups are substituted by =NH groups, i.e., imino groups.

[0218] In some embodiments, the tetraamine is selected from, but not limited to, 2,2-bis(aminomethyl)-1,3-propylenediamine; 1,2,3,4-butanetetraamine; 3,3-bis(2-aminoethyl)-1,5-pentanediamine; 2,4-bis(aminomethyl)-1,5-pentanediamine; 2,3-dimethyl-1,2,3,4-butanetetraamine; succinimide amide; glutarimide; adipimidimide amide; pimelimide; suberimide; nonanediimide; and / or sebacimide amide.

[0219] Cyclic compounds

[0220] The first gas phase reactant includes a cyclic compound containing at least two primary amine groups. In some embodiments, the cyclic compound includes a bicyclic ring. In some embodiments, the bicyclic compound includes a condensed ring. In some embodiments, the bicyclic compound includes an independent ring. In some embodiments, the cyclic compound includes a monocyclic ring with at least two NH2 substituents. In some embodiments, the cyclic compound includes a carbocyclic ring. In some embodiments, the carbocyclic ring is a C3 to C8 ring. In some embodiments, the carbocyclic ring is a 3-membered ring. In some embodiments, the carbocyclic ring is a 4-membered ring. In some embodiments, the carbocyclic ring is a 5-membered ring. In some embodiments, the carbocyclic ring is a 6-membered ring. In some embodiments, the carbocyclic ring is a 7-membered ring. In some embodiments, the carbocyclic ring is an 8-membered ring. In some embodiments, the carbocyclic ring is aliphatic (i.e., alicyclic compound). The alicyclic carbocyclic ring can be saturated or unsaturated.

[0221] In some embodiments, the cyclic compound includes an aromatic ring. In some embodiments, the cyclic compound does not include an aromatic ring. In some embodiments, the cyclic compound does not include p-phenylenediamine. In some embodiments, the cyclic compound includes an alicyclic ring. In some embodiments, the cyclic compound includes a six-membered carbocyclic ring, which includes two primary amine groups directly or indirectly bonded to positions 1 and 4 of the carbocyclic ring, respectively. In some embodiments, the cyclic compound includes a six-membered carbocyclic ring, which includes two primary amine groups directly bonded to positions 1 and 4 of the carbocyclic ring, respectively. In some embodiments, the cyclic compound includes a six-membered carbocyclic ring, which includes three primary amine groups directly or indirectly bonded to positions 1, 3 and 5 of the carbocyclic ring, respectively. In some embodiments, the cyclic compound includes a six-membered carbocyclic ring, which includes three primary amine groups directly bonded to positions 1, 3 and 5 of the carbocyclic ring, respectively. In some embodiments, the cyclic compound includes at least one of the following: cyclopentanedialkylamine, cyclohexanedialkylamine, cyclopentadienedialkylamine, phenylenedialkylamine, cyclopentanetrialkylamine, cyclohexanetrialkylamine, cyclopentadienetrialkylamine and phenyltrialkylamine. Each alkyl group of the alkylamine may be independently selected from methyl, ethyl, propyl (including n-propyl and isopropyl) and butyl (including n-butyl, sec-butyl, isobutyl and tert-butyl).

[0222] In some embodiments, the non-aromatic cyclic diamine compound is a trans isomer of the compound. In some embodiments, the non-aromatic cyclic diamine compound is a cis isomer of the compound. In some embodiments, the non-aromatic cyclic diamine compound is a mixture of cis and trans isomers of the compound. Without limiting the present disclosure to any particular theory, the trans isomer of the cyclic compound may have more desirable reactivity and availability in the process according to the present disclosure.

[0223] In some embodiments, the cyclic compound is selected from the group consisting of: 1,3-cyclopentadiamine, 3,5-cyclopentadiene-1,3-diamine, 2,4-cyclopentadiene-1,3-diamine, 1,3-cyclopentadiene diamine, 3,5-cyclopentadiene-1,3-diamine, 2,4-cyclopentadiene-1,3-diamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,2-cyclohexane diamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,2-cyclohexane diamine, 1,3-cyclohexane diamine, 1,2-cyclohexane diamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,2-cyclohexane diamine, 1,3-cyclohexane diamine, 1,2 ,3-cyclopentanetriamine, 1,2,4-cyclopentanetriamine, 1,3-cyclopentadiene-1,2,4-triamine, 1,2,3-cyclohexanetriamine, 1,2,4-cyclohexanetriamine, 1,3,5-cyclohexanetriamine, 1,3,5-cyclohexanetriamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 1,2,3-phenyltriamine, 1,2,4-phenyltriamine, 1,3,5-phenyltriamine, 1,2,3-phenyltrimethylamine, 1,2,4-phenyltrimethylamine and 1,3,5-phenyltrimethylamine.

[0224] In some embodiments, the first precursor is selected from a compound having a cyclopentane, cyclopentadiene, cyclohexane or benzene ring and two substituents containing a primary amine, wherein the amine-containing substituents are independently selected from -NH2, -CH2NH2 and -CH2CH2NH2. Therefore, the substituents can be the same, for example, both substituents are -NH2, or both substituents are -CH2NH2, or both substituents are -CH2CH2NH2. The substituents can be different. For example, one substituent can be -NH2 and the second substituent can be -CH2NH2. One substituent can be -NH2 and the second substituent can be -CH2CH2NH2. One substituent can be -CH2CH2NH2 and the second substituent can be -CH2NH2.

[0225] In some embodiments, the first precursor is selected from a compound having a cyclopentane, cyclopentadiene, cyclohexane or benzene ring and three substituents containing primary amines, wherein the amine-containing substituents are independently selected from -NH2, -CH2NH2 and -CH2CH2NH2. Therefore, the substituents may be the same, for example, all three substituents are -NH2, or all three substituents are -CH2NH2, or all three substituents are -CH2CH2NH2. The substituents may be different. For example, one substituent may be -NH2, the second substituent may be -CH2NH2, and the third substituent may be -CH2CH2NH2. One substituent may be -NH2, and the other two substituents may be -CH2NH2. One substituent may be -CH2NH2, and the other two substituents may be -NH2. One substituent may be -NH2, and the other two substituents may be -CH2CH2NH2. One substituent may be -CH2CH2NH2, and the other two substituents may be -NH2. One substituent may be -CH2NH2 and the other two substituents may be -CH2CH2NH2. One substituent may be -CH2CH2NH2 and the other two substituents may be -CH2NH2.

[0226] In some examples, the reactants may have a vapor pressure greater than about 0.5 Torr, 0.1 Torr, 0.2 Torr, 0.5 Torr, 1 Torr, or more at a temperature of about 20° C. or room temperature. In some examples, the reactants may have a boiling point less than about 400° C., less than 300° C., less than about 250° C., less than about 200° C., less than about 175° C., less than about 150° C., or less than about 100° C.

[0227] Polyamide deposition

[0228] In some examples, the deposition process taught herein may include the deposition of a polyamide film. In some examples, this deposition process may include a vapor deposition process. In some examples, this deposition process may include a molecular layer deposition (MLD) process. In some examples, this deposition process may be a selective deposition process. However, in some examples, this deposition process may be a non-selective deposition process.

[0229] In some examples, the first precursor is evaporated to form a first precursor vapor. Under standard temperature and pressure conditions (room temperature and atmospheric pressure), the evaporated reactant can be a liquid or a solid. In some examples, the evaporated first precursor includes an organic precursor, such as an organic chloride, such as adipoyl chloride (AC). In some examples, the reactant can include an organic precursor selected from oxalyl chloride (I), malonyl chloride and fumaryl chloride.

[0230] In some examples, the first precursor can be evaporated at a first temperature to form a first vapor precursor. In some examples, the first precursor vapor is transported to the substrate through a gas pipeline at a second temperature. In some examples, the second transport temperature is higher than the first evaporation temperature. In some examples, the substrate is contacted with the first vapor precursor or reactant for a first exposure time. In some examples, the substrate can be contacted with the first vapor precursor at a third temperature higher than the first temperature.

[0231] In some examples, the first precursor exposure time is about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds, or about 0.2 seconds to about 1.0 seconds. A person skilled in the art can easily determine the optimal exposure time according to specific circumstances.

[0232] In some examples, the second organic reactant is evaporated to form a second precursor vapor. Under standard temperature and pressure conditions (room temperature and atmospheric pressure), the evaporated reactant can be a liquid or a solid. In some examples, the evaporated reactant includes an organic precursor, such as an organic amine, such as ethylenediamine (EDA). In some examples, the reactant can include an organic precursor selected from 1,2-diaminoethane (1), 1,3-diaminopropane (1), 1,4-diaminobutane (1), 1,5-diaminopentane (1), 1,2-diaminopropane (1), 2,3-butylene diamine, 2,2-dimethyl-1,3-propylene diamine (1).

[0233] The second precursor

[0234] In some examples, the second precursor can be an anhydride.The second precursor can contact the first surface before, simultaneously with, or after the first surface is contacted with the first precursor.

[0235] In some examples, the second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by formula (1):

[0236] (1)

[0237] Wherein, R and R' may independently include hydrocarbon groups. In some examples, at least one hydrocarbon group may independently include one or more of the following: O, N or S or a combination thereof. In one example, R and / or R' may independently be limited to compounds within the range of C1 to C8, C1 to C10 or C1 to C15 or a combination thereof.

[0238] In some examples, the second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by formula (2):

[0239] (2)

[0240] Wherein, R may include a hydrocarbon group. In some examples, the hydrocarbon group may include one or more of the following: O, N or S or a combination thereof. In one example, R may be limited to compounds within the range of C1 to C8, C1 to C10 or C1 to C15.

[0241] In some examples, the second precursor includes a compound including a thioanhydride group and an acid anhydride group, the compound including a structure represented by formula (3):

[0242] (3)

[0243] Wherein, R and R' may independently include hydrocarbon groups. In some examples, at least one hydrocarbon group may independently include one or more of the following: O, N or S or a combination thereof. In one example, R and / or R' may independently be limited to compounds within the range of C1 to C8, C1 to C10 or C1 to C15 or a combination thereof.

[0244] In some examples, the second precursor includes a compound including a thioanhydride group and an acid anhydride group, the compound including a structure represented by formula (4):

[0245] (4)

[0246] Wherein, R may include a hydrocarbon group. In some examples, the hydrocarbon group may include one or more of the following: O, N or S or a combination thereof. In one example, R may be limited to compounds within the range of C1 to C8, C1 to C10 or C1 to C15.

[0247] In some examples, the second precursor includes a compound including at least one thioanhydride group, the compound including a structure represented by formula (5):

[0248] (5)

[0249] wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of: O, N or S or a combination thereof; and wherein X is selected from S or O.

[0250] In some examples, the second precursor includes a compound including two or more anhydride groups, the compound including a structure represented by formula (6):

[0251] (6)

[0252] wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of the following: O, N or S or a combination thereof; and wherein X' and X" are independently selected from S, Se, Te, NH, NR" or O, wherein R" is a C1 to C6 compound.

[0253] In some examples, the second precursor includes a compound including a structure represented by formula (7):

[0254] (7)

[0255] Wherein, R1, R2 and R3 independently include hydrocarbon groups. In some examples, at least one hydrocarbon group may independently include one or more of the following: O, N or S or a combination thereof; wherein Y is selected from S, Se, Te, NH, NR" or O, wherein R" may be limited to C1 to C6 compounds. In one example, R1, R2 and / or R3 may be independently limited to compounds within the range of C1 to C8, C1 to C10 or C1 to C15 or a combination thereof.

[0256] Table 1 includes non-limiting examples of compounds according to formula (1)-(7):

[0257]

[0258] Table 1

[0259] In some examples, a polyamide film of desired thickness is deposited on a substrate. Those skilled in the art will appreciate that the deposition of the polyamide film is the result of the above-mentioned contact action, rather than the result of a separate action. In some examples, the above-mentioned contact action can be considered as a deposition cycle. In some examples, the deposition cycle can be repeated until an organic film of desired thickness is selectively deposited. Such a deposition cycle can be repeated until a film of sufficient thickness is left on the substrate and the deposition ends. The deposition cycle can include additional actions that do not need to be performed in the same order or in the same manner in each repetition, and can be easily extended to more complex vapor deposition techniques. For example, a deposition cycle can include additional reactant supply processes, such as supplying and removing (relative to the substrate) additional reactants in each cycle or selected cycle. Although not shown, the process can also include treating the deposited film to form a polymer (e.g., UV treatment, annealing, etc.).

[0260] In some examples of selective deposition, the passivation layer is selectively deposited on the first surface of the substrate relative to the second surface of the substrate by contacting the first precursor and the second precursor. In some examples, as described above, the first precursor is an amine, such as a diamine, a triamine, a tetraamine, a cyclic amine, etc. or a combination thereof.

[0261] Subsequent processing

[0262] In some examples, further processing may be performed after the organic film deposition process, such as the selective deposition process described herein. For example, in some examples, the substrate may be subjected to an etching process to remove at least a portion of the deposited organic film. In some examples, the etching process after the selective deposition of the organic film may remove the deposited organic material from the first surface and the second surface of the substrate. In some examples, the etching process may be isotropic.

[0263] In some examples, the etching process can remove the same amount or thickness of material from the first and second surfaces. That is, in some examples, the etching rate of the organic material deposited on the first surface can be substantially similar to the etching rate of the organic material deposited on the second surface. Due to the selectivity of the deposition process described herein, the amount of organic material deposited on the second surface of the substrate can be significantly less than the amount of material deposited on the first surface of the substrate. Therefore, the etching process can completely remove the deposited organic material from the second surface of the substrate, while the deposited organic material can remain on the first surface of the substrate.

[0264] In some examples, the etching process may include an etching process known in the art, such as a dry etching process, such as a plasma etching process. In some examples, the etching process may include exposing the substrate to hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. For example, in some examples, the etching process may include exposing the substrate to a plasma generated by H2 using a power from about 10W to about 5000W, from about 25W to about 2500W, from about 50W to about 500W, or from about 100W to about 400W. In some examples, the etching process may include exposing the substrate to a plasma generated using a power from about 1W to about 1000W, from about 10W to about 500W, from about 20W to about 250W, or from about 25W to about 100W.

[0265] In some examples, the etching process may include exposing the substrate to a plasma. In some examples, the plasma may include active species, such as oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof. In some examples, in addition to the active species, the plasma may also include a rare gas species, such as an Ar or He species. In some examples, the plasma may include a rare gas species that does not contain an active species. In some cases, the plasma may include other substances, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or a combination thereof. In some examples, the etching process may include exposing the substrate to an oxygen-containing etchant, such as O3. In some examples, 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. In some examples, the etchant may be supplied in one continuous pulse, or may be supplied in multiple shorter pulses.

[0266] One skilled in the art can readily determine the optimal exposure time, temperature, and power to remove a desired amount of deposited organic material from a substrate.

[0267] Although exemplary examples of the present disclosure are described herein, it should be understood that the present disclosure is not limited thereto. Various modifications, changes and enhancements may be made to the systems and methods described herein without departing from the spirit and scope of the present disclosure.

[0268] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A process for forming a passivation layer on a substrate, comprising: Providing a substrate in a reaction chamber, the substrate comprising a first surface and a second surface; contacting the substrate with a first precursor comprising an amine compound comprising at least two amine groups; as well as contacting the substrate with a second precursor comprising at least one thioanhydride, wherein contacting the substrate with first and second precursors selectively forms a film on the first surface relative to the second surface.

2. The process of claim 1, wherein: The passivation layer includes a polyimide film.

3. The process of claim 2, wherein: The passivation layer includes a polyimide film and pyromellitic dithioanhydride.

4. The process of claim 1, wherein: The contacting operation includes a deposition cycle, and the process includes one or more deposition cycles.

5. The process of claim 4, further comprising repeating the contacting operation until a passivation layer of a desired thickness has been formed.

6. The process of claim 1, wherein: The first surface is a metal carbide, a metal oxide, a metal nitride, a metal boride, an elemental metal, a metallic surface, amorphous carbon, or a combination thereof.

7. The process of claim 1, wherein: The first surface comprises a metal, and the metal comprises aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr) or vanadium (V) or a combination thereof.

8. The process of claim 1, wherein: The first surface is a dielectric surface, which contains SiCOx, SiOx, silicon, SiO2, zirconium oxide (ZrO2), hafnium oxide (HfO2), aluminum oxide (Al2O3), titanium nitride (TiN) and titanium oxide (TiO2) or aluminum nitride (AlN) or a combination thereof.

9. The process of claim 1, wherein: The first surface comprises RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN or TiN or a combination thereof.

10. The process of claim 1, wherein: The second surface includes a passivation barrier layer formed thereon.

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

12. The process of claim 10, wherein: The second surface is a dielectric surface, which contains SiCOx, SiOx, silicon, SiO2, zirconium oxide (ZrO2), hafnium oxide (HfO2), aluminum oxide (Al2O3), titanium nitride (TiN) and titanium oxide (TiO2) or aluminum nitride (AlN) or a combination thereof.

13. The process of claim 10, wherein: The second surface includes RuOx, NiOx, CoOx, NbOx, MoOx, WOx, NbBx, NbCx, WNCx, TaN or TiN or a combination thereof.

14. The process of claim 10, wherein: The passivation barrier layer includes a self-assembled monolayer (SAM) or an alkylsilane having at least one alkoxy group bonded to a silicon atom.

15. The process of claim 1, wherein: The first precursor includes a diamine, a triamine, a tetraamine, a cyclic compound including at least two primary amines, or a combination thereof.

16. The process of claim 1, wherein: The second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by the general formula (1): (1) wherein R and R' independently comprise a hydrocarbon group.

17. The process of claim 16, wherein: At least one of the hydrocarbon groups independently comprises one or more of the following: O, N or S or a combination thereof.

18. The process of claim 1, wherein: The second precursor includes a compound including two thioanhydride groups, the compound including a structure represented by general formula (2): (2) Here, R includes a hydrocarbon group.

19. The process of claim 18, wherein: The hydrocarbon group comprises one or more of the following: O, N or S or a combination thereof.

20. The process of claim 1, wherein: The second precursor includes a compound including a thioanhydride group and an acid anhydride group, the compound including a structure represented by the general formula (3): (3) wherein R and R' independently comprise a hydrocarbon group.

21. The process of claim 20, wherein: At least one of the hydrocarbon groups independently comprises one or more of the following: O, N or S or a combination thereof.

22. The process of claim 1, wherein: The second precursor includes a compound including a thioanhydride group and an acid anhydride group, the compound including a structure represented by the general formula (4): (4) Here, R includes a hydrocarbon group.

23. The process of claim 22, wherein: The hydrocarbon group contains one or more of the following: O, N or S or a combination thereof.

24. The process of claim 1, wherein: The second precursor includes a compound including at least one thioanhydride group, the compound including a structure represented by the general formula (5): (5) wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of the following: O, N or S or a combination thereof; and wherein X is selected from S or O.

25. The process of claim 1, wherein: The second precursor includes a compound including two or more anhydride groups, the compound including a structure represented by general formula (6): (6) wherein L is a tetravalent hydrocarbon group, which optionally comprises one or more of the following: O, N or S or a combination thereof; and wherein X' and X" are independently selected from S, Se, Te, NH, NR" or O, wherein R" is a C1 to C6 compound.

26. The process of claim 1, wherein: The second precursor includes a compound represented by the general formula (7): (7) wherein R1, R2 and R3 independently comprise hydrocarbon groups, which optionally include one or more of the following: O, N or S or a combination thereof; and wherein Y is selected from S, Se, Te, NH, NR" or O, wherein R" is a C1 to C6 compound.

27. The process of claim 1 further comprising depositing a material selectively on the second surface of the substrate relative to the passivation layer.

28. The process of claim 27, wherein: The material is a first dielectric and the second surface is a second dielectric.

29. The process of claim 27, wherein: The material is a dielectric and the second surface is a metal.

30. The process of claim 27, wherein: The material is a metal and the second surface is a dielectric.

31. The process of claim 27, wherein: The material is a metal, and the second surface is a metal comprising a conductive metal nitride.

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