Selective deposition of aluminum-containing dielectric materials on

Abstract

A method for selectively passivating a surface of a substrate, wherein the surface of the substrate comprises at least one first surface comprising a metal and at least one second surface comprising a dielectric material. The method includes the step of exposing the surface to at least one alkyne, where the alkyne selectively reacts with the metal to passivate the first surface, leaving a substantially unreacted second surface.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 520,228, filed August 17, 2023, and U.S. Provisional Patent Application No. 63 / 560,138, filed March 1, 2024, the disclosures of which are incorporated herein by reference. Technical Field

[0002] This application relates to selectively forming a passivation layer on a first surface of a substrate relative to a second surface. Additionally, further processing can be used to subsequently deposit different materials on the second surface relative to the first surface. Background Technology

[0003] Selective deposition has gained significant momentum, primarily due to the limitations of contemporary photolithography processes, enabling the fabrication of advanced semiconductor devices based on ever-shrinking physical dimensions. Traditionally, patterning in the microelectronics industry has been accomplished using various photolithography and etching processes. However, as photolithography becomes exponentially more complex and expensive, the appeal of using selective deposition to form self-aligned features has become far greater. The fabrication of self-aligned via structures benefits significantly from the manufacturability of selective deposition processes. Another potential application of selective deposition is gap filling. In gap filling, a dielectric “fill” film is selectively grown from the bottom of the trench towards the top. Selective deposition can be used for other applications, such as selective sidewall deposition, where a film is selectively deposited on the exposed surfaces of a three-dimensional FIN-FET structure. This allows for the deposition of sidewall spacers without the need for complex patterning steps. Selective deposition processes for metal and metal oxide films used as gate and capacitor dielectrics are also very useful in semiconductor device fabrication.

[0004] Prior examples exist in the technical literature involving the selective formation of surface passivation coatings on wafers with multiple exposed surfaces of different chemicals. The aim is to delay or prevent film deposition on these passivated surfaces via an ALD process, but not to prevent deposition on surfaces where an ALD deposition process is required. Typically, process selectivity is insufficient due to incomplete surface passivation and / or due to the physical adsorption of ALD precursor molecules and the subsequent formation of ALD film material within the passivation layer itself or on surfaces where deposition is not desired.

[0005] Due to the similarity of their surface chemical properties, selective passivation of metals relative to dielectrics to achieve zone-selective deposition (ASD) of dielectrics on dielectrics remains a significant challenge. To date, relatively few passivation chemistry studies have been reported that can selectively passivate metals relative to dielectrics to successfully allow atomic-layer deposition of dielectric films on dielectrics.

[0006] This disclosure attempts to overcome the limitations of the prior art and provides an improved method for selectively depositing ultrathin film materials using ALD deposition processes. Invention Overview In a first aspect, a method is provided for selectively forming an aluminum-containing dielectric film on at least one surface of a substrate. The method comprises: (a) providing a substrate in a reaction vessel having a first surface comprising a metal and a second surface comprising a dielectric material, wherein the first and second surfaces are coplanar; and (b) forming at least one passivation layer on the first surface by exposing the first and second surfaces to a passivation composition comprising an alkyne having one of the following formula: Where R 1 and R 2 Each is selected from straight or branched chains C6 to C 14 Alkyl or straight-chain or branched C6 to C5 14 (c) arylalkyl; (d) purging the reactor with an inert gas; (e) introducing an aluminum precursor into the reactor to react with the dielectric material to form an aluminum-containing layer; (f) purging the reactor with an inert gas; (g) introducing water vapor into the reactor to react with the aluminum-containing layer to form an alumina layer; (h) purging the reactor with an inert gas; and (d) repeating steps (d) to (g) to deposit an aluminum-containing dielectric film of the desired thickness on top of the dielectric material.

[0008] In a further aspect of the first principal aspect, the thickness of the aluminum-containing dielectric film may be in the range of about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

[0009] In a further aspect of the first main aspect, the aluminum precursor is selected from triethylaluminum, dimethylaluminum isopropoxide, and diethylaluminum isopropoxide.

[0010] In a further aspect of the first principal aspect, the alkyne of formula IA is selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecanyne, 1-dodecyne, 1-tridecyne, 1-tetradecyne, ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne and 6-phenyl-1-hexyne.

[0011] In a further aspect of the first principal aspect, the alkyne of formula IB is selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecanyne, 2-dodecyne, 2-tridecyne and 2-tetradecyne.

[0012] In a further aspect of the first principal aspect, the passivating composition comprises, or is substantially composed of, 1-decyne, 1-dodecyne, or 5-phenyl-1-pentyne.

[0013] In a further aspect of the first principal aspect, the deposition selectivity of the second surface relative to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.6.

[0014] In a further aspect of the first principal aspect, the deposition selectivity of the second surface relative to the first surface is greater than about 0.6, and the thickness of the aluminum-containing dielectric film is about 50 Å or less.

[0015] In a second principal aspect, a method is provided for selectively forming an aluminum-doped silicon oxide dielectric film on at least one surface of a substrate. The method includes: (a) loading a substrate into a reactor, the substrate comprising a first surface containing a metal and a second surface containing a dielectric material, wherein the first and second surfaces are coplanar; and (b) introducing an alkyne into the reactor to selectively form an organic layer on the metal surface, the alkyne having the following formula: Where R 1 and R 2 Each is selected from straight or branched chains C6 to C 14 Alkyl or straight-chain or branched C6 to C5 14 (c) arylalkyl; (d) purging the reactor with an inert gas; (e) introducing an aluminum precursor into the reactor to react with the dielectric material to form an aluminum-containing layer; (f) purging the reactor with an inert gas; (g) introducing a vapor containing an alkoxysilanol into the reactor to react with the aluminum-containing layer to form an aluminum-silicon oxide layer; and (h) purging the reactor with an inert gas; and optionally (h) repeating steps (d) to (g) to deposit an aluminum-doped silicon oxide dielectric film of the desired thickness on top of the dielectric material.

[0016] In a further aspect of the second main aspect, the thickness of the aluminum-doped silicon oxide dielectric film ranges from about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

[0017] In a further aspect of the second main aspect, the aluminum precursor is selected from triethylaluminum, dimethylaluminum isopropoxide, and diethylaluminum isopropoxide.

[0018] In a further aspect of the second main aspect, the alkyne of formula IA is selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecanyne, 1-dodecyne, 1-tridecyne, 1-tetradecyne, ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne and 6-phenyl-1-hexyne.

[0019] In a further aspect of the second main aspect, the alkyne having formula IB can be selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecanyne, 2-dodecyne, 2-tridecyne and 2-tetradecyne.

[0020] In a further aspect of the second main aspect, the alkoxysilanol is selected from tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert-pentoxy)silanol and bis(tert-pentoxy)(tert-butoxy)silanol.

[0021] In a further aspect of the second main aspect, the dielectric material is selected from silicon oxide, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, silicon nitride, and metal oxides such as zirconium oxide, hafnium oxide, silicon-doped zirconium oxide, or silicon-doped hafnium oxide, or combinations thereof.

[0022] In a further aspect of the second main aspect, the metal or metal oxide is selected from cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or combinations thereof.

[0023] In a further aspect of the second main aspect, the deposition selectivity of the second surface relative to the first surface is greater than about 0.6, more preferably greater than about 0.8, most preferably greater than about 0.9, and the thickness of the aluminum-doped silicon oxide dielectric film is about 100 Å or less.

[0024] In a further aspect of the second main aspect, steps (d) to (g) are carried out at a temperature of about 150 to about 350 degrees Celsius.

[0025] In a further aspect of the second main aspect, a pre-cleaning step is performed prior to step (a), which includes exposing the first surface to an acid, a reducing environment, heating, or a combination thereof.

[0026] In a further aspect of the second main aspect, the pre-cleaning step includes exposing the substrate to citric acid, followed by exposing the substrate to H2 at a temperature ranging from about 250 to about 500 degrees Celsius.

[0027] In a further aspect of the second main aspect, the substrate undergoes a chemical mechanical planarization step, wherein the chemical mechanical planarization step is performed prior to the pre-cleaning step in order to provide coplanarity between the first and second surfaces.

[0028] In a third key aspect, a method for passivating a metal-containing surface of a substrate is provided. The method includes: (a) providing a substrate in a reaction vessel at a temperature ranging from 20°C to 400°C, the substrate having a first surface comprising a metal and a second surface comprising a dielectric material; and (b) forming at least one passivation layer on the first surface by exposing the first and second surfaces to a passivation composition comprising an alkyne having the following formula: Where R 1 Is it a straight chain or a branched chain C6 to C? 14 (c) Arylalkyl; and (d) purging the reactor with an inert gas.

[0029] In a further aspect of the third main aspect, steps (a) to (c) are repeated to provide a fully covered passivation layer on the second surface.

[0030] In a further aspect of the third principal aspect, the first surface comprises a metal or metalloid selected from ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof, or wherein the first surface comprises a metal nitride selected from tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), silicon, germanium, and combinations thereof.

[0031] In a further aspect of the third main aspect, the second surface is selected from silicon oxide and carbon-doped silicon oxide, or wherein the second surface is selected from silicon nitride.

[0032] In a further aspect of the third main aspect, the alkyne is selected from ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne and 6-phenyl-1-hexyne.

[0033] The embodiments disclosed herein can be used alone or in combination with each other. Brief description of the attached diagram The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and form part of this specification. They illustrate embodiments of the disclosed subject matter and, together with the description, serve to explain the principles of the disclosed subject matter. In the drawings: Figure 1 An example is illustrated, which includes: surface pre-cleaning, metal passivation, and selective deposition, wherein a dielectric film is selectively deposited on the dielectric film while the metal surface is passivated; Figure 2 The selectivity of 1-alkynes and 5-alkynes on alumina films of different thicknesses (Å) was compared.

[0035] Figure 3The selectivity of 1-alkynes on alumina films of different thicknesses (Å) at different temperatures was compared. Figure 4 The selectivity of 5-phenyl-1-pentyne and 1-dodecyne at 250 °C was compared for various thicknesses (Å); and Figure 5 The selectivity of various thicknesses (Å) of aluminum-doped silica films of 5-phenyl-1-pentyne and 1-dodecyne at 250 °C was compared. Invention Details All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference as if each reference were individually and specifically indicated to be incorporated by reference and fully elaborated in this article.

[0037] In the context of describing the disclosed subject matter (particularly in the context of the following claims), the use of the terms “a” and “an”, as well as “the” and similar designations, should be interpreted as encompassing both singular and plural, unless otherwise stated herein or obviously contradicted by the context. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including, but not limited to”). Unless otherwise stated herein, the descriptions of numerical ranges herein are intended only as a shorthand method for individually referring to each individual value falling within that range, and each individual value is incorporated into the specification as if it were individually described herein. Unless otherwise stated herein or obviously contradicted by the context, all methods described herein can be performed in any suitable order. The use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better elucidate the disclosed subject matter and, unless otherwise expressly stated, does not constitute a limitation on the scope of the disclosed subject matter. No language in the specification should be construed as indicating any unclaimed element as necessary for implementing the subject matter of this disclosure.

[0038] This document describes preferred embodiments of the present disclosure, including the best modes known to the inventors for implementing the claimed subject matter. Variations of those preferred embodiments will be apparent to those skilled in the art after reading the foregoing description. The inventors anticipate that those skilled in the art will appropriately employ such variations, and the inventors intend to implement the claimed subject matter in a manner different from that specifically described herein. Therefore, this disclosure includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, any combination of the foregoing elements in all their possible variations is included in the claimed subject matter unless otherwise stated herein or the context clearly contradicts it.

[0039] Various methods are available for selective deposition. Embodiments of this invention relate to a method for surface deactivation by utilizing the surface chemistry of two different surfaces. Since the two different surfaces have different reactive handles, this difference can be exploited by employing molecules that react with one surface (to deactivate that surface) but not with the other.

[0040] In this disclosure, it has been envisioned and demonstrated that metals such as copper can be selectively passivated using 1-alkyne, thus allowing for the greatly suppressed growth of dielectrics on the passivated metal surface, but only at relatively higher temperatures than thiol-based inhibitors, the dielectric film, such as an aluminum-containing dielectric film, can be grown with high selectivity on dielectric surfaces such as silicon oxide or carbon-doped silicon oxide.

[0041] Various aspects of this disclosure will now be described with reference to the accompanying drawings and tables disclosed herein (where applicable), wherein similar reference numerals refer to similar elements unless otherwise stated. As described above, in the art there is a need for heat treatment without plasma at temperatures ranging from 150 to 350°C to selectively deposit aluminum-containing dielectric materials, such as alumina or silicon-doped alumina, on top of a dielectric surface relative to a metal surface in semiconductor manufacturing processes with high selectivity.

[0042] In the illustrative embodiment, selectivity is defined as (thickness of aluminum-containing film on dielectric material (growth surface) - thickness of aluminum-containing film on metallic material (non-growth surface)) / (thickness of aluminum-containing film on dielectric material (growth surface) + thickness of aluminum-containing film on metallic material (non-growth surface)).

[0043] Selectivity is calculated using the following formula: .

[0044] The selectivity is preferably 80% or greater, more preferably 85% or greater, 90% or greater, or most preferably 95% or greater.

[0045] Therefore, this paper discloses a novel and non-obvious selective thermal atomic layer deposition (ALD) method for selectively depositing aluminum-containing dielectric materials on top of dielectric materials relative to metals in an ALD reactor. The method includes: (a) Loading a substrate containing dielectric material and metal into the reactor; (b) Introducing a passivation composition comprising an alkyne having one of the following formula to selectively form an organic layer on a metal surface: Where R 1 and R 2 Each is selected from straight or branched chains C6 to C 14Alkyl or arylalkyl; (c) Purge the reactor with inert gas; (d) Introducing an aluminum precursor into a reactor to react with a dielectric material to form an aluminum-containing layer; (e) Purge the reactor with inert gas; (f) Introducing water-containing vapor into the reactor to react with the aluminum-containing layer, thereby forming an alumina layer; and (g) Purge the reactor with an inert gas.

[0046] Steps (d) through (g) can be repeated to deposit the desired aluminum-containing dielectric film on top of the dielectric material. In some embodiments, steps (b) and (c) can be performed after repeating steps (d) through (g) to deposit the desired alumina, followed by repeating steps (d) through (g) to provide a thicker alumina. The thickness of the aluminum-containing dielectric film can range from about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å, depending on the target thickness for the desired selectivity. The aluminum precursor can be selected from triethylaluminum, dimethylaluminum isopropoxide, and diethylaluminum isopropoxide. Examples of alkynes having formula IA may be selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecyne, 1-dodecyne, 1-tridecyne, 1-tetradecyne, ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne, and 6-phenyl-1-hexyne. Examples of alkynes having formula IB may be selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2-dodecyne, 2-tridecyne, and 2-tetradecyne.

[0047] In a second aspect, a thermal atomic layer deposition (ALD) method is provided for selectively depositing an aluminum-containing dielectric material on top of a dielectric material relative to a metal in an ALD reactor. The method includes: (a) Loading a substrate containing dielectric material and metal into the reactor; (b) Introducing a passivation composition comprising an alkyne to selectively form an organic layer on a metal surface, the alkyne comprising one of the following formulas: Where R 1 and R 2 Each is selected from straight or branched chains C6 to C 14 Alkyl or arylalkyl; (c) Purge the reactor with inert gas; (d) Introducing an aluminum precursor into a reactor to react with a dielectric material to form an aluminum-containing layer; (e) Purge the reactor with inert gas; (f) Introducing vapors containing alkoxysilanols into the reactor to react with the aluminum-containing layer, thereby forming an alumina-silicon layer; and (g) Purge the reactor with an inert gas.

[0048] Steps (d) to (g) can be repeated to deposit an aluminum-doped silicon oxide dielectric film of the desired thickness on top of the dielectric material. In some embodiments, steps (b) and (c) can be performed after repeating steps (d) to (g) to deposit the desired alumina, followed by repeating steps (d) to (g) to provide a thicker alumina silicon. The thickness of the aluminum-containing dielectric film can range from about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å, depending on the target thickness for the desired selectivity. The aluminum precursor is selected from triethylaluminum, dimethylaluminum isopropoxide (DMAI), and diethylaluminum isopropoxide. Examples of alkynes having formula IA may be selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecyne, 1-dodecyne, 1-tridecyne, and 1-tetradecyne. Examples of alkynes having formula IB may be selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecyne, 2-dodecyne, 2-tridecyne, 2-tetradecyne, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne, and 6-phenyl-1-hexyne. Alkoxysilanols are selected from tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert-pentoxy)silanol, and bis(tert-pentoxy)(tert-butoxy)silanol.

[0049] In a preferred embodiment of the method, the dielectric material may be selected from silicon oxide, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, silicon nitride, and metal oxides such as zirconium oxide, hafnium oxide, silicon-doped zirconium oxide, silicon-doped hafnium oxide, or any other high-k material. In a preferred embodiment, the metal may be selected from cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or combinations thereof.

[0050] As used in this specification and the appended claims, the terms "substrate" and "wafer" are used interchangeably, both referring to a surface or portion of a surface on which a process is performed. Those skilled in the art will also understand that, unless the context clearly indicates otherwise, reference to a substrate may also refer only to a portion of the substrate. Furthermore, references to deposition on a substrate can refer to a bare substrate and a substrate on which one or more films or features are deposited or formed.

[0051] As used herein, “substrate” refers to any substrate or material surface formed on a substrate on which film processing is performed during the manufacturing process. For example, substrate surfaces on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, but are not limited to, semiconductor wafers. Substrates may be exposed to pretreatment processes such as polishing, etching, reduction, oxidation, hydroxylation, annealing, and / or baking of the substrate surface. In addition to film processing directly on the surface of the substrate itself, any of the disclosed film processing steps may also be performed on an underlying layer formed on the substrate, as disclosed in more detail below, and the term “substrate surface” is intended to include such an underlying layer as indicated by the context. For example, where a film / layer or a portion of a film / layer has already been deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface contains depends on what film is to be deposited and the specific chemistry used. In one or more embodiments, the first substrate surface comprises a metal and the second substrate surface comprises a dielectric, or vice versa. In some embodiments, the substrate surface may contain certain functional groups (e.g., -OH, -NH, etc.).

[0052] Similarly, the metal-containing surfaces that can be used in the methods described herein are quite diverse. In some embodiments, the film may comprise or consist substantially of a metal or a metal nitride. Examples of metal surfaces include, but are not limited to, ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof. Examples of metal nitride films include, but are not limited to, tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), and combinations thereof.

[0053] In some embodiments, the deposited film contains a dielectric. Examples include SiO2, carbon-doped silicon oxide, SiN, HfO2, ZrO2, etc.

[0054] In embodiments of this disclosure, the substrate has at least two discrete surfaces, each characterized by a different chemical property. For example, in one embodiment, the substrate surface includes at least a first surface comprising copper and at least a second surface comprising a dielectric material such as silicon dioxide.

[0055] At least one second surface comprising a dielectric material may be, for example, any material selected from SiO2, metal oxides, copper, cobalt, tungsten, amorphous silicon, polycrystalline silicon, monocrystalline silicon, germanium, and amorphous germanium hydride. In some embodiments, the at least one second surface comprises SiO2, which is a dielectric surface, such as a SiO2 surface. In some embodiments, the surface comprising SiO2 may comprise silicon oxide, silicon fluoride glass (FSG), carbon-doped silicon oxide (SiOC), and / or materials containing more than about 50% silicon oxide. In some embodiments, the surface comprising SiO2 comprises -OH groups and may also comprise, for example, an alumina (Al2O3) surface having -OH surface groups.

[0056] Embodiments of this disclosure provide a method for selectively depositing a film (e.g., a dielectric film) onto a surface of the same substrate relative to a second surface on the substrate, wherein the two surfaces are coplanar, resulting from chemical mechanical planarization. As used in this specification and the appended claims, the term "selectively depositing a film on one surface relative to another surface" means that one of the first or second surfaces is passivated to substantially prevent deposition on the passivation layer, and the film is deposited on the second (non-passivated) surface. The term "relative" as used in this aspect does not imply a physical orientation of one surface on top of another surface, but rather a relationship of the thermodynamic or kinetic properties of the chemical reactions of one surface relative to the other. For example, selectively depositing a cobalt film on a copper surface relative to a dielectric surface means that a cobalt film is deposited on the copper surface, while less or no cobalt film is deposited on the dielectric surface; or that the formation of a cobalt film on the copper surface is thermodynamically or kinetically advantageous relative to the formation of a cobalt film on the dielectric surface.

[0057] The methods disclosed herein include the optional step of contacting a substrate surface with a wet chemical composition to obtain a treated substrate. Exemplary wet chemical treatments include known chemical treatments such as, for example, RCA cleaning chemicals SC-1 and SC-2, aqueous HF solutions, peroxides, H2SO4 / H2O2, NH4OH, buffered HF solutions, and mixtures thereof.

[0058] In a preferred embodiment, the wet chemical composition comprises at least one selected from compositions comprising: H2O2 (28% aqueous solution), NH4O4 (28-30%) and H2O; HF (0.01%-10% aqueous solution); peroxides; RCA cleaning chemicals SC-1 and SC-2; and mixtures of H2SO4 / H2O2.

[0059] As is known in the art, "RCA Cleaning Chemicals" refers to compositions comprising a mixture of ammonium hydroxide and hydrogen peroxide, wherein the basic cleaning process was developed by Radio Corporation of America in the 1960s. The RCA Standard-Clean-1 (SC-1) process uses a solution of ammonium hydroxide and hydrogen peroxide heated to approximately 70°C and water. The SC-1 process dissolves the film and removes Group I and Group II metals. Group I and Group II metals are removed by combining with reagents in the SC-1 solution. The RCA Standard-Clean-2 (SC-2) process utilizes a mixture of hydrogen peroxide, hydrochloric acid, and water heated to approximately 70°C. The SC-2 process removes metals not removed by the SC-1 process.

[0060] Contact with the wet chemical composition can be made by any method known to those skilled in the art, such as impregnation or spraying. The contact step can be a single step or more than one step.

[0061] In some embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from approximately ambient temperature to about 100°C. In other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 55°C to about 95°C. In still other embodiments, the temperature of the wet chemical composition during the contact step can be, for example, from about 60°C to about 90°C.

[0062] The embodiment also includes a step of rinsing the substrate surface with deionized water after the step of contacting the substrate surface with the wet chemical composition. The rinsing step is typically performed by any suitable method, such as rinsing the substrate surface with deionized water by immersion or spraying techniques.

[0063] The implementation also includes a step of drying at least the surface of the substrate after the rinsing step. The drying step is typically carried out by any suitable means, such as application of heat, isopropanol (IPA) vapor drying, or centrifugal force.

[0064] The embodiments may also optionally include a step of treating the surface with hydrogen plasma, argon plasma, or ammonia plasma. Suitable treatments include plasma treatment (hydrogen plasma, NH3 / NF3 plasma, water plasma, etc.). The optional plasma step is used to remove unwanted deposits on the surface and activate the surface for subsequent deposition of passivating agents. Such plasma treatment is most preferably performed after some deposition has been made on the surface to remove non-selectively deposited material from the previously passivated surface and to remove residual passivating agents after the desired deposition thickness has been reached.

[0065] As used throughout this specification, the term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. In some embodiments, the alkyl group has 1 to 20 carbon atoms, 2 to 20 carbon atoms, 1 to 10 carbon atoms, 2 to 10 carbon atoms, 1 to 8 carbon atoms, 2 to 8 carbon atoms, 1 to 6 carbon atoms, 2 to 6 carbon atoms, 1 to 4 carbon atoms, 2 to 4 carbon atoms, 1 to 3 carbon atoms, or 2 or 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, tert-butyl, isobutyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl, octyl, nonyl, 4,4-dimethylpentyl, 2,2,4-trimethylpentyl, decyl, undecyl, dodecyl, 2-methyl-1-propyl, 2-methyl- 2-Propyl, 2-Methyl-1-Butyl, 3-Methyl-1-Butyl, 2-Methyl-3-Butyl, 2-Methyl-1-pentyl, 2,2-Dimethyl-1-Propyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2,2-Dimethyl-1-Butyl, 3,3-Dimethyl-1-Butyl, 2-Ethyl-1-Butyl, etc.

[0066] As used throughout this specification, the term "cycloalkyl" refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0067] As used herein, the term "aryl" refers to an aromatic hydrocarbon that is monocyclic, bicyclic, or polycyclic (e.g., having 2, 3, or 4 fused rings). In some embodiments, the aryl group has 6 to 20 carbon atoms or 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracene, phenanthryl, indanyl, indenyl, and tetrahydronaphthyl.

[0068] As used herein, the term "arylalkyl" refers to an alkyl group in which hydrogen is replaced by an aryl group. In some embodiments, the alkyl group is C10. 1-6 Alkyl group. It can be further substituted with halogens (such as Cl, F, or Br). In other embodiments, one or more hydrogens in the aryl ring can be substituted with alkyl groups or halogens or halogen-containing alkyl groups.

[0069] As used throughout this specification, the term "alkenyl" means a group having one or more carbon-carbon double bonds and having 2 to 18 or 2 to 10 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl.

[0070] As used herein, the term "alkynyl" refers to a straight-chain or branched alkyl group having 2 to 20 carbon atoms and one or more carbon-carbon triple bonds. In some embodiments, the alkynyl group has 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, acetylene, 1-propene, 2-propene, etc.

[0071] As used herein, the phrase “optionally substituted” means that substitution is optional and therefore includes both unsubstituted and substituted atoms and portions. A “substituted” atom or portion means that any hydrogen atom on a specified compound or portion can be replaced by a choice of indicated substituents, provided that the substitution does not exceed the normal valence of the specified compound or portion and that the substitution produces a stable compound. For example, if the methyl group is optionally substituted, one, two, or three hydrogen atoms on the carbon atom within the methyl group can be replaced by one, two, or three of the stated substituents.

[0072] As used herein, the term "phenyl" refers to -C6H5. A phenyl group may be unsubstituted or substituted with one, two, or three suitable substituents.

[0073] As used herein, the term "halogenated" refers to a halogen group, including but not limited to fluorine, chlorine, bromine, and iodine.

[0074] Vapor-phase or gas-phase reactions involve exposing a heated substrate to precursor molecules and / or co-reactants in a suitable chamber that must be able to provide the necessary pressure control and also provide heat to the substrate and / or chamber walls; the chamber should also provide suitable purity for the reaction to occur, typically through high leak integrity and the use of ultra-high purity carriers and reactive gases.

[0075] As used in this specification and the appended claims, the terms “reactive gas,” “precursor,” “reactant,” etc., are used interchangeably to refer to a gas comprising a substance reactive with the substrate surface. For example, a first “reactive gas” may simply be adsorbed onto the surface of the substrate and may be used for further chemical reactions with a second reactive gas. They may be used in combination with ultra-high purity carrier gases (as defined above) or in any desired mixture of them (i.e., more than one type of precursor may be used together or in discrete, independent steps to form the desired passivation layer, regardless of the desired order of precursor introduction).

[0076] Precursors and / or co-reactants can be delivered to the reactor using a mass flow controller (possibly with heated piping), a liquid injection evaporator (possibly with heated piping), or without metering (i.e., by net introduction of vapors and / or gases from a separate vessel using simple valves). Any of the above can also be used in combination. Gases and / or vapors can be supplied to the reaction chamber (providing sufficient purity and repeatability) using any method.

[0077] Precursors and / or co-reactants may be introduced into the reactor independently, mixed prior to introduction into the reactor, mixed in the reactor, or introduced in any combination of the foregoing in multiple independent steps (which may include differences in how the precursors are introduced between steps).

[0078] The reaction temperature range can be between room temperature and 400°C. In some cases, the reaction temperature range can be between room temperature and 200°C. In other cases, the reaction temperature range can be between room temperature and 100°C. The pressure can be 10... -10 The pressure can range from 1000 Torr to 3000 Torr and can be maintained under dynamic flow conditions (i.e., using valves and butterfly valves) or under static conditions (i.e., the emptied chamber is exposed to the desired precursors and / or co-reactants until the desired total pressure is reached, then the chamber is isolated from the precursor and / or co-reactant source and vacuum pump). The reactor can be completely emptied and re-exposed to fresh precursors and / or co-reactants multiple times as needed. Precursors and / or co-reactants can be introduced using any desired mixture and / or concentration.

[0079] Surface exposure can last from 0.1 to 60 minutes, preferably 1 to 5 minutes, and most preferably 1 minute. The partial pressure of the organohalide in the reaction chamber can vary from about 1% to almost 100% of its saturated vapor pressure at the substrate temperature. Most preferably, it is between 20% and 50% of its saturated vapor pressure. The chamber pressure can be the same as the partial pressure of the organohalide vapor, but can be higher as the atmosphere containing the carrier gas becomes balanced. Preferred carrier gases include N2, He, and Ar, but other gases such as H2, CO2, and dry O2 can also be used. The exposed vapor can be static (non-flowing) for the entire or partial exposure period. A preferred embodiment is to allow the organohalide vapor to flow through the exposure chamber along with an optional carrier gas, such that fresh vapor is exposed to the substrate surface for at least a portion of the exposure period.

[0080] The exposure chamber can be maintained at near ambient temperature or optionally heated. Heat can be supplied to the outer walls of the chamber (hot walls) or only to the substrate (cold wall reactor). Substrate heating in the cold wall reactor can be achieved by using incident radiation through a transparent window (lamp heating), resistance heating of the substrate itself or from resistance heating elements in a platform in contact with the substrate, by induction, or by other means known in the art. The processing temperature is preferably between about 20°C and about 400°C, more preferably between 20°C and about 200°C, and most preferably between 20°C and about 100°C. The temperature can be kept constant during exposure or can be varied within a specified temperature range.

[0081] Then, before removing the substrate from the chamber or before chemical vapor deposition or atomic layer deposition, unreacted vapors of at least one organohalide may optionally be removed by purging the chamber or purging it with a suitable inert gas. Optionally, the exposed chamber may also be used for subsequent processing steps to improve processing efficiency, such that the process can be repeated from step c) (if necessary) to strip the protective film and any non-selective ALD deposits, and then reform the protective film.

[0082] The selection of at least one alkyne used in this method and the exposure conditions should be optimized through standard experiments to optimize the selectivity of the protection provided by the metal surface against potential non-selective passivation, processing time, reagent costs, etc., based on the requirements imposed by subsequent processing steps. For example, selectivity can be tuned / optimized by changing the properties of the R' or R'' group of at least one alkyne having a structure represented by formula IA or IB. Typically, since reactivity and selectivity are usually negatively correlated, it may be necessary to experiment with R groups to optimize the method if two surfaces are chemically similar. For example, there is a difference in reactivity between alkyl R-groups and aryl R-groups; generally, aryl groups are more reactive with surfaces carrying active hydrogen than alkyl groups. Therefore, in some cases, alkyl groups may be needed to selectively passivate the metal without simultaneously passivating adjacent surfaces with less reactive active hydrogen atoms.

[0083] The disclosed and claimed passivation compositions In view of the foregoing, in one embodiment, the disclosed and claimed subject matter relates to passivation compositions comprising, substantially composed of, and / or composed of alkynes. Passivation compositions are particularly suitable for enhancing the passivation of metal substrates. In one aspect of this embodiment, the alkynes are substantially composed of, or composed of, one or more 1-alkynes (alkynes having a triple bond at the 1-position) or 2-alkynes (alkynes having a triple bond at the 2-position).

[0084] In one embodiment, the alkyne having formula IA or IB is a high-purity alkyne that is substantially anhydrous. In one aspect of this embodiment, the residual water concentration of the high-purity alkyne is less than about 500 ppm. In one aspect of this embodiment, the residual water concentration of the high-purity alkyne is less than about 100 ppm. In one aspect of this embodiment, the residual water concentration of the high-purity alkyne is less than about 50 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual water concentration of less than about 25 ppm. In one aspect of this embodiment, the residual water concentration of the high-purity alkyne is less than about 10 ppm. In one aspect of this embodiment, the high-purity alkyne does not contain detectable water. In one aspect of this embodiment, the high-purity alkyne is anhydrous.

[0085] In one embodiment, the alkyne having formula IA or IB is substantially free of carboxylic acid. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual carboxylic acid concentration of less than about 1000 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual carboxylic acid concentration of less than about 500 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual carboxylic acid concentration of less than about 100 ppm. In one aspect of this embodiment, the alkyne having formula IA or IB is free of detectable carboxylic acid. In one aspect of this embodiment, the alkyne having formula IA or IB is free of carboxylic acid.

[0086] In one embodiment, the alkyne having formula IA or IB is substantially free of impurities that may react with the metal surface during the passivation process. In another embodiment, the alkyne having formula IA or IB is substantially free of impurities that may react with the precursor during the deposition process.

[0087] In one embodiment, the alkynes having formula IA or IB are substantially free of impurities that passivate nonmetallic surfaces and inhibit growth on nonmetallic surfaces.

[0088] In one embodiment, the alkyne having formula IA or IB is substantially free of halogen-containing impurities. In one aspect of this embodiment, the halogen-containing impurity is one or more of fluorinated hydrocarbons, chlorinated hydrocarbons, bromine hydrocarbons, and iodinated hydrocarbons. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 1000 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 500 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 100 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 50 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 25 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkyne having formula IA or IB has a residual concentration of less than about 10 ppm of halogen-containing impurities. In one aspect of this embodiment, the alkynes having formula IA or IB do not contain halogen-containing impurities. In the foregoing, the residual concentration of halogen-containing impurities is detected by one or more of the following methods: gas chromatography (GC) and related coupling techniques, including but not limited to GC-FID, GC-ECD, and GC-MS; liquid chromatography (defined as including LC, HPLC, or UPLC variants) and related coupling techniques, including but not limited to LC-DAD and LC-MS; ion chromatography (IC) and related forms; spectroscopic techniques, including but not limited to infrared (IR), ultraviolet / visible (UV / Vis), near-infrared (NIR), Raman, and nuclear magnetic resonance (NMR) spectroscopy; inductively coupled plasma spectroscopy or spectroscopic analysis (ICP) and related coupling techniques, including but not limited to ICP-MS, ICP-OES, GC-ICP-MS, and GC-ICP-OES; elemental analysis, such as X-ray fluorescence spectroscopy (XRF) and related forms (e.g., WD-XRF) or atomic absorption spectroscopy (AA) and its forms; and finally, wet chemical techniques, including but not limited to titration (e.g., halogen titration with silver nitrate) and electrochemical detection (e.g., cyclic voltammetry, ion-selective electrodes, etc.). In one embodiment of the foregoing aspect, the residual concentration of halogen-containing impurities is detected by one or more of GC-MS, GC-ICP-MS, GC-ICP-OES, GC-FID, GC-ECD, HPLC, and UV / Vis.

[0089] In one embodiment, alkynes having formula IA or IB are purified by exposure to a molecular sieve. In one embodiment, alkynes having formula IA or IB are purified by exposure to silica gel. In one embodiment, alkynes having formula IA or IB are purified by exposure to one or more adsorbent materials.

[0090] In one embodiment, an alkyne having formula IA or IB is purified by treating it with one or more Group I metals, followed by a distillation process. In one aspect of this embodiment, the alkyne is treated with metallic sodium. In another embodiment, the metal and alkyne are separated by filtration, and the alkyne is distilled to remove non-volatile products of the reaction between impurities and the metal.

[0091] In one embodiment, alkynes having formula IA or IB are purified by treatment with one or more Group (II) metals followed by a distillation process. In one aspect of this embodiment, the alkynes are treated with metallic magnesium. In another embodiment, the metal and alkynes are separated by filtration, and the alkynes are distilled to remove non-volatile products of the reaction between impurities and the metal.

[0092] In one embodiment, alkynes having formula IA or IB are purified by exposure to activated carbon. In one aspect of this embodiment, after treatment with activated carbon, the alkynes are separated by filtration and non-volatile products are removed by distillation.

[0093] Accumulation of terminal alkynes Xtb-GFN simulations were performed to compare the increased packing density of 1-decyne and 1-dodecyne on copper surfaces compared to 4-decyne, 5-decyne, and 6-dodecyne. Anchored alkynes were packed as close as possible to the size of the alkyne molecules in a chemisorption geometry containing copper atoms. The packing density is shown by comparing the amount that can be packed on the surface and optimized in Xtb-GFN. The results shown in the table below demonstrate that 1-alkynes have a significantly higher packing density than alkynes in which the carbon-carbon triple bond is located outside the 1-position, indicating that 1-alkynes can provide better closure and higher selectivity than other alkynes.

[0094] Once the metal surface is passivated, a second surface containing, for example, silicon oxide is active for further selective reactions, such as selective ALD deposition of an aluminum oxide-containing film on the silicon oxide surface.

[0095] The selective deposition according to this disclosure can be, for example, metal and metal oxide layers disclosed in Hamalarenen et al., “Atomic Layer Deposition of Noble Metals and Their Oxides”, Chem. Mater. 2014, 26, 786-801; and Johnson et al., “A Brief review of Atomic layer Deposition: From Fundamentals to Applications”, Materials Today, Vol. 17, No. 5, June 2014 (both are incorporated herein by reference in their entirety).

[0096] In some embodiments, the metal film is selectively deposited on the second surface. In one example, the metal film may serve as a capping layer on the second surface. In another example, the metal film may serve as a conductive path (i.e., a wire, pad, or plug) on ​​the second surface. In yet another example, the metal film may be deposited, for example, by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. According to one embodiment, the metal film may be selected from Ru, Al, Ti, Ta, Mo, Co, Rh, Ir, Fe, Ru, Os, Mo, Mn, Tc, Re, Cu, Ag, Au, Ni, Pd, Pt, and combinations thereof.

[0097] In some embodiments, a metal or metal nitride film is selectively deposited on the second surface. In one example, the metal or metal nitride film may serve as a capping layer on the second surface. In another example, the metal or metal nitride film may serve as a diffusion barrier layer. For example, the metal or metal nitride film can be deposited by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. Examples are found, for example, in IBM Research Report, “Atomic Layer Deposition of Metal and Metal Nitride Thin Films: Current Research Efforts and Applications for Semiconductor Device Processing,” RC22737 (W0303-012), March 5, 2003.

[0098] During selective deposition, the aforementioned protective surface, previously selectively deposited on the silicon nitride surface with at least one organohalide, may begin to react or otherwise become less inert. With or without any aqueous or plasma pretreatment steps, optional reapplication of at least one organohalide may be performed to prevent or delay non-selective deposition on the silicon nitride surface.

[0099] In some embodiments, passivation on a first surface of the substrate (such as the copper surface of the substrate) relative to a second surface of the substrate, as described herein, is at least about 90% selective, at least about 95% selective, and at least about 96%, 97%, 98%, or 99% or higher selective. In some embodiments, passivation occurs only on the first surface and not on the second surface. In some embodiments, passivation on the first surface of the substrate is at least about 50% selective or at least about 60% selective relative to the second surface of the substrate, which may be sufficiently selective for some specific applications. In some embodiments, passivation on the first surface of the substrate is at least about 50% selective relative to the second surface of the substrate, which may be sufficiently selective for some specific applications.

[0100] The passivation layer can be removed using wet chemical cleaning. Exemplary wet chemical cleaning includes acidic, basic, and oxidizing (e.g., peroxide-containing) wet chemical compositions known in the art, and optional steps described above for contacting the substrate with the wet chemical composition. Another method for removing the passivation layer is by applying heat or other energy.

[0101] Example Alkynes (e.g., 1-alkynes, 2-alkynes, or 1-arylkynes) selectively passivate metal surfaces relative to silicon oxide (SiO2) surfaces. Figure 1 This process is described in [the document]. This method results in the selective growth of dielectric films of the desired thickness on SiO2.

[0102] process: Figure 1 The illustration shows an illustrative process. Step 1 includes pre-cleaning of the first surface (Cu) and the second surface (SiO2), preferably using acid, H2, high temperature, or a combination thereof. After pre-cleaning, preferably, the first and second surfaces are coplanar, which is as described before the pre-cleaning step. Figure 1 The results of chemimechanical planarization (CMP) are shown.

[0103] Step 2 involves passivating the metal surface by exposing copper to form a passivation / sealing organic layer using a passivation composition preferably containing a 1-alkyne (such as 1-decyne or 1-dodecyne) or a 1-arylalkyne (such as 5-phenyl-1-pentyne). Following passivation of the first surface, step 3 involves depositing an aluminum-containing dielectric layer on the second surface (SiO2), preferably formed via an aluminum precursor and an ALD containing an oxygen or alkoxysilanol.

[0104] Implementation method: Example: Adsorption of 1-acetylenes on a "bare" copper surface, dielectric-on-dielectric (DoD) of alumina. This example evaluates the adsorption of 1-decyne (3E) on a "bare" copper surface. Calculations show that 5-decyne exhibits strong chemisorption on copper (100) with an adsorption energy of -43 kcal / mol, and on copper (111) with an adsorption energy of -40 kcal / mol.

[0105] In this embodiment, the first surface containing copper is pre-cleaned by immersing the PVD copper substrate in a 2% wt% citric acid solution for 3 minutes. Then, the copper, along with SiO2 serving as the growth substrate, is loaded into a pre-cleaning chamber over 10 minutes to minimize air exposure. After loading, the copper and SiO2 are further cleaned by H2 thermal annealing at 350°C for 10 minutes. Following surface preparation, the substrate is moved to a passivation chamber without an air break and subjected to SAM grafting in immersion mode at 250°C for 15 minutes until the passivation layer is saturated. The substrate is then transferred to a deposition chamber where a dielectric (preferably alumina or aluminum-doped silicon oxide) is deposited at 250-350°C using a DMAI-H2O ALD process. The DMAI-H2O ALD sequence consists of a 1-second DMAI dose and a 40-second Ar purge, followed by a 1-second H2O dose and a 60-second Ar purge, at a 1 Torr process pressure. The thickness of alumina on Cu (non-grown surface, NGS) and SiO2 (grown surface, GS) was measured using XRF-XRR thickness calibration, and selectivity was calculated using the following formula: .

[0106] Figure 2 The relationship between the selectivity of the dielectric on the dielectric and the thickness of the alumina film (in Å) is shown, demonstrating that for aluminum-containing films with a thickness of less than 6 nm (60 Å), 1-acetylene has a much better selectivity than 5-acetylene. Figure 3 It shows that selectivity greater than 0.6 can be obtained even at higher deposition temperatures such as 350°C.

[0107] Figure 4 It shows that at 250°C, it has formula IA alkynes (of which R) 1Is it a straight chain or a branched chain C6 to C? 14 A comparison of the selectivity of alkyl or arylalkyl groups (such as 5-phenyl-1-pentyne and 1-dodecyne) for alumina films of various thicknesses showed that copper surfaces passivated with 5-phenyl-1-pentyne at a deposition temperature of 250 °C exhibited a slight DoD selectivity of up to 90% for 25 Å alumina, which was slightly better than that of 1-dodecyne. Importantly, for thicker alumina films, the DoD selectivity of copper surfaces passivated with 5-phenyl-1-pentyne was significantly better than that of 1-dodecyne.

[0108] Figure 5 It shows that at 250°C, it has formula IA alkynes (of which R) 1 Is it a straight chain or a branched chain C6 to C? 14 A comparison of the selectivity of arylalkyl groups (such as 5-phenyl-1-pentyne and 1-dodecyne) for aluminum-doped silicon oxide films of various thicknesses showed that, at a deposition temperature of 250 °C, copper surfaces passivated with 5-phenyl-1-pentyne exhibited a slight DoD selectivity of up to 95% for 80 Å aluminum-doped silicon oxide. Surprisingly, for thicker aluminum-doped silicon oxide films, the DoD selectivity of copper surfaces passivated with 5-phenyl-1-pentyne was significantly better than that of 1-dodecyne. Figure 4 and Figure 5 Both studies indicate that 1-arylalkylynes are better passivation compositions than other alkynes, and suggest that aryl groups appear to provide better passivation layer deposition than straight-chain alkyl groups. For the purposes of this disclosure and the claims, the selectivity of the second surface relative to the first surface is determined by the following equation: Selectivity = (film thickness on the second surface (SiO2) - film thickness on the first surface (Cu)) / (film thickness on the second surface (SiO2) + film thickness on the first surface (Cu)). In the illustrated embodiment, the deposition selectivity of the second surface relative to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.6.

[0109] The disclosed and claimed methods are intended to be used in conjunction with deposition equipment typically found in semiconductor manufacturing sites to produce molybdenum-containing layers for logic applications and other potential functions.

[0110] The foregoing description is primarily for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described with reference to exemplary embodiments thereof, those skilled in the art will understand that various foregoing and other changes, omissions, and additions may be made to its form and details without departing from the spirit and scope of the disclosed and claimed subject matter.

[0111] Although the principles of the invention have been described above in conjunction with preferred embodiments, it should be clearly understood that the description is given by way of example only and is not intended to limit the scope of the claimed subject matter.

Claims

1. A method for selectively forming an aluminum-containing dielectric film on at least one surface of a substrate, comprising: (a) The substrate is provided in a reaction vessel, the substrate having a first surface comprising a metal and a second surface comprising a dielectric material, wherein the first surface and the second surface are coplanar; (b) Forming at least one passivation layer on the first surface by exposing the first surface and the second surface to a passivation composition comprising an alkyne having one of the following formulas: Where R 1 and R 2 Each is selected from straight chains or branches C6 to C 14 Alkyl or straight-chain or branched C6 to C6 14 Arylalkyl; (c) Purge the reactor with an inert gas; (d) Introducing an aluminum precursor into the reactor to react with the dielectric material to form an aluminum-containing layer; (e) Purge the reactor with an inert gas; (f) Introducing water-containing vapor into the reactor to react with the aluminum-containing layer to form an alumina layer; (g) Purge the reactor with an inert gas; and (h) Repeat steps (d) to (g) to deposit the aluminum-containing dielectric film of the desired thickness on top of the dielectric material.

2. The method of claim 1, wherein the thickness of the aluminum-containing dielectric film may be in the range of about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

3. The method of claim 1, wherein the aluminum precursor is selected from triethylaluminum, dimethylaluminum isopropoxide, and diethylaluminum isopropoxide.

4. The method of claim 1, wherein the alkyne of formula IA is selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecanyne, 1-dodecyne, 1-tetaneyne, 1-tetradecyne, ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne, and 6-phenyl-1-hexyne.

5. The method of claim 1, wherein the alkyne of formula IB is selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecanyne, 2-dodecyne, 2-tridecyne, and 2-tetradecyne.

6. The method of claim 1, wherein the passivating composition comprises, or is substantially composed of, 1-decyne, 1-dodecyne, or 5-phenyl-1-pentyne.

7. The method of claim 1, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.3, more preferably greater than about 0.5, and most preferably greater than about 0.

6.

8. The method of claim 1, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.6, and the thickness of the aluminum-containing dielectric film is about 50 Å or less.

9. A method for selectively forming an aluminum-doped silicon oxide dielectric film on at least one surface of a substrate, comprising: (a) Loading the substrate into a reactor, the substrate comprising a first surface containing a metal and a second surface containing a dielectric material, wherein the first surface and the second surface are coplanar; (b) An alkyne is introduced into the reactor to selectively form an organic layer on a metal surface, the alkyne having the following formula: Where R 1 and R 2 Each is selected from straight chains or branches C6 to C 14 Alkyl or straight-chain or branched C6 to C6 14 Arylalkyl; (c) Purge the reactor with an inert gas; (d) Introducing an aluminum precursor into the reactor to react with a dielectric material to form an aluminum-containing layer; (e) Purge the reactor with an inert gas; (f) Introducing vapors containing alkoxysilanols into the reactor to react with the aluminum-containing layer, thereby forming an aluminum-silicon oxide layer; (g) Purge the reactor with an inert gas; and (h) Optionally repeat steps (d) to (g) to deposit the aluminum-doped silicon oxide dielectric film of the desired thickness on top of the dielectric material.

10. The method of claim 9, wherein the thickness of the aluminum-doped silicon oxide dielectric film ranges from about 1 Å to about 100 Å, or about 5 Å to about 90 Å, or about 5 Å to about 80 Å, or about 5 Å to about 70 Å, or about 5 Å to about 60 Å, or about 5 Å to about 50 Å, or about 5 Å to about 40 Å, or about 5 Å to about 30 Å, or about 5 Å to about 20 Å.

11. The method of claim 9, wherein the aluminum precursor is selected from triethylaluminum, dimethylaluminum isopropoxide, and diethylaluminum isopropoxide.

12. The method of claim 9, wherein the alkyne having formula IA is selected from 1-octyne, 1-nonyne, 1-decyne, 1-undecanyne, 1-dodecyne, 1-tetaneyne, 1-tetradecyne, ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne, and 6-phenyl-1-hexyne.

13. The method of claim 9, wherein the alkyne having formula IB may be selected from 2-octyne, 2-nonyne, 2-decyne, 2-undecanyne, 2-dodecyne, 2-tridecyne, and 2-tetradecyne.

14. The method of claim 9, wherein the alkoxysilanol is selected from tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, bis(tert-butoxy)(tert-pentoxy)silanol and bis(tert-pentoxy)(tert-butoxy)silanol.

15. The method of claim 9, wherein the dielectric material of the second surface is selected from silicon oxide, carbon-doped silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, silicon nitride, and metal oxides such as zirconium oxide, hafnium oxide, silicon-doped zirconium oxide, or silicon-doped hafnium oxide, or combinations thereof.

16. The method of claim 9, wherein the metal of the first surface is selected from cobalt, aluminum, copper, tantalum, ruthenium, molybdenum, tungsten, platinum, iridium, nickel, titanium, silver, gold, or combinations thereof.

17. The method of claim 9, wherein the deposition selectivity of the second surface relative to the first surface is greater than about 0.6, more preferably greater than about 0.8, most preferably greater than about 0.9, and the thickness of the aluminum-doped silicon oxide dielectric film is about 100 Å or less.

18. The method of claim 9, wherein steps (d) to (g) are performed at a temperature of about 150 to about 350 degrees Celsius.

19. The method of claim 9, wherein a pre-cleaning step is performed prior to step (a), the pre-cleaning step comprising exposing the first surface to an acid, a reducing environment, heating, or a combination thereof.

20. The method of claim 19, wherein the pre-cleaning step comprises exposing the substrate to citric acid, and subsequently exposing the substrate to H2 at a temperature ranging from about 250 to about 500 degrees Celsius.

21. The method of claim 19, wherein the substrate is subjected to a chemical mechanical planarization step, wherein the chemical mechanical planarization step is performed prior to the pre-cleaning step to provide coplanarity between the first surface and the second surface.

22. A method for passivating a metal-containing surface of a substrate, comprising: (a) The substrate is provided in a reaction vessel at a temperature ranging from 20°C to 400°C, the substrate having a first surface comprising a metal and a second surface comprising a dielectric material; (b) Forming at least one passivation layer on the first surface by exposing the first surface and the second surface to a passivation composition comprising an alkyne having the following formula: Where R 1 Is it a straight chain or a branched chain C6 to C? 14 arylalkyl; and (c) Purge the reactor with an inert gas.

23. The method of claim 22, wherein steps (a) through (c) are repeated to provide a fully covering passivation layer on the second surface.

24. The method of claim 22, wherein the first surface comprises a metal or metalloid selected from ruthenium (Ru), cobalt (Co), copper (Cu), titanium (Ti), tantalum (Ta), nickel (Ni), tungsten (W), molybdenum (Mo), and combinations thereof, or wherein the first surface comprises a metal nitride selected from tantalum nitride (TaN), titanium nitride (TiN), tungsten nitride (WN), tungsten carbonitride (WCN), molybdenum nitride (MoN), copper silicon nitride (CuSiN), silicon, germanium, and combinations thereof.

25. The method of claim 22, wherein the second surface is selected from silicon oxide and carbon-doped silicon oxide, or wherein the second surface is selected from silicon nitride.

26. The method of claim 22, wherein the alkyne is selected from ethynylbenzene, 3-phenyl-1-propyne, 4-phenyl-1-butyne, 5-phenyl-1-pentyne, and 6-phenyl-1-hexyne.

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