Material selective deposition process

Abstract

A method and a reactor system for selectively depositing a material on the surface of a substrate are disclosed. Exemplary methods include the steps of: using a first silanol to selectively form a blocking layer on a first region for a second region; selectively depositing a first material on the second region; and providing a second silanol to selectively remove the blocking layer from the first region or providing an activating compound to enhance the growth of the second material on the first region.

Description

Technology Field

[0001] The present disclosure generally relates to a method for selectively forming a material on a first region of a substrate compared to a second region of a substrate. More specifically, the present disclosure relates to a method for selectively depositing a material by selectively forming a passivation layer on the surface of a substrate. Background Technology

[0002] In some semiconductor device manufacturing processes, it may be desirable to form a material only on specific areas of a substrate. Typically, this result is achieved by depositing a continuous film of material and then patterning the continuous film using lithography and etching steps. These lithography and etching processes can be time-consuming and costly. Furthermore, these processes may not provide the desired precision or resolution for many applications.

[0003] Recently, a technique has been developed that enables the selective deposition of material on a first region of a substrate relative to a second region of a substrate without using photolithography. The selective deposition process can take many forms, including but not limited to selective dielectric deposition (DoD) on dielectric surfaces, selective dielectric deposition (DoM) on metal surfaces, selective metal deposition (MoD) on dielectric surfaces, and selective metal deposition (MoM) on metal surfaces.

[0004] Selective deposition on metallic surfaces (i.e., DoM or MoD) may be of interest to provide a simple method for selectively depositing materials on metallic surfaces without requiring complex patterning and etching steps. Some techniques for selectively depositing materials on metallic surfaces include the use of a blocking layer and a plasma process to remove said blocking layer. While these techniques may work for some applications, the use of a plasma process can cause unwanted damage to the surface of the substrate. Therefore, an improved method is required for selectively forming materials on a first region of the substrate compared to a second region of the substrate.

[0005] Any discussion regarding the problems and solutions described in this section is included in this disclosure solely for the purpose of providing context for the present disclosure. Any or all discussion should not be construed as an acknowledgment that any or all discussion is prior art or known at the time the present invention was made.

[0006] The content of the present invention is provided to introduce selected concepts in a simplified form. Exemplary concepts are described in more detail in the following detailed description of exemplary embodiments of the present disclosure. The content of the present invention is not intended to necessarily distinguish the principal or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] According to various embodiments of the present disclosure, a method is provided, wherein the method comprises the steps of: providing a substrate in a reaction chamber of a reactor, wherein the substrate comprises a first region and a second region; providing a first silanol to selectively form a blocking layer on the first region relative to the second region; selectively depositing a first material on the second region; and providing a second silanol to modify the blocking layer.

[0008] In some embodiments, the first region includes metal.

[0009] In some embodiments, the second region comprises silicon or is essentially made of carbon.

[0010] In some embodiments, the first material comprises a polymer.

[0011] In some embodiments, the method further includes the step of selectively depositing a second material on a first region relative to a second region.

[0012] In some embodiments, the second silanol optionally removes the blocking layer from the first region and / or activates the blocking layer to enhance the growth of the second material on the first region.

[0013] In some embodiments, the first silanol is a chemical formula It includes a compound represented by, where a is 1, 2, or 3, x is 1, 2, or 3, y is 1 or 2, z = 4-xy for each silicon atom of the compound, each R is independently selected from a linear or branched C1-C8 alkyl group, and each R' is independently selected from a linear or branched C1-C8 alkyl group.

[0014] In some embodiments, the first silanol comprises one or more of bis(tert-pentoxy)methylsilanol, tert-butyl(tert-butoxy)silanediol, tert-pentyl(tert-pentoxy)silanediol, or tert-pentyl(tert-butoxy)silanediol.

[0015] In some embodiments, the second silanol is the chemical formula It includes compounds represented by, where x is 1 or 2, y is 2 or 3, and each R is independently selected from linear or branched C1-C6 alkyl groups.

[0016] In some embodiments, the second silanol comprises one or more of tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol.

[0017] In some embodiments, the method further comprises a processing step prior to the step of providing a second silanol, and the processing step comprises one or more of direct plasma treatment, remote plasma treatment, UV treatment, or e-beam treatment.

[0018] In some embodiments, the method further comprises a processing step after the step of providing a second silanol, wherein the processing step comprises one or more of direct plasma treatment, remote plasma treatment, UV treatment, or e-beam treatment.

[0019] In some embodiments, the second material comprises a metal, a semiconductor, a metal oxide, a semiconductor oxide, a metal nitride, a semiconductor nitride, a metal carbide, or a semiconductor carbide.

[0020] In some embodiments, the second material is silicon oxide, aluminum oxide, yttrium oxide, titanium nitride, or silicon nitride.

[0021] In some embodiments, the second material is a conductive or high dielectric constant material.

[0022] In some embodiments, the step of selectively depositing a second material comprises a cyclic deposition process, and one or more cycles of the cyclic deposition process comprise a step of providing a metal precursor and a step of providing a reactant comprising one or more of a reducing agent, an oxidizing agent, a carbide, or a nitriding agent.

[0023] In some embodiments, the metal precursor comprises a metal and one or more ligands.

[0024] According to various embodiments of the present disclosure, a reactor system is provided, wherein the reactor system comprises: a reaction chamber; a first silanol source comprising a first vessel and a first silanol and coupled to the reaction chamber; a second silanol source comprising a second vessel and a second silanol; at least one first material precursor source; and a controller configured to provide the first silanol to selectively form a blocking layer on a first region of a substrate relative to a second region of a substrate and selectively deposit a first material on the second region, and to provide the second silanol to selectively remove the blocking layer.

[0025] According to various embodiments of the present disclosure, a method is provided, wherein the method comprises the steps of: providing a substrate in a reaction chamber of a reactor, wherein the substrate comprises a first region and a second region; providing a first silanol to selectively form a blocking layer on the first region relative to the second region; selectively depositing a first material on the second region; providing an activating compound to modify the blocking layer; and selectively depositing a second material on the first region relative to the second region; wherein the activating compound enhances the growth of the second material on the first region; and wherein the activating compound comprises a group 13 element and the second material comprises a group 14 element, or wherein the activating compound comprises a group 14 element and the second material comprises a group 13 element.

[0026] In some embodiments, the group 14 element is silicon.

[0027] In some embodiments, the activating compound contains a group 14 element and is a second silanol.

[0028] In some embodiments, the group 13 element is aluminum.

[0029] In some embodiments, the second material is aluminum oxide.

[0030] For the purpose of summarizing the invention and highlighting the advantages achieved over the prior art, specific objectives and advantages of the invention may be described. Of course, it should be understood that not all such objectives or advantages may necessarily be achieved according to any specific embodiment of the invention. Accordingly, for example, those skilled in the art will recognize that the invention may be implemented or practiced in a manner that achieves or optimizes one of the advantages or advantages taught or suggested herein, and may not necessarily achieve other objectives or advantages taught or suggested herein.

[0031] All of these embodiments are intended to be within the scope of the invention as disclosed herein. These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of specific embodiments with reference to the accompanying drawings, and the invention is not limited to any specific embodiment disclosed. Brief explanation of the drawing

[0032] A more complete understanding of the embodiments of the present disclosure can be obtained by referring to the detailed description of the invention and the claims in conjunction with the following exemplary drawings. FIG. 1 illustrates a method according to an exemplary embodiment of the present disclosure. FIGS. 2 to 7 illustrate a structure formed according to an example of the present disclosure. FIG. 8 illustrates another method according to an example of the present disclosure. FIGS. 9 to 12 illustrate a structure formed according to additional examples of the present disclosure. FIG. 13 illustrates a schematic diagram of a reactor system according to an example of the present disclosure. FIG. 14 illustrates a schematic diagram of a reactor system having multiple reaction chambers according to an example of the present disclosure. FIG. 15 illustrates another structure according to an example of the present disclosure. It should be understood that the elements of the drawings are depicted in a simplified and clear manner and are not necessarily depicted in actual proportion. For example, to aid in understanding the embodiments illustrated in this disclosure, the dimensions of some components in the drawings may be exaggerated compared to other components. The examples presented herein are not intended to represent the actual appearance of any specific material, structure, or system, but are merely representations used to describe the embodiments of this disclosure. Specific details for implementing the invention

[0033] Although specific embodiments and examples are disclosed below, those skilled in the art will understand that the scope of the invention extends to the embodiments and / or uses of the invention specifically disclosed and obvious variations and equivalents thereof. Accordingly, the scope of the disclosed invention should not be limited by the specific embodiments disclosed below.

[0034] As described in more detail below, various embodiments of the present disclosure provide a method for selectively depositing a material on one surface or region compared to other surfaces or regions. The method described herein can be used to form a structure that can be used to form electronic devices, such as semiconductor devices, microelectromechanical devices, optoelectronic devices, etc.

[0035] As used herein, the term substrate may refer to any underlying material or materials that can be used to form a device, circuit, or film, or upon which a device, circuit, or film may be formed. The substrate may include a bulk material such as silicon (e.g., single-crystal silicon), other Group IV materials such as germanium, or other semiconductor materials such as Group II-VI or Group III-V semiconductor materials, and may include one or more layers placed on or beneath the bulk material. Additionally, the substrate may include various features formed within or on at least a portion of the layer of the substrate, such as indentations and protrusions, etc. As an example, the substrate may include a semiconductor material. An exemplary substrate comprises a first region of a first substrate material and a second region of a second substrate material, wherein the first substrate material and the second substrate material are different. The first region has a surface that may be called a "first surface," and deposition "on the first region" is deposition "on the first surface." The second region has a surface that may be referred to as a "second surface," and deposition "on the second region" is deposition "on the second surface." As the process proceeds, for example, when a material is deposited on the first region, the properties of the material on the surface of the first region may change. Typically, the material of the first region is initially a first substrate material and may change to include a blocking layer and / or a second material. As the process proceeds, for example, when a material is deposited on the second region, the properties of the material on the surface of the second region may change. Typically, the material of the second region is initially a second substrate material and may change to include the first material.

[0036] As used herein, the structure may be a substrate as described herein or may include such a substrate. The structure may include a substrate and one or more layers disposed on the substrate, for example, one or more layers formed by a method according to the present disclosure.

[0037] As used herein, the term film and / or layer may refer to any continuous or discontinuous structure and material, such as a material deposited by the method disclosed herein. For example, the film and / or layer may comprise a two-dimensional material, a three-dimensional material, nanoparticles, a partial or whole molecular layer or a partial or whole atomic layer or an atomic and / or molecular cluster. The film or layer may be partially or wholly composed of a plurality of dispersed atoms embedded on the surface of a substrate and / or within the substrate, or embedded in a device fabricated on the substrate. The film or layer may comprise a material or layer having pinholes and / or isolated islands.

[0038] As used herein, the term metallic surface may refer to a surface containing a metallic component, including but not limited to metal surfaces (e.g., metal elements or metal alloys), metal oxide surfaces, metal silicide surfaces, metal nitride surfaces and metal carbide surfaces, and mixtures thereof. The term metallic surface may also include a surface of a natural oxide of a metallic material.

[0039] As used herein, the terms silicon surface or silicon-containing surface may refer to a surface containing silicon and may contain additional elements. Exemplary silicon-containing materials include, for example, silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, silicon carbonitride, and mixtures thereof.

[0040] The terms periodic deposition process or cyclic deposition process may refer to the deposition of a layer on a substrate by sequentially introducing precursors (and / or reactants) into a reaction chamber, and include processing techniques such as atomic layer deposition (ALD), molecular layer deposition (MLD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes including ALD and cyclic CVD components. In some cases, a cyclic deposition process may include a step of continuously flowing one or more precursors, reactants, or inert gases, and a step of pulse-injecting something other than said precursors or reactants. The term MLD may refer to a vapor deposition process in which one or more deposition cycles are performed in a reaction chamber. Typically, during each cycle, an organic precursor is chemiosorbed onto a deposition surface (e.g., a substrate surface, or a previously deposited underlying surface, such as material from a previous MLD cycle) and typically forms a single molecular layer that does not readily react with additional organic precursors (i.e., a self-limiting reaction). Subsequently, if desired, another precursor (e.g., another organic precursor) can be subsequently introduced into the process chamber to be used to form the desired organic material on the deposition surface. Additionally, a purge step may be used during each cycle to remove excess organic precursors from the process chamber and / or remove excess reaction byproducts from the process chamber after the formation of the desired organic material.

[0041] As used herein, the term purging may refer to a procedure in which an inert or substantially inert gas is supplied to a reaction chamber between two pulses of gases that may react differently. For example, purging using an inert gas, such as a noble gas, may be provided between a precursor pulse and a reactant pulse to reduce gas-phase interactions that may otherwise occur between the precursor and the reactant. It should be understood that purging may be performed temporally, spatially, or both. For example, in the case of temporal purging, the purging step may be used in a temporal sequence of steps, for example, providing a precursor to the reaction chamber, providing a purging gas to the reaction chamber, and providing a reactant or other precursor to the reaction chamber, and the substrate on which the layer is deposited does not move. In the case of spatial purging, the purging step may take the following form, namely, moving the substrate from a first location where the precursor is supplied (e.g., continuously) to a second location where the reactant or other precursor is supplied (e.g., continuously) through a purging gas curtain.

[0042] Additionally, in this disclosure, any two numeric values ​​of a variable may constitute an actionable range of the variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable may refer to an exact or approximate value (whether indicated by the term "approximately"), may include equivalents, and may refer to an average value, median, representative, or majority, etc. For example, the term "approximately" may refer to + / - 20, 10, 5, 2, or 1 percent of the value. The terms "comprising," "constituting," and "having" independently refer to "typically or approximately comprising," "comprising," "essentially made of," or "made of" in some embodiments. In this disclosure, any arbitrarily defined meaning does not necessarily exclude the general and conventional meaning in some embodiments.

[0043] Although many exemplary materials are given through embodiments of the present disclosure, it should be noted that the chemical formula given for each exemplary material should not be understood as limiting, and that a given non-limiting exemplary material should not be limited by the given exemplary stoichiometry.

[0044] As described above, various examples of the present disclosure relate to the selective formation of a material on one surface compared to another surface. Selectivity for the formation or deposition of a material may refer to a relatively larger amount of material formed or deposited on one surface compared to another surface. For example, deposition selectivity on surface A compared to surface B may be given as a percentage calculated by [(deposition on surface A) - (deposition on surface B)] / (deposition on surface A). Deposition may be measured in any various manner. For example, deposition may be given as a measured thickness of the deposited material or as a measured amount (e.g., weight) of the deposited material.

[0045] As described in more detail below, in an embodiment described herein, the selective deposition of a passivation film may be performed on a first region (A) relative to a second region (B). Subsequently, a first material may be selectively deposited on the second region (B) relative to the passivation film (A). Additionally, a second material may be selectively deposited on the first region (A) relative to the first material / second region (B). In some embodiments, the selectivity is greater than about 10%, or greater than about 50%, or greater than about 75%, or greater than about 85%, or greater than about 90%, or greater than about 93%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or even greater than about 99.5%.

[0046] In some embodiments, deposition occurs on only one surface and not on another surface. It will be understood that a partially selective process can result in a completely selective structure, for example, by post-deposition treatment.

[0047] Now, looking at the drawings, FIG. 1 illustrates a method (100) for selectively depositing a material on the surface of a substrate according to an embodiment of the present disclosure. The method (100) comprises the steps of providing a substrate in a reaction chamber of a reactor (102), providing a first silanol to selectively form a blocking layer (104), selectively depositing a first material (106), selectively performing a processing step (108), providing a second silanol and / or an activating compound (110), selectively performing a processing step after step (110) (112), selectively depositing a second material (114), and removing the first material (116).

[0048] During step (102), a substrate is provided within a reaction chamber. The reaction chamber may be a standalone reaction chamber or part of a cluster tool, such as a cluster tool described in more detail below. The reaction chamber may include a substrate heater for heating the substrate to the temperature mentioned herein. Additionally, or alternatively, the reaction chamber may include a rapid heat treatment device, such as a lamp, for heating the substrate.

[0049] A reaction chamber may be configured to perform all or part of the steps of the method (100). In some embodiments of the present disclosure, a first reaction chamber may be configured to perform one or more steps of the method (100), and additional reaction chamber(s) may be used for other steps of the method (100). However, in further embodiments of the present disclosure, the first reaction chamber may be configured to perform all steps of the method (100).

[0050] Reactor and associated reaction chamber(s) capable of performing one or more steps of the method (100) include an atomic / molecular layer deposition (ALD / MLD) reaction chamber, a plasma-enhanced atomic layer deposition (PEALD) reaction chamber, as well as a chemical vapor deposition (CVD) reaction chamber equipped with suitable equipment and means for providing a precursor. In some embodiments, a showerhead reaction chamber may be used. In some embodiments, a plasma reaction chamber, such as a PEALD reaction chamber, may be used. In these embodiments, the plasma may be direct to, remote from, or near the substrate. In some embodiments, the reactor is a spatially separated ALD reactor in which the substrate moves or rotates during the process. In some cases, the reactor is a thermal reactor.

[0051] In some embodiments, a batch reactor may be used. In some embodiments, a vertical batch reactor in which a boat rotates during process processing is used. For example, a vertical batch reactor may include a reaction chamber, and an elevator configured and arranged to move a boat configured to support a batch of 10 to 200 substrates inside or outside the reaction chamber.

[0052] In another embodiment, the batch reactor comprises a mini-batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 wafers. In some embodiments where the batch reactor is used, the wafer-to-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0053] The method (100) may be optionally performed in a reactor and associated reaction chamber forming a cluster tool. In the cluster tool, each reaction chamber may be dedicated to one type of process, so, for example, the temperature of the reaction chamber within each module may be maintained constant, which can improve throughput compared to a reaction chamber where the substrate is heated to the process temperature before each process run. Additionally, in the cluster tool, the time required to pump the reaction space to a desired process pressure level between substrates may be reduced. In some embodiments of the present disclosure, the standalone reactor may be equipped with a load-lock. In this case, it may not be necessary to cool the reaction space between each process run.

[0054] FIG. 2 illustrates a substrate (200) that may be supplied during step (102). The substrate (200) provided during step (102) may include a first region (202) and a second region (204). The first region (202) may include a first substrate material (206), and the second region (204) may include a second substrate material (208) that is different from the first substrate material (206). For example, the first region (202) may be a metal or may include it. In some cases, the first substrate material (206) is a metallic material. In some cases, the first region (202) may be or may include a (e.g., transition) metal oxide, (e.g., transition) metal nitride, (e.g., transition) metal carbide, etc. In some cases, the first region (202) may comprise a high dielectric constant material (e.g., a dielectric constant higher than that of silicon oxide). Exemplary high dielectric constant materials include transition metal oxides such as, for example, hafnium oxide, zirconium oxide, yttrium oxide, aluminum oxide, titanium oxide, and mixtures thereof. As a specific example, the first region may be W, Co, Cu, TiN, TaN x , TiO x , AlOx , HfO x , ZrO x , or YO x It may include one or more of the following.

[0055] In some cases, the first region may include a plurality of metal-containing materials. For example, the first region may include a liner or barrier layer material and a filler material, such as a metal or a metal alloy.

[0056] The second region (204) and / or the second substrate material (208) may be silicon or may include silicon. As an example, the second region (204) is silicon, a silicon surface having a natural oxide (also in the form of silicon oxide) formed thereon, SiCO x , SiO x It may be SiO2, SiC, SiOC, SiCN, SiON, SiOCN, SiGe, SiN, etc., or a combination thereof, or may include. Alternatively, the second region and / or the second substrate material may be made of carbon or essentially made of carbon. For example, the second region may contain mainly carbon and other elements, such as hydrogen. In this case, the second region may contain a carbon layer or an amorphous carbon layer.

[0057] Once the substrate is loaded into a suitable reaction chamber, the substrate may be heated to a suitable temperature for, for example, degassing or a subsequent step (104). As an example, the substrate may be heated to a temperature of about 150°C to about 250°C or about 250°C to about 400°C. During step (102), the pressure inside the reaction chamber may be about 1 to about 5 or about 5 to about 10 Torr.

[0058] During step (104), a first silanol is provided to the reaction chamber to selectively form a blocking layer on the first region relative to the second region. FIG. 3 illustrates a structure (300) comprising a blocking layer (302) selectively formed on the first region (202) relative to the second region (204).

[0059] The first silanol may be an organic silanol. As an example, the first silanol may be a compound represented by the following chemical formula or may include the same:

[0060] Si a R x (OH) y (OR') z

[0061] Here, a is 1, 2, or 3, x is 1, 2, or 3, y is 1 or 2, z is an integer satisfying z = 4-xy for each silicon atom of the compound, each R is independently selected from a linear or branched C1-C8 or C1-C6 alkyl group, and each R' is independently selected from a linear or branched C1-C8 or C1-C6 alkyl group. The alkyl and alkoxy ligands may or may not contain internal or terminal alkene or alkyne functional groups.

[0062] As a specific example, the first silanol may be one or more of bis(tert-pentoxy)methylsilanol, tert-butyl(tert-butoxy)silanediol, tert-pentyl(tert-pentoxy)silanediol, or tert-pentyl(tert-butoxy)silanediol, or may include the same.

[0063] During step (104), the temperature inside the reaction chamber may be about 200°C to about 300°C or about 300°C to about 400°C. The pressure inside the reaction chamber may be about 0 Torr to about 5 Torr or about 5 Torr to about 20 Torr.

[0064] The thickness of the blocking layer (e.g., blocking layer (302)) on the first region may be about 0.1 nm to about 1 nm or about 0.2 nm to about 1 nm. The selectivity of the material deposited on the first region compared to the second region may be as described above.

[0065] During step (106), the first material is selectively deposited on the second region relative to the first region / blocking layer. FIG. 4 illustrates a structure (400) comprising the first material (402) placed on the second region (204). In this context, the deposited first material is distinguished from the first substrate material of the substrate.

[0066] According to an example of the present disclosure, the first material is a polymer or comprises the same. According to a further example, the first material is an organic material or comprises the same. According to a specific example, the first material comprises one or more of polyimide, polyamide, dimer, trimer, polyurethane, polythiourea, polyester, polyimine, or self-assembled monolayer material, or other polymers that may optionally be formed on the region (204).

[0067] Various precursors and reactants may be used to deposit the first material. Exemplary first material precursors and / or reactants include polyimide precursors, SAM precursors, small molecule inhibitor precursors, and region-selective deposition precursors. In some cases, the first material is selectively deposited using the first material precursor and the first material reactant.

[0068] In some embodiments, the (e.g., organic) polymer is deposited by a cyclic process. For example, the deposition of the organic polymer may be an MLD process. In some embodiments, a cyclic deposition process for depositing the organic polymer includes the step of providing a first material reactant and a first material precursor into a reaction chamber in an alternating sequential manner.

[0069] In some embodiments, the organic polymer precursor / reactant for use in the selective deposition of an organic polymer may be an aliphatic compound comprising 1 to 6 carbon atoms, 2 to 5 carbon atoms, 2 to 4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms. In some embodiments, the bonds between carbon atoms in the reactant or precursor may be single bonds, double bonds, triple bonds, or some combination thereof. In some embodiments, the first material reactant may comprise two amino groups.

[0070] In some embodiments, the amino group of the first material reactant may be present at one or both end positions on the aliphatic carbon chain. However, in some embodiments, the amino group of the first material reactant may not be present at either end position on the aliphatic carbon chain. In some embodiments, the first material reactant may comprise a diamine. In some embodiments, the first material reactant may comprise an organic polymer precursor selected from the group consisting of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopropane, 2,3-butanediamine, and 2,2-dimethyl-1,3-propanediamine.

[0071] The first material reactant according to the present disclosure may comprise at least two carbon atoms and may be, for example, 1,2-diaminoethane. In some embodiments, the first material reactant comprises three carbon atoms. In some embodiments, the first material reactant comprises four carbon atoms. For example, the first material reactant may be selected from 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, and 2,4-diaminobutane. Thus, in some embodiments, at least one of the amino groups is attached to one carbon atom bonded to two other carbon atoms. That is, at least one of the amino groups may be located at the end of the carbon chain. In some embodiments, the diamine according to the present disclosure comprises five carbon atoms. In some embodiments, the diamine according to the present disclosure comprises six carbon atoms.

[0072] In some embodiments, the carbon chain of the first material reactant is branched. Thus, there is at least one carbon atom bonded to three or four other carbon atoms. In some embodiments, the first material reactant has one such branching position. In some embodiments, the first material reactant has two such branching positions. In some embodiments, there are three or more branching points. In some embodiments, the side chain from the long carbon chain is a methyl group. In some embodiments, the side chain from the long carbon chain is an ethyl group. In some embodiments, the side chain from the long carbon chain is a propyl group. In some embodiments, the side chain from the long carbon chain is an isopropyl group. In some embodiments, the side chain from the long carbon chain is a butyl group. In some embodiments, the side chain from the long carbon chain is a tert-butyl group. In some embodiments, the side chain from the long carbon chain is a tert-butyl group. In some embodiments, the side chain of the first material reactant is a linear alkyl chain. In some embodiments, the side chain of the first material reactant is a branched alkyl chain. In some embodiments, the side chain of the first material reactant is a cyclic alkyl chain.

[0073] In some embodiments, the first material reactant is a C2 to C11 compound. The number of carbon atoms in the first material reactant typically affects the volatility of the compound, so that a higher weight compound may not be as volatile as a smaller compound. However, it has been found that a medium-sized first material reactant containing, for example, four, five, or six carbon atoms may have characteristics suitable for use as the first material reactant in the selective deposition process according to the present disclosure. For example, 1,3-diaminopentane is a liquid at room temperature, has a boiling point of 164°C under atmospheric pressure, a vapor pressure of about 2.22 Torr at 25°C, and reaches a vapor pressure of 1 Torr at temperatures below 20°C. Therefore, when 1,3-diaminopentane is used as the first material reactant for organic polymer deposition according to the present disclosure, the precursor container does not need to be heated. This may be advantageous for the tool-use life of the precursor, as the precursor may have a lower tendency to decompose during continuous use. In addition, liquid precursors have the advantage that precursor container loading is cheaper than in the case of solid precursors. In some embodiments, the first material reactant comprises 1,3-diaminopentane.

[0074] In some embodiments of the present disclosure, the amine group of the first material reactant is attached to a non-adjacent carbon atom. This may have the advantage of availability of the amine group for reaction with the first material precursor. In some embodiments, there is one carbon atom between the amino group-bonded carbon atoms. In some embodiments, there is at least one carbon atom between the amino group-bonded carbon atoms. In some embodiments, there are two carbon atoms between the amino group-bonded carbon atoms. In some embodiments, there are at least two carbon atoms between the amino group-bonded carbon atoms. In some embodiments, there are three carbon atoms between the amino group-bonded carbon atoms. In some embodiments, there are at least three carbon atoms between the amino group-bonded carbon atoms. In some embodiments, there are four carbon atoms between the amino group-bonded carbon atoms. In some embodiments, there are at least four carbon atoms between the amino group-bonded carbon atoms.

[0075] In some embodiments, the first material reactant comprises 1,5-diamino-2-methylpentane. Although the vapor pressure of 1,5-diamino-2-methylpentane is lower than that of 1,3-diaminopentane, it is also liquid at ambient temperature and requires a suitable temperature of about 40°C to reach a vapor pressure of 1 tor.

[0076] In some embodiments, the carbon atom bonded to the amine nitrogen in the first material reactant is bonded to at least two carbon atoms. Thus, in some embodiments where the first material reactant comprises five or more carbons, at least one of the amino groups may be located far from the end of the carbon chain. The structure of the first material reactant affects its properties in the vapor deposition process. Branching of the first material reactant, including the number of branches and the relative position of the amino group to the branches, can cause the deposited organic polymer to have different properties. Unless the present disclosure is limited to any specific theory, e.g., steric factors, a specific reaction may be preferred. This can provide the possibility to design a deposition process suitable for a given purpose by using different first organic polymer precursors, for example, taking into account the thermal budget, organic polymer growth rate requirements, and the required degree of selectivity.

[0077] In some embodiments, the first material reactant is a cyclic diamine. In some embodiments, the first material reactant comprises one or more of cyclopentanedialkylamine, cyclohexanedialkylamine, cyclopentadienedialkylamine, benzenedialkylamine, cyclopentanetrialkylamine, cyclohexanetrialkylamine, cyclopentadienetrialkylamine, or benzenetrialkylamine.

[0078] In some embodiments, the first material reactant is an aromatic diamine. In some embodiments, the aromatic diamine is diaminobenzene, e.g., 1,2-diaminobenzene, 1,3-diaminobenzene, or 1,4-diaminobenzene. In some embodiments, the aromatic diamine comprises an alkylamino group at at least one position. For example, the alkylamino group may be a C1 to C3 alkylamino group, e.g., -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2, or -CH2CH(CH3)NH2.

[0079] In some embodiments, the first material reactant is 1,3-diaminopentane, 1,4-diaminopentane, 2,4-diaminopentane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diaminobutane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,4-diamino-4-methylpentane, 1,3-diaminobutane, 1,5-diaminohexane, 1,3-diaminohexane, 2,5-diaminohexane, 1,3-diamino-5-methylhexane, 4,4,4-trifluoro-1,3-diamino-3-methylbutane, 2,4-diamino-2-methylpentane, 4-(1-methylethyl)-1,5-diaminohexane, 3-aminobutanamide, It is selected from the group consisting of 1,3-diamino-2-ethylhexane, 2,7-diamino-2,7-dimethyloctane, 1,3-diaminobenzene, and 1,4-diaminobenzene. In some embodiments, the first material reactant comprises a halogen.

[0080] In some embodiments, triamines may be used as a first material reactant in the deposition of the organic polymer according to the present invention. The provision of such molecules may favorably affect the availability of polymerization sites in the second vapor-phase organic polymer precursor. The availability of three amine groups in a single molecule may lead to a denser polymer network, which in turn may reduce metal migration through the organic polymer. These characteristics may be advantageous in embodiments utilizing the organic polymer according to the present disclosure as a passivation layer. Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (having amines on carbons 1, 2, and 3 or carbons 1, 2, and 4), and triaminopentane (particularly having an amine on any one of carbons 1 and 5 + carbons 2, 3, or 4). Similarly, triaminohexane may contain an amine group at any one of positions 2, 3, 4, or 5 as well as carbons 1 and 6, triaminoheptane may contain an amine group at any one of positions 2, 3, 4, 5, or 6 as well as carbons 1 and 7, and triaminooctane may contain an amine group at any one of positions 2, 3, 4, 5, 6, or 7 as well as carbons 1 and 8. In addition, branched carbon chains, particularly 2-aminomethyl-1,3-diaminopropane, 2-aminomethyl-1,4-diaminobutane (or alternatives having two amino groups elsewhere in the butane chain), 2-aminomethyl-1,5-diaminopentane (or alternatives having two amino groups elsewhere in the pentane chain), 3-aminomethyl-1,5-diaminopentane (or alternatives having two amino groups elsewhere in the pentane chain), 2-aminomethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain), 3-aminomethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain), and 3-aminoethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain).In addition, aromatic triamines, such as 1,3,5-triaminobenzene, may be alternatives to certain embodiments.

[0081] In some embodiments, a first material reactant for use in the selective cyclic deposition process described herein may have the following chemical formula:

[0082] R 1 (NH2)2

[0083] Here, R 1 It may be an aliphatic carbon chain containing 1 to 5 carbon atoms, 2 to 5 carbon atoms, 2 to 4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms.

[0084] As a specific example, the first material reactant may be selected from the group consisting of 1,2-diaminoethane (l), 1,3-diaminopropane (l), 1,4-diaminobutane (l), 1,5-diaminopentane (l), 1,2-diaminopropane (l), 2,3-butanediamine, 2,2-dimethyl-1,3-propanediamine (l), 1,6-diaminohexane, 1,4-diaminocyclohexane, or any other monomer having two reactive groups, tris(2-aminoethyl)amine, or a cyclic compound having at least two primary amine groups, e.g., 1,4-diaminocyclohexane (mentioned above) or p-phenylenediamine).

[0085] In some embodiments, the first material precursor is an organic reactant capable of reacting with the first material reactant species adsorbed under deposition conditions. In some cases, the terms reactant and precursor may be used interchangeably.

[0086] In some embodiments, the first material precursor is an anhydride, e.g., furan-2,5-dione (maleic anhydride). The anhydride may be a dianhydride, e.g., pyromellitic dianhydride. In some embodiments, the first material precursor may be any other monomer having two reactive groups to react with the first reactant.

[0087] In some embodiments, the first material precursor and / or reactant does not contain metal atoms. In some embodiments, the first material precursor and / or reactant does not contain semimetal atoms. In some embodiments, one of the first material precursor and / or reactant comprises a metal or semimetal atom. In some embodiments, the first material precursor and / or reactant contains carbon and hydrogen, and one or more of the following elements: N, O, S, P, or halides, e.g., Cl or F.

[0088] In some embodiments, the first material precursor comprises an organic compound selected from the group consisting of 1,4-diisocyanatobutane or 1,4-diisocyanatobenzene. In some embodiments, the first material precursor comprises an organic precursor selected from the group consisting of terephthaloyl dichloride, alkyldioyl dichloride, e.g., hexanedioyl dichloride, octanedioyl dichloride, nonandioyl dichloride, decandioyl dichloride, or terephthaloyl dichloride. In some embodiments, the first material precursor comprises an organic precursor selected from the group consisting of 1,4-diisothiocyanatobenzene or terephthalaldehyde. In some embodiments, the first material precursor to be vaporized may be a diamine such as, for example, 1,4-diaminobenzene, decane-1,10-diamine, 4-nitrobenzene-1,3-diamine, 4,4'-oxydianiline, or ethylenediamine. In some embodiments, the first material precursor may be a terephthalic acid bis(2-hydroxyethyl) ester. In some embodiments, the first material precursor may be a carboxylic acid, e.g., an alkyl-, alkenyl-, alkadienyl-dicarboxylic acid, or a tricarboxylic acid, e.g., ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, or propane-1,2,3-tricarboxylic acid. In some embodiments, the first material precursor may be an aromatic carboxylic acid or a dicarboxylic acid, e.g., benzoic acid, benzene-1,2-dicarboxylic acid, benzene-1,4-dicarboxylic acid, or benzene-1,3-dicarboxylic acid. In some embodiments, the first material precursor may comprise one or more OH- groups bonded to a hydrocarbon. In some embodiments, the first material precursor may be selected from the group consisting of diols, triols, aminophenols, e.g., 4-aminophenol, benzene-1,4-diol, or benzene-1,3,5-triol. In some embodiments, the first material precursor may be 8-quinolinol. In some embodiments, the first material precursor may include an alkenylchlorosilane such as alkenyltrichlorosilane, e.g., 7-octenyltrichlorosilane.

[0089] Exemplary SAM precursors include octadecyl-tris(dimethylamino)silane, octyl-tris(dimethylamino)silane, octadecyltrichlorosilane, octyl-trichlorosilane, octyl-trimethoxysilane, other trihalosilanes having C1 to C20 alkyl chains, and other trialkoxysilanes having C1 to C20 alkyl chains.

[0090] An exemplary small molecule inhibitor precursor comprises a silylating agent. The silylating agent according to the present disclosure may be provided in a gas phase. In some embodiments, the silylating agent comprises one or more of allyltrimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)diethylsilane, halosilane, e.g., chlorotrimethylsilane or octadecyltrichlorosilane, imidazole, e.g., N-(trimethylsilyl)imidazole, silazane, e.g., hexamethyldisilazane, silylamine, e.g., N-(trimethylsilyl)dimethylamine or 1,1,1-trimethoxy-N,N-dimethylsilanamine, or pyrrole, e.g., 1-(triisopropylsilyl)pyrrole. The substrate may be in contact with a sufficient amount of the blocking agent for a sufficient time during which the top surface is selectively blocked by silicon species. In some embodiments, the second substrate material is not passivated to a self-assembled monolayer (SAM).

[0091] An exemplary region-selective deposition precursor may comprise one or more metal precursors, such as Group 13 (e.g., Al, Ga, and / or In) precursors, transition metal (e.g., Ti, Zr, and / or Hf, excluding technetium) precursors, rare earth metal (e.g., Y, La, and / or Sc) precursors, and / or Group 14 metal or metalloid (e.g., Si) precursors. One or more suitable reactants may be used to form oxides, nitrides, and / or carbides comprising one or more of these metals. For example, the selective deposition precursor and reactants may be used to deposit one or more of AlO, SiO, TiO, ZrO, HfO, YO, LaO, ScO, TiN, SiN, AlN, ZrN, HfN, LaN, ScN, etc.

[0092] An exemplary metal precursor suitable for zone-selective deposition comprises a heteroleptic precursor comprising a metal, at least one cyclopentadienyl ligand, and at least one amidinato ligand. In this context, Si may be considered a metal. In some embodiments, the cyclopentadienyl ligand comprises at least one C1 to C5 alkyl substituent. In some embodiments, the alkyl substituent is selected from the group consisting of methyl, ethyl, and linear or branched alkyl groups containing three, four, or five carbon atoms. In some embodiments, the metal precursor comprises two ethylcyclopentadienyl ligands. In some embodiments, the amidinato ligand comprises an acetamidinato ligand. In some embodiments, the acetamidinato ligand is an alkylacetamidinato ligand. In some embodiments, the alkylacetamidinato ligand is a dialkylacetamidinato ligand. In some embodiments, one or two alkyl groups of the alkylacetamidinato ligand are methyl, ethyl, n-propyl, isopropyl, n-butyl, Burst - Butyl and Sekh- It is selected from the group consisting of butyl. The reactant or oxygen precursor may be selected from the group consisting of molecular oxygen, ozone, hydrogen peroxide and water as described herein, or nitrating agents or carbonizing agents.

[0093] During step (106), the temperature inside the reaction chamber may be about 100°C to about 200°C or about 200°C to about 400°C. The pressure inside the reaction chamber may be about 0 Torr to about 5 Torr or about 5 Torr to about 20 Torr.

[0094] The thickness of the first material layer (e.g., the first material (402)) on the second region (204) may be about 0.1 nm to about 2.5 nm or about 2.5 nm to about 7.5 nm. The selectivity for the first material to be deposited on the second region relative to the first region may be as described above.

[0095] During step (108), optional treatment of the deposited first material is performed, for example, prior to step (110). In some cases, step (108) includes one or more of direct plasma treatment, remote plasma treatment, UV treatment, e-beam treatment, or the use of other energy beams. In some cases, step (108) includes the step of providing one or more gases to a reaction chamber. One or more gases may be used to form excited species using one or more of the excitation techniques mentioned herein. These gases may include one or more of Ar, N2, He, Ne, O2, H2, and any mixture thereof.

[0096] During step (110), a second silanol and / or an activating compound is provided. As described in more detail below, the second silanol may optionally remove the blocking layer from the first region and / or enhance or increase the growth of the second material on the first (or activated first) region. The activating compound, which may be the second silanol, enhances or increases the growth of the second material on the first (or activated first) region, which may still contain, may not contain, or may only partially contain the blocking layer.

[0097] The second silanol may be an organic silanol. As an example, the second silanol may be a compound represented by the following chemical formula or may include:

[0098] Si(OH) x (OR) y

[0099] Here, x is 1 or 2, y is 2 or 3, and each R is independently selected from linear or branched C1-C8 or C1-C6 alkyl groups. As a specific example, the second silanol may include one or more of tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol.

[0100] In an embodiment, the provided activating compound comprises a Group 13 element and is configured to enhance the growth of a material containing a Group 14 element during step (114). The activating compound may include an aluminum-containing species capable of forming a surface aluminoxy or aluminate termination on the first region (202). Examples include a vapor phase aluminum alkoxide or a low-dose pulsed aluminum organometallic precursor. For example, if the Group 14 element is silicon, the presence of the aluminum-derived surface site modifies the barrier layer and increases the reactivity of the first region to a silicon precursor used to form a silicon-containing second material, such as silicon oxide.

[0101] In an embodiment, the provided activating compound comprises a Group 14 element and is configured to enhance the growth of a material containing a Group 13 element during step (114). In particular, a silicon-containing activating compound, e.g., a second silanol, may be provided to form surface siloxy and / or silanol terminations on the first region (202) without substantially depositing a bulk silicon-containing film. Suitable activating species include gaseous silanols and alkoxysilanes, e.g., tris(tert-butoxy)silanol or tris(tert-pentoxy)silanol. The presence of silicon-derived -Si-O(H) surface sites modifies the blocking layer and increases the reactivity of the first region to an aluminum precursor used to form an aluminum-containing second material, e.g., aluminum oxide, thereby increasing the nucleation density per cycle and initial growth while maintaining selectivity.

[0102] FIG. 5 illustrates a structure (500) comprising a surface (502) that is removed and / or activated using a second silanol (e.g., for subsequent material deposition).

[0103] During step (110), the temperature inside the reaction chamber may be about 100°C to about 200°C or about 200°C to about 400°C. The pressure inside the reaction chamber may be about 0 Torr to about 5 Torr or about 5 Torr to about 20 Torr. In some cases, steps (104 and 110) may be performed in the same reaction chamber. In some cases, the deposition and / or processing steps of different materials may be performed in the same or different reaction chambers.

[0104] As illustrated in FIG. 1, the method (100) may include a processing step (112) after step (110). The processing step (112) may be any processing step described above in relation to step (108) or may include such a step. If the method (100) includes both steps (108 and 112), each processing step may be the same or different, for example, the time, type, power, etc. used to form the species here may be different.

[0105] During step (114), the second material is optionally deposited on the first region (202). FIG. 6 illustrates a structure (600) comprising a second material (602) formed on a first substrate material (206). Depending on the example, the second material comprises a metal or a semiconductor. Depending on further examples, the second material is a conductive or high dielectric constant material. In some cases, the second material is or comprises a metal oxide, a semiconductor oxide, a metal nitride, or a metal carbide. In some cases, the second material is or comprises silicon oxide, aluminum oxide, yttrium oxide, titanium nitride, or silicon nitride. The second material may be doped and / or oxidized. For example, the second material may be carbon-doped silicon nitride or carbon oxide-doped silicon nitride.

[0106] The step (114) of selectively depositing a second material on a first region relative to a second region may include a cyclic deposition process. The step (114) may include providing a metal precursor and providing a reactant comprising one or more of a reducing agent, an oxidizing agent, a carbonizing agent, or a nitrating agent. These steps may be separated by a purge step.

[0107] An exemplary metal precursor suitable for use in step (114) comprises a metal and one or more ligands. As an example, the ligand may comprise one or more of alkyl, alkoxide, diketonate, acetamidinate, formamidinate, guanidinate, amide, alkoxyamine, aryl, cyclopentadienyl, and halogen.

[0108] Exemplary reducing agents suitable for use during step (114) include H2, etc. Exemplary oxidizing agents suitable for use during step (114) include O2, H2O, H2O2, O radicals, O ions, alcohols, e.g., ethanol, isopropanol, tert-butanol, etc. Exemplary carbonizing agents suitable for use during step (114) include methane, ethane, etc. Exemplary nitrating agents suitable for use during step (114) include N2, NH3, NH2-NH2, alkyl hydrazine.

[0109] When step (110) includes an activating compound comprising a group 14 element, silicon (e.g., the activating compound is a second silanol), the second material selectively deposited on the first region may include, for example, aluminum oxide. In some embodiments, the cyclic deposition process includes an aluminum precursor, e.g., trimethylaluminum, and alternating pulses of an oxidizing agent, e.g., water, hydrogen peroxide, ozone, or oxygen plasma, along with an intermediate purge. Without being bound by theory, the activation achieved by the second silanol is determined to increase growth per cycle, reduce incubation delay, improve selectivity of Al2O3 on the first region compared to the second region, while maintaining blocking performance over the first material on the second region.

[0110] If step (110) includes an activating compound comprising a group 13 element, such as aluminum, the second material selectively deposited on the first region may include, for example, silicon oxide. In some embodiments, the cyclic deposition process includes alternating pulses of a silicon precursor, such as silanol or alkoxysilane (e.g., tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, or tetraethyl orthosilicate), and an oxidizing agent, such as water, hydrogen peroxide, ozone, or oxygen plasma, along with an intermediate purge. Without being bound by theory, the activation achieved by the aluminum-containing species is determined to increase growth per cycle, reduce incubation delay, and improve selectivity of SiO2 on the first region compared to the second region, while maintaining blocking performance over the first material on the second region.

[0111] During step (116), the first material is optionally removed. FIG. 7 illustrates a structure (700) in which the first material (402) is optionally removed from the second region (204). Step (116) may include any suitable process, such as a direct, indirect, or remote plasma process that generates excited hydrogen species. As a specific example, step (116) may include a hydrogen (e.g., H2) plasma process.

[0112] FIG. 15 illustrates a structure (1500) comprising a second material (1502) optionally formed on a first region (1504) comprising a barrier or liner layer (1506) (e.g., metal nitride, e.g., TiN, TaN, MoN, Ru) as described herein) and a bulk metallic surface (1508). The surface (1510) may be a silicon-containing surface as described above.

[0113] FIG. 8 illustrates another method (800) for selectively depositing a material on the surface of a substrate. The method (800) comprises the steps of providing a substrate within a reaction chamber of a reactor (802), providing a first silanol to selectively form a blocking layer (804), selectively depositing a first material (806), selectively performing a processing step (808), and providing a second silanol and / or an activating compound (810). FIG. 9 through 12 illustrate a structure that can be formed using the method (800).

[0114] Steps (802, 804, 808, and 810) may be identical or similar to the aforementioned steps (102, 104, 108, and 110). Method (800) differs from method (100) in that it does not require the deposition of a second material and may include the deposition of a different type of material during step (806) compared to the material deposited during step (106).

[0115] FIG. 9 illustrates a substrate that may be provided during step (802). The substrate (900) may be identical or similar to the aforementioned substrate (200). Similar to the substrate (200), the substrate (900) comprises a first region (902), a second region (904), a first substrate material (906), and a second substrate material (908), which may be identical or similar to the aforementioned first region (202), second region (204), first substrate material (206), and second substrate material (208).

[0116] FIG. 10 illustrates a structure (1000) formed during step (804). The structure (1000) may be identical or similar to the aforementioned structure (300). The structure (1000) includes a blocking layer (1002) optionally formed over the first region (902) relative to the second region (904).

[0117] Similar to step (106), during step (806), the first material is optionally deposited on the second region. FIG. 11 illustrates a structure (1100) formed during step (806). As illustrated, the structure (1100) includes the first material (1102) optionally formed on the second region (904).

[0118] The first material (1102) may be a metal oxide, a metal nitride, a metal carbide, a metal oxide, a metal nitride, or a metal carbide, or may include the same. As an example, the metal oxide, nitride, or carbide may include one or more metals, e.g., one or more Group 13, transition metals, and / or rare earth metals. The metal oxide, nitride, or carbide may include one or more of Si, Ge, etc.

[0119] According to an example of the present disclosure, step (806) includes providing a metal (or metalloid) precursor and providing a reactant comprising one or more of a reducing agent, an oxidizing agent, a carbide, or a nitriding agent. Step (806) may be a cyclic deposition process or may include such a process.

[0120] According to an example of the present disclosure, the metal or metalloid precursor may comprise a metal or one or more ligands. Exemplary ligands may comprise alkyl, alkoxide, diketonate, acetamidinate, formamidinate, guanidinate, amide, alkoxyamine, aryl, cyclopentadienyl, and halogen. As an example, the metal precursor may comprise one or more metal precursors, e.g., a Group 13 (e.g., Al, Ga, and / or In) precursor, a transition metal (e.g., Ti, Zr, and / or Hf, excluding technetium) precursor, a rare earth metal (e.g., Y, La, and / or Sc) precursor, and / or a Group 14 metal or metalloid (e.g., Si) precursor. Exemplary reducing agents, oxidizing agents, carbizing agents, or nitrating agents include those provided above in connection with step (114).

[0121] During step (810), a second silanol and / or an activating compound is provided. The second silanol may optionally remove the blocking layer from the first region and / or enhance or increase the growth of the second material on the first (or activated first) surface. The activating compound, which may be the second silanol, enhances or increases the growth of the second material on the first (or activated first) surface, which may still contain, may not contain, or may only partially contain the blocking layer. FIG. 12 illustrates a structure (1200) after step (810). The structure (1200) includes an activated surface (1202).

[0122] Now, referring to FIG. 13, in various examples, a reactor system (1300) comprises a reaction chamber (1304), a susceptor (1306) for securing a substrate (1330) during processing, a fluid distribution system (1308) (e.g., a showerhead) for dispensing one or more precursors and / or reactants onto the surface of the substrate (1330), one or more precursor or reactant sources (1310, 1312 and / or 1313) fluidly coupled to the reaction chamber (1304) through respective lines (1316, 1318, 1319 and 1320), and / or a transport and / or purge gas source (1314), and respective valves or controllers (1322, 1323, 1325 and 1326). The substrate (1330) may comprise a substrate or structure as described herein. The purge / carry gas (1324) from the gas source (1314) may flow into the reaction chamber (1304) and pass through it to act as a carrier gas, or may purge or remove any excess reactant or other unwanted material from the reaction chamber (1304). The sources (1310, 1312, and 1313) may include a vessel and a precursor or reactant as described herein. For example, the source (1310) may include a vessel and a first silanol (1315), the source (1312) may include a vessel and a second silanol (1317), and the source (1313) may include a vessel and a first material precursor (1321). The reactor system (1300) may include additional sources. The system (1300) may also include a vacuum source (1328) fluidly coupled to the reaction chamber (1304). The vacuum source (1328) may be configured to exhaust reactants, purge gas, or other materials from the reaction chamber (1304).

[0123] Additionally, the reactor system (1300) may include a controller (1352). The controller (1352) may be configured to perform various functions and / or steps as described herein. The controller (1352) may include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although illustrated as a single unit, the controller (1352) may alternatively include multiple elements. The controller (1352) may be used to control gas flow (e.g., by monitoring flow rate and controlling valves (1322, 1323, 1325 and / or 1326)), motors, heaters, cooling devices, and / or vacuum sources (1328) to execute various processes (e.g., method (100) or method (800)). Additionally, if the system includes two or more reaction chambers, the two or more reaction chambers may be coupled to the same / shared controller, as described in more detail below. As an example, the controller (1352) may be configured to provide a first silanol to selectively form a blocking layer on a first region of the substrate relative to a second region of the substrate, selectively deposit a first material on the second region, and selectively provide a second silanol to remove the blocking layer and / or activate the first region.

[0124] FIG. 14 illustrates a reactor system (1440) comprising a plurality of reaction chambers (1402 to 1408), each of which may be an example of the reaction chamber (1304) of FIG. 13. The reaction chambers (1402 to 1408) may be positioned around a transfer chamber (1410) comprising a transfer tool (1412) for transferring a substrate between the reaction chambers (1402 to 1408) and the load lock chamber (1414) and between the reaction chambers (1402 to 1408) (e.g., through the transfer chamber (1410)). For example, the substrate (1330) may be positioned in different chambers for different steps of the method described herein. For example, one of the reaction chambers (1402 to 1408) may be used to form or provide a first silanol and / or a second silanol as described herein, another of the reaction chambers (1402 to 1408) may be used to selectively deposit a first material, another of the reaction chambers (1402 to 1408) may be used to selectively deposit a second material, and another of the reaction chambers (1402 to 1408) may be used to form a process as described herein. Other configurations are also possible in which one or more steps of the method (100 or 800) are performed within a single reaction chamber.

[0125] The exemplary embodiments of the foregoing disclosure do not limit the scope of the invention, for these embodiments are merely examples of embodiments of the invention as defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of the invention. In fact, in addition to what is shown and described herein, various variations of the disclosure, such as alternative useful combinations of the described elements, may become apparent from the description to those skilled in the art. Such variations and embodiments are also intended to be within the scope of the appended claims.

Claims

Claim 1 A method for selectively depositing a material on the surface of a substrate, the method comprising: providing a substrate within a reaction chamber of a reactor, wherein the substrate comprises a first region and a second region; providing a first silanol to selectively form a blocking layer on the first region relative to the second region; selectively depositing a first material on the second region; and providing a second silanol to modify the blocking layer. Claim 2 A method according to claim 1, wherein the first region comprises a metal. Claim 3 A method according to claim 1, wherein the second region comprises silicon or is essentially composed of carbon. Claim 4 A method according to claim 1, wherein the first material comprises a polymer. Claim 5 A method according to claim 1, further comprising the step of selectively depositing a second material on the first region compared to the second region. Claim 6 A method according to claim 5, wherein the second silanol is an activating compound that optionally removes the blocking layer from the first region and / or activates the blocking layer to enhance the growth of the second material on the first region. Claim 7 In paragraph 5, the method wherein the second material comprises a metal, a semiconductor, a metal oxide, a semiconductor oxide, a metal nitride, a semiconductor nitride, a metal carbide, or a semiconductor carbide. Claim 8 In claim 7, the method wherein the second material is silicon oxide, aluminum oxide, yttrium oxide, titanium nitride, or silicon nitride. Claim 9 In paragraph 5, the method wherein the second material is a conductive or high dielectric constant material. Claim 10 A method according to claim 5, wherein the step of selectively depositing the second material comprises a cyclic deposition process, and one or more cycles of the cyclic deposition process comprise: a step of providing a metal precursor; and a step of providing a reactant comprising one or more of a reducing agent, an oxidizing agent, a carbide, or a nitriding agent. Claim 11 In claim 10, the method wherein the metal precursor comprises a metal and one or more ligands. Claim 12 Method of claim 1, wherein the first silanol comprises a compound represented by the following chemical formula: Si a R x (OH) y (OR') z Here, a is 1, 2, or 3; x is 1, 2, or 3; y is 1 or 2; z is an integer satisfying z = 4-xy for each silicon atom of the compound; each R is independently selected from a linear or branched C1-C8 alkyl group; and each R' is independently selected from a linear or branched C1-C8 alkyl group. Claim 13 In claim 12, the method wherein the first silanol comprises one or more of bis(tert-pentoxy)methylsilanol, tert-butyl(tert-butoxy)silanediol, tert-pentyl(tert-pentoxy)silanediol, or tert-pentyl(tert-butoxy)silanediol. Claim 14 In claim 1, the second silanol comprises a compound represented by the following chemical formula: Si(OH) x (OR) y Here, x is 1 or 2; y is 2 or 3; and each R is independently selected from linear or branched C1-C6 alkyl groups. Claim 15 In claim 14, the method wherein the second silanol comprises one or more of tris(tert-pentoxy)silanol or tris(tert-butoxy)silanol. Claim 16 A method for selectively depositing a material on the surface of a substrate, the method comprising the step of providing a substrate within a reaction chamber of a reactor, wherein the substrate comprises a first region and a second region; the step of selectively forming a blocking layer on the first region relative to the second region by providing a first silanol; the step of selectively depositing a first material on the second region; the step of modifying the blocking layer by providing an activating compound; and the step of selectively depositing a second material on the first region relative to the second region, wherein the activating compound enhances the growth of the second material on the first region, and the activating compound comprises a group 13 element and the second material comprises a group 14 element, or the activating compound comprises a group 14 element and the second material comprises a group 13 element. Claim 17 In paragraph 16, the above Group 14 element is silicon, method. Claim 18 In claim 17, the method wherein the activating compound comprises the group 14 element and is a second silanol. Claim 19 In paragraph 16, the above-mentioned Group 13 element is aluminum, method. Claim 20 In paragraph 19, the method wherein the second material is aluminum oxide.

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