Pretreatment substrate for selective deposition

Abstract

An example provides a method for processing a substrate. The method includes performing a pre-treatment of a surface of a multi-region substrate, the multi-region substrate including regions including two or more of a polycrystalline silicon-containing semiconductor, a silicon-containing nitride, or a silicon-containing oxide. The surface on each region includes a natural silicon oxide layer. The pretreatment comprises a solvent-based vapor phase etching process in which at least hydrogen fluoride, a hydroxyl group-containing solvent, and an organic base flow through the surface. The method also includes performing selective deposition of a first molecular species on the pretreated surface such that the first molecular species is adsorbed to one or more regions and not to one or more other regions.

Description

Background Technology

[0001] Semiconductor device manufacturing processes involve many steps, including material deposition, patterning, and removal, to form integrated circuits on a substrate. Various methods can be used to selectively deposit material onto the substrate according to a pattern. One such method is photolithography. Photolithography involves exposing a photoresist layer on the substrate to a light pattern, and then developing the exposed photoresist layer. The development process removes certain areas of the photoresist but not others. The result is that some areas of the substrate are exposed, while other areas are protected by the photoresist. Material can then be deposited onto the exposed areas of the substrate.

[0002] Other methods utilize chemical differences between substrate surface regions to selectively adsorb processing chemicals onto certain substrate areas while sparing others. Utilizing substrate surface properties for selective deposition allows for patterned deposition of material without the use of photolithography. Furthermore, such methods facilitate precise alignment of the edges of the deposited film with the edges of the selected substrate material regions on which the film is deposited. Summary of the Invention

[0003] This invention is provided to introduce the chosen concepts in a simplified form, which will be further described in the following detailed implementations. This invention is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Furthermore, the claimed subject matter is not limited to implementations that address any or all of the shortcomings mentioned in any part of this disclosure.

[0004] An example provides a method for processing a substrate. The method includes performing a pretreatment of the surface of a multi-region substrate, the multi-region substrate including regions containing polycrystalline silicon semiconductors, silicon nitrides, or two or more of silicon oxides. The surface in each region contains a natural silicon oxide layer. The pretreatment includes a solvent-based vapor-phase etching process, wherein at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base are flowed through the surface. The method further includes performing selective deposition of a first molecule on the pretreated surface, such that the first molecule is adsorbed onto one or more regions but not onto one or more other regions.

[0005] In some such examples, the polysilicon semiconductor contains one or more of polysilicon or polysilicon germanium.

[0006] In some such examples, silicon nitrides contain one or more of silicon nitride or silicon germanium nitride.

[0007] In some such examples, the silicon oxide contains one or more of silicon oxide or silicon germanium oxide.

[0008] In some such examples, the first molecule contains a dielectric film precursor.

[0009] In some such examples, the dielectric film precursor comprises one or more of the following: aluminum oxide, titanium oxide, zinc oxide, silicon dioxide, silicon carbide, silicon carbide, silicon oxynitride, silicon carbonitride, hafnium oxide, tantalum nitride, titanium nitride, or silicon nitride.

[0010] In some such examples, the first molecule contains an inhibitor molecule.

[0011] In some such examples, the inhibitor molecule contains one or more of alkylsilane inhibitors or aminosilane inhibitors.

[0012] In some such examples, the organic base comprises one or more of imidazole, benzimidazole, histidine, guanidine, methylamine, aniline, dimethylamine, diphenylamine, aziridine, piperidine, pyridine, 2-aminopentane, triethylamine, cyclodiphosphazane, hexachlorophosphazene, or polyphosphazene.

[0013] In some such examples, the hydroxyl-containing solvent includes one or more of water, butanol, ethanol, methanol, isopropanol, diethylene glycol, ethylene glycol, methyl tert-butyl ether, or phenol.

[0014] In some such examples, the method further includes performing selective deposition of a second molecule on a pretreated surface, such that the second molecule is adsorbed onto one or more regions where the first molecule has not been adsorbed.

[0015] Another example provides a processing tool. The processing tool includes: a processing chamber, a substrate holder configured to hold a substrate positioned within the processing chamber; flow control hardware configured to control the flow rate of each of one or more processing chemicals into the processing chamber; and a controller. The controller is configured to control the processing tool to perform a solvent-based vapor-phase etching pretreatment by allowing at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base to flow over the surface of the substrate. The controller is further configured to control the processing tool to perform selective deposition of a first molecule onto the surface after the pretreatment, such that the first molecule adsorbs onto one or more regions and not onto one or more other regions.

[0016] In some of these examples, selective deposition is performed in a dry deposition manner.

[0017] In some of these examples, selective deposition is performed using a wet deposition method.

[0018] In some such examples, the flow controller is configured to co-vaporize the organic base with the hydroxyl-containing solvent.

[0019] In some of these examples, preprocessing is performed in a continuous flow manner.

[0020] In some such examples, the surface is not exposed to air between the pretreatment and selective deposition processes.

[0021] In some such examples, the first molecule contains a dielectric film precursor.

[0022] In some such examples, the first molecule contains an inhibitor molecule.

[0023] In yet another example, a method for processing a substrate is provided. The method includes performing a pretreatment of the surface of a multi-region substrate comprising regions of polysilicon, silicon nitride, or silicon oxide, or more thereof. The surface in each region comprises a natural silicon oxide layer. The pretreatment includes a solvent-based vapor phase etching process, wherein at least a halogen source, an organic solvent, and an additive are flowed through the surface. The method further includes performing selective deposition of a first molecule on the surface after pretreatment, such that the first molecule adsorbs onto one or more regions but not onto one or more other regions. Attached Figure Description

[0024] Figure 1A An exemplary multi-region substrate with a natural oxide layer is schematically shown.

[0025] Figure 1B The illustration shows the effect after the exemplary differential preprocessing. Figure 1A Possible surfaces of an exemplary multi-region substrate.

[0026] Figure 1C The illustration schematically shows the selective deposition of an exemplary first molecule. Figure 1B An exemplary pretreated multi-region substrate.

[0027] Figure 1D The illustration schematically shows the selective deposition of an exemplary second molecule. Figure 1C An exemplary pretreated multi-region substrate.

[0028] Figure 2 A flowchart depicts an exemplary method comprising a processing substrate that performs differential preprocessing.

[0029] Figure 3 It is a histogram depicting the surface differences between polycrystalline silicon and silicon nitride after a series of pretreatments and inhibitor exposures.

[0030] Figure 4 It is a histogram depicting the surface differences between polysilicon and silicon nitride after an exemplary differential pretreatment.

[0031] Figure 5 It is a histogram depicting the surface differences between polycrystalline silicon and silicon nitride after exemplary differential pretreatment using different reaction conditions.

[0032] Figure 6 It is a histogram depicting the surface differences between polysilicon and silicon nitride after exemplary differential pretreatment and selective inhibitor treatment.

[0033] Figure 7 It is a histogram depicting the surface stability of polycrystalline silicon and silicon nitride substrates over time after exemplary differential pretreatment.

[0034] Figure 8 The illustration schematically shows the effect of an exemplary differential pretreatment on alumina deposition compared to omitting the differential pretreatment.

[0035] Figure 9 The illustration schematically shows the effect of an exemplary differential preprocessing on silicon nitride deposition compared to omitting differential preprocessing.

[0036] Figure 10 Examples of processing tools that can be used to perform differentiated pretreatment and selective deposition on substrates are shown.

[0037] Figure 11 An exemplary computing device is shown schematically. Detailed Implementation

[0038] The term "alcohol" generally refers to a hydrocarbon containing the general formula R-OH, where R is an aryl or aliphatic group. Alcohols may have more than one OH (hydroxyl) functional group (polyols); for example, a diol is a polyol having two OH functional groups. Exemplary alcohols include methanol, ethanol, and propanol.

[0039] The term "controller" typically refers to a computing device configured to control one or more functions of another device, such as a processing tool.

[0040] The term “deposition” and its variants generally refer to the process that causes a film to be formed on a substrate.

[0041] The term "dielectric film precursor" generally refers to a chemical substance that can be introduced into a processing chamber to form a dielectric film on a substrate.

[0042] The term "flow control hardware" typically refers to components configured to fluidly communicate one or more chemical sources with a processing chamber. For example, flow control hardware may include one or more mass flow controllers and / or valves.

[0043] The terms “inhibitor” and “inhibitor molecule” generally refer to compounds that can be introduced into a processing chamber, adsorbed onto the substrate surface, and, when adsorbed onto the substrate surface, inhibit the adsorption of other molecules onto the substrate surface.

[0044] The term "natural oxide" typically refers to an oxide surface layer that forms on a substrate when the substrate is exposed to air.

[0045] The term "organic base" generally refers to an organic compound that acts as a proton acceptor and / or electron pair donor in solution.

[0046] The term "pretreatment" generally refers to the process of modifying the substrate surface before performing the deposition process.

[0047] The term "processing chamber" generally refers to a housing in which chemical and / or physical processes are performed on a substrate. The pressure, temperature, and atmospheric composition within the processing chamber can be controlled to perform the chemical and / or physical processes.

[0048] The term "processing apparatus" generally refers to a mechanism that includes a processing chamber and other hardware configured to enable processing to be performed within the processing chamber.

[0049] The term "processing chemicals" generally refers to chemical substances used in the pretreatment and / or processing of substrates in a processing chamber.

[0050] The term "region" typically refers to a continuous portion of a substrate having the same surface chemistry. The term "multi-region" typically refers to a substrate having two or more regions, each with different surface chemistry.

[0051] The term "substrate" generally refers to any object on which a film can be deposited.

[0052] The term "substrate holder" generally refers to any structure configured to support a substrate in a processing chamber.

[0053] In the context of substrates, the term "surface" generally refers to the portion of the substrate exposed to process conditions within the processing chamber.

[0054] The term "vapor phase etching process" generally refers to a dry etching process that uses process chemicals introduced into a processing chamber in a vapor phase to etch a substrate in the absence of plasma. Vapor phase etching processes can use process chemicals that form a liquid layer on the substrate surface.

[0055] Substrates in integrated circuit manufacturing processes can comprise multiple surface regions of different materials. Despite their different compositions, the different materials in different substrate surface regions may sometimes be indistinguishable by processing chemicals. For example, a substrate may contain regions of silicon, silicon oxide, and silicon nitride. When exposed to air, all three of these bulk materials will grow a natural oxide layer. Consequently, each surface region exhibits similar behavior to many processing chemicals, such as film precursors and inhibitors. This makes region-selective deposition of films on substrates with regions composed of two or more of these materials difficult.

[0056] Current processing techniques for removing native oxide layers from such distinct regions result in similar surface terminations across those regions. For example, dilute hydrofluoric acid etching can be used to remove native oxide layers from substrates containing two or more of the following: silicon, silicon oxide, or silicon nitride regions. However, dilute hydrofluoric acid etching leaves each substrate region with hydrogen and fluorine (F) terminations. Other types of etching make these regions similarly indistinguishable to incoming processing chemicals. Consequently, selective deposition is challenging.

[0057] Therefore, the disclosed examples involve differentiated pretreatments utilizing a dry solvent-based vapor phase etching pretreatment. The disclosed differentiated pretreatments remove native oxides from different regions of the substrate, including from silicon, silicon nitride, and silicon oxide regions. Based on the chemical properties of each underlying region, the disclosed differentiated pretreatments further form different surface terminations. As an example, a substrate containing regions of polycrystalline silicon, silicon nitride, and silicon oxide, after being differentiated pretreated according to this disclosure, will produce hydrogen-terminated (polycrystalline silicon) surfaces, nitride-terminated (silicon nitride) surfaces, and oxide-terminated (silicon oxide) surfaces. This allows for selective adsorption of processing chemicals such as inhibitors and film precursors. Therefore, this allows for selective deposition of films on certain surface regions but not on others.

[0058] Figure 1A An exemplary multi-region substrate 100 having a native oxide layer 105 is schematically shown. The multi-region substrate 100 includes a polysilicon region 110, a silicon oxide region 112, and a silicon nitride region 114. The native oxide layer 105 is located on the surface 115 of the substrate.

[0059] Because of the native oxide layer 105 on surface 115, the polysilicon region 110, silicon oxide region 112, and silicon nitride region 114 are not significantly different for incoming processing chemicals. Therefore, each portion of the native oxide layer 105 exhibits similar behavior for processing chemicals such as film precursors and inhibitors.

[0060] Therefore, a differential pretreatment can be applied to the multi-region substrate 100 to remove the native oxide layer and differentiate the underlying regions. Figure 2 A flowchart illustrating an exemplary method 200 for processing a substrate using differential preprocessing is shown. Method 200 can be executed using a processing tool controlled by a controller comprising one or more computing devices. The following refers to... Figure 10 The exemplary processing tools are described in more detail here. This document discusses... Figure 11 An exemplary computing device is described.

[0061] In step 210, method 200 includes performing a pretreatment on the surface of a multi-region substrate, the multi-region substrate comprising regions containing polycrystalline silicon semiconductors, silicon nitrides, or two or more of silicon oxides. The surface of each of the two or more regions contains a natural oxide layer.

[0062] The pretreatment is a process that includes at least a solvent-based vapor phase etching process, wherein at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base are flowed through the surface. When additionally or alternatively combined with the deposition of one or more inhibitors, the pretreatment may allow the differentiation of three or more material surfaces. In addition to the examples of silicon nitride, silicon oxide, and polycrystalline silicon surfaces described above, the disclosed exemplary pretreatments may also allow other surfaces to be differentiated. Examples include polycrystalline silicon germanium, silicon germanium oxide, and silicon germanium nitride surfaces.

[0063] In some examples, the hydroxyl-containing solvent may include one or more of water, butanol, ethanol, methanol, isopropanol, diethylene glycol, ethylene glycol, methyl tert-butyl ether, or phenol. In other examples, any other suitable alcohol (including polyols) that is volatile under the processing conditions may be used.

[0064] In addition, in some examples, the organic base may comprise one or more of imidazole, benzimidazole, histidine, guanidine, methylamine, aniline, dimethylamine, diphenylamine, aziridine, piperidine, pyridine, 2-aminopentane, triethylamine, cyclodiphosphazene, hexachlorophosphazene, or polyphosphazene. In other examples, any other suitable amine or nitrogen-containing compound that is volatile under the treatment conditions may be used.

[0065] The solvent-based vapor phase etching process of Method 200 does not require wet etching or wet treatment. Various methods can be used to vaporize the hydroxyl-containing solvent and organic base. Examples include feeding the solution of the hydroxyl-containing solvent and organic base into a vaporizer before introducing it into the treatment chamber. A flow-over vapor approach can also be used, in which a carrier gas is passed through a heated solution of the hydroxyl-containing solvent and organic base. In some examples, gaseous hydrofluoric acid can be flowed separately from the hydroxyl-containing solvent and organic base into the treatment chamber. In other examples, hydrofluoric acid can be mixed with the hydroxyl-containing solvent and organic base before being introduced into the treatment chamber. The flow of the pretreatment chemicals can be continuous or pulsed. In some examples, the total chamber pressure during pretreatment can range from 0.1 Torr to 10 Torr. Furthermore, in some examples, the substrate temperature during pretreatment can range from 60°C to 180°C. In other examples, pressures and / or temperatures outside these ranges can be used.

[0066] A hydroxyl-containing solvent creates a solvent layer on the surface of the substrate. This allows hydrofluoric acid to dissolve into the solvent layer and perform etching of the native oxide layer. An organic base acts as a catalyst, causing the etching to favor the oxide or nitride layer. Once the native oxide layer has been removed and these regions are terminated with hydrogen and amine, respectively, this allows etching to be stopped or slowed down on silicon and silicon nitride. In some examples, the concentration of the organic base in the hydroxyl-containing solvent may be 1% or less. In other examples, the concentration of the organic base in the hydroxyl-containing solvent may be greater than 1%.

[0067] The exemplary pretreatment process according to method 200 facilitates the formation of silicon tetrafluoride (SiF4) at equilibrium. SiF4 is a gas and thus evaporates to remove it from the substrate once formed. Hydrogen from hydrofluoric acid reacts with oxygen in the natural oxide layer to form water. This water can also be removed by evaporation. In contrast, some wet etching processes may use ammonia and hydrofluoric acid. This may form SiF6 with diammonium cations. 2- Anion (diammonium hexafluoride silicate). This compound is a solid. Therefore, wet etching may leave similar surface chemistry in different substrate regions.

[0068] Figure 1B The image shows the results after differential preprocessing 120 according to this disclosure. Figure 1AAn exemplary multi-region substrate 100. As shown at 122, the polysilicon region 110 is H-terminated. As shown at 124, the silicon oxide is OH-terminated. As shown at 126, the silicon nitride is NH2-terminated. This pretreatment thus differentiates the surfaces of the three substrate regions. These surfaces can then selectively react with the molecular material that will subsequently enter. For example, selective inhibition and / or film deposition are possible. It should be noted that there may be other end groups after such differential pretreatment, and such differential pretreatment does not necessarily produce a surface with uniform end groups.

[0069] return Figure 2 At 220, method 200 includes selectively depositing a first molecular substance onto a pretreated surface such that the first molecular substance adsorbs to one or more regions and not to one or more other regions. For example, the first molecular substance may comprise a dielectric film precursor. Exemplary dielectric film precursors include precursors of one or more of alumina, titanium oxide, zinc oxide, silicon dioxide, silicon carbide, silicon carbide, silicon oxynitride, silicon carbonitride, hafnium oxide, tantalum nitride, titanium nitride, or silicon nitride. In some examples, the surface region differences resulting from the disclosed exemplary differential pretreatment can be used to selectively deposit a film on certain surface regions but not on others without the use of inhibitors. In other examples, the first molecular substance may comprise inhibitor molecules. Examples of inhibitor molecules include alkylsilane inhibitors and aminosilane inhibitors. Several examples of alkylsilane inhibitors and aminosilane inhibitors are listed below. Inhibitors can be used to inhibit the adsorption of film precursors to the substrate surface. Therefore, the selective adsorption of inhibitor molecules onto the substrate surface in certain regions but not others allows film deposition to occur on the uninhibited surface rather than the inhibited surface. However, whether using inhibitors or selectively adsorbing film precursors without using inhibitors, region-selective deposition can be performed without photolithographic patterning.

[0070] In some examples, selective deposition of the first molecule can be applied wet or dry. Certain processing tools can perform this step without exposure to air (e.g., using loading locks or transfer zones, where the substrate is under inert gas or vacuum while awaiting the next stage of processing). However, the pretreated surface can possess inherent stability without instantaneous re-oxidation. Therefore, it can tolerate a degree of air exposure. Consequently, different processing tools can be used for differentiated pretreatment, application of inhibitors, and deposition. Additionally or alternatively, a single tool with multiple modules and / or processing chambers can be used.

[0071] Figure 1C Schematally shown after selective deposition of the first molecule 130 Figure 1BAn exemplary pretreated multi-region substrate. In this example, a first molecular substance 130 is selectively adsorbed onto a silicon nitride region 114 to form a layer 132 of the first molecular substance 130.

[0072] In some examples, layer 132 may be a membrane precursor layer. In such examples, the membrane precursor layer may then be converted into a membrane layer, for example, by oxidation.

[0073] In other examples, layer 132 may be a layer of inhibitor molecules. In such an example, layer 132 may inhibit the adsorption of the film precursor on the silicon nitride region 114. Therefore, briefly returning to the reference... Figure 2 At 230, method 200 optionally includes selectively depositing a second molecule onto the pretreated surface. The second molecule may be a membrane precursor and may adsorb onto one or more regions where the first molecule 130 (an inhibitor in this example) has not been adsorbed.

[0074] Figure 1D This shows the selective deposition of the second molecule 140. Figure 1C In an exemplary pretreated multi-region substrate, the second molecular material 140 comprises a film precursor. In this example, a layer 132 of the first molecular material (an inhibitor in this example) prevents the film precursor from adsorbing onto the surface of the silicon nitride region 114. In this example, the second molecular material 140 selectively adsorbs onto the silicon oxide region 112 to form layer 142. Layer 142 can then be converted into a film material, for example, by oxidation or other processes. Furthermore, in some examples, the hydrogen-terminating surface of the polysilicon region 110 may prevent the film precursor (e.g., the second molecular material 140) from adsorbing onto the polysilicon region 110. In other examples, the film precursor may not exhibit selectivity between the polysilicon region 110 and the silicon oxide region 112.

[0075] Figure 3 Figure 300 shows experimental data on the enhanced selectivity between polycrystalline silicon and silicon nitride substrates, measured by water contact angle (WCA), under a series of pretreatment and inhibitor exposure conditions. This measurement indicates the hydrophobicity of the surfaces, thus indicating the potential deposition selectivity of these surfaces after each pretreatment. The substrates underwent different processing flows, none of which involved exposure to hydroxyl-containing solvents, organic bases, or hydrofluoric acid.

[0076] Figure 3The process includes no pretreatment, hydrogen (H2) plasma pretreatment, ammonia (NH3) plasma pretreatment, exposure to a first aminosilane inhibitor (Inh1), H2 plasma pretreatment followed by exposure to a first aminosilane inhibitor, exposure to a second aminosilane inhibitor (Inh2), exposure to a third aminosilane inhibitor (Inh3), exposure to an alkylsilane inhibitor (Inh4), or H2 plasma pretreatment followed by exposure to an alkylsilane inhibitor.

[0077] According to the WCA measurements, polycrystalline silicon and silicon nitride surfaces exhibited similar properties after each of the pretreatment and inhibitor exposure. In fact, “no pretreatment” (“NONE”) resulted in a larger difference in WCA compared to any of the pretreatments or inhibitor exposures. Differences in inhibitor adsorption are expected to alter the surface hydrophobicity of one material relative to the other. However, in all instances, the measured WCA for polycrystalline silicon and silicon nitride were similar. Therefore, selective inhibitor adsorption between polycrystalline silicon and silicon nitride using these pretreatments is not feasible.

[0078] Figure 4 Figure 400 shows experimental data on surface differences between polycrystalline silicon and silicon nitride substrates, measured by WCA via an exemplary differential pretreatment. The substrates underwent untreated, differential pretreatment (e.g., a solvent-based vapor phase etching process, wherein a vapor containing at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base was passed through the substrate), exposure to a third aminosilane inhibitor, and differential pretreatment followed by exposure to a third aminosilane inhibitor. As described above, the differential pretreatment was used to remove native oxides from both the polycrystalline silicon and silicon nitride surfaces.

[0079] According to the WCA measurements, a single exemplary differential pretreatment is sufficient to increase the WCA difference between silicon nitride and polycrystalline silicon by approximately 10°. Inhibitor adsorption onto each surface individually produces similar WCA. When inhibitors are applied after the differential pretreatment, inhibitor adsorption differs on each surface, resulting in a WCA difference of approximately 29°, with inhibitors more readily adsorbed onto polycrystalline silicon than silicon nitride. Therefore, the application of inhibitors alone does not differentiate between silicon nitride and polycrystalline silicon, but the differential pretreatment does achieve selective inhibitor adsorption. This can then be further used to selectively adsorb film precursor molecules onto polycrystalline silicon instead of silicon nitride.

[0080] Figure 5Figure 500 shows experimental data on surface differences between polycrystalline silicon and silicon nitride substrates, measured by WCA, after exemplary differential pretreatments of varying durations. The substrates underwent no pretreatment, differential pretreatment (e.g., a solvent-based vapor phase etching process in which at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base flowed through the substrate) for 20 seconds, differential pretreatment for 30 seconds, differential pretreatment for 60 seconds, and differential pretreatment for 162 seconds. In these examples, the differential pretreatments were performed at temperatures between 50°C and 150°C and pressures of several Torr.

[0081] According to the WCA measurements, a differential pretreatment of 20 seconds was sufficient to significantly increase the WCA of polycrystalline silicon compared to silicon nitride. Minimal changes were observed with longer pretreatment times. Furthermore, the WCA of polycrystalline silicon remained increased compared to silicon nitride even after longer pretreatment times. Higher temperature pretreatment also showed differences between silicon nitride and polycrystalline silicon, demonstrating that a variety of conditions can be used to effectively perform differential pretreatment on the substrate to differentiate the surface.

[0082] In practice, lower temperature pretreatment is compatible with a wider range of surface types. Etching rates can increase with increasing temperature. However, at higher temperatures, the solvent may boil and escape from the substrate, reducing solvent thickness and etching capability.

[0083] Figure 6 Figure 600 shows experimental data on the surface differences between polycrystalline silicon and silicon nitride, measured by water contact angle, following exemplary differential pretreatment and selective inhibitor treatment. The substrates underwent no treatment, differential treatment alone for 30 seconds, no treatment followed by exposure to a third aminosilane inhibitor, differential treatment for 30 seconds followed by exposure to a third aminosilane inhibitor, no treatment followed by exposure to an alkylsilane inhibitor, differential treatment for 20 seconds followed by exposure to an alkylsilane inhibitor, differential treatment for 30 seconds followed by exposure to an alkylsilane inhibitor, or differential treatment for 60 seconds followed by exposure to an alkylsilane inhibitor.

[0084] According to the WCA measurements, differential pretreatment enhanced the inhibitor adsorption selectivity between polycrystalline silicon and silicon nitride for both teraminosilane and alkylsilane inhibitors. In contrast, with inhibitor exposure alone, both teraminosilane and alkylsilane inhibitors adsorbed similarly to polycrystalline silicon and silicon nitride. Therefore, differential pretreatment can enhance selectivity for a variety of inhibitor molecules.

[0085] Figure 7Figure 700 shows experimental data on the surface stability of polycrystalline silicon and silicon nitride substrates, measured by WCA, after a period of time following an exemplary differential pretreatment. The substrates underwent either a separate differential pretreatment or a differential pretreatment followed by exposure to a third aminosilane inhibitor. Following pretreatment, WCA measurements were performed on the substrates after 20 minutes, 3 hours, or 25 hours of air exposure.

[0086] As shown in the figure, the WCA on silicon nitride did not change significantly with air exposure time. The WCA on polycrystalline silicon began to decrease slightly after 3 hours of air exposure. After inhibitor exposure, the WCA on silicon nitride actually increased with increasing air exposure time, while the WCA on polycrystalline silicon began to decrease slightly after 3 hours of air exposure.

[0087] This data indicates that the differential pretreatment produces a stable surface condition for several hours. This allows for the use of process tools that subject the substrate to relatively brief exposure to air prior to molecular deposition during the differential pretreatment.

[0088] As described above, the combination of differentiated pretreatment and selective inhibitor exposure enables selective deposition of dielectric film precursors. Exemplary inhibitors include alkylsilane inhibitors and aminosilane inhibitors. Exemplary dielectric film precursors include alumina and silicon nitride precursors. Figure 8 The effect of differentiated pretreatment on alumina deposition is schematically shown. At 800, Figure 8 An exemplary multi-region substrate 801 with a native oxide layer 805 is shown. The multi-region substrate 801 includes a polysilicon region 810, a silicon oxide region 812, and a silicon nitride region 814. The native oxide layer 805 extends over each of the polysilicon region 810, the silicon oxide region 812, and the silicon nitride region 814.

[0089] At 820, Figure 8 A multi-region substrate 801 is shown with inhibitor application but no differentiated pretreatment. In this example, the inhibitor is deposited onto each region via a reaction with the native oxide layer 805. Therefore, selective adsorption of the film precursor is not feasible in this example.

[0090] At 830, Figure 8 The multi-region substrate 801 after differential pretreatment is shown. The native oxide layer 805 has been removed. The polysilicon region 810 has been hydrogen-terminated. The silicon oxide region 812 has been hydroxyl-terminated, and the silicon nitride region 814 has been amine-terminated. However, in this example, the alumina precursor is not selective for these surfaces. Therefore, at 840, Figure 8The multi-region substrate 801 after differential pretreatment and adsorption of an alumina precursor (schematically indicated by Al) is shown. As shown, the alumina film precursor is adsorbed onto each of regions 810, 812, and 814.

[0091] Given the lack of selectivity of alumina precursors for different surface chemistry properties, inhibitors can be selectively adsorbed onto the surface to allow selective adsorption of alumina film precursors on uninhibited surfaces. At 850, Figure 8 The multi-region substrate 801 is shown after differential pretreatment and after inhibitor application. Inhibitor molecules are schematically indicated by "X". As shown, the inhibitor adsorbs onto the polysilicon region 810 and the silicon oxide region 812. However, the inhibitor does not adsorb onto the silicon nitride region 814.

[0092] At 860, Figure 8 A multi-region substrate 801 is shown after differential pretreatment and inhibitor exposure, as well as further exposure to an alumina precursor (“Al”). In this example, the alumina precursor is selectively adsorbed onto silicon nitride regions 814. Thus, the differential pretreatment allows for selective deposition of alumina onto silicon nitride, at least by preventing inhibitor adsorption onto the silicon nitride surface when the inhibitor is adsorbed onto both polysilicon and silicon oxide.

[0093] Figure 9 The effect of differentiated pretreatment on exemplary silicon nitride deposition is schematically shown. At 900, Figure 9 An exemplary multi-region substrate 901 with a native oxide layer 905 is shown. The multi-region substrate 901 includes polysilicon regions 910 and silicon nitride regions 814. The native oxide layer 905 extends over the polysilicon regions 910 and the silicon nitride regions 914.

[0094] At 920, Figure 9 A multi-region substrate 901 is shown exposed to a silicon nitride precursor but without differentiated pretreatment. In this example, the silicon nitride precursor (SiN) is deposited onto each region via a reaction with a native oxide layer 905. For example, atomic layer deposition (ALD) can be used to form the silicon nitride film. In the silicon nitride ALD deposition process, a silicon-containing precursor is adsorbed onto the substrate. The adsorbed precursor is then chemically converted into silicon nitride. For example, the chemical conversion can be performed by exposure to ammonia and nitrogen.

[0095] At 930, Figure 9 The multi-region substrate 901 after differential pretreatment is shown. The native oxide layer 905 has been removed. The polysilicon region 910 has been H-terminated. The silicon nitride region 914 has been N-terminated.

[0096] At 940, Figure 9A multi-region substrate 901 is shown after differential pretreatment and exposure to a silicon nitride film precursor. The silicon nitride film can be deposited using any suitable precursor. For example, ALD deposition of silicon nitride can use precursors such as aminosilane precursors, silane halides, and / or other silicon-containing precursors. The precursor can be converted into a silicon nitride layer via thermal and / or plasma methods. Silicon nitride can also be deposited using chemical vapor deposition (CVD). As shown, although some silicon nitride is deposited on polycrystalline silicon region 910, silicon nitride is selectively deposited on silicon nitride region 914 instead of polycrystalline silicon region 910.

[0097] At 950, Figure 9 The multi-region substrate 901 is shown after differential pretreatment and inhibitor application. As shown, the inhibitor is adsorbed onto the polysilicon region 810 but not onto the silicon nitride region 814.

[0098] At 960, Figure 9 The multi-region substrate 901 is shown after differential pretreatment and inhibitor application, and further adsorption of silicon nitride precursors. As shown, silicon nitride precursors are selectively adsorbed onto silicon nitride regions 914.

[0099] Figure 10 An example of a processing tool 1000 that can be used to perform differentiated pretreatment on a substrate is shown. The processing tool can also be used to selectively adsorb inhibitors onto the substrate and / or selectively deposit dielectric film precursors onto the substrate. The processing tool 1000 is a reference. Figure 2 Examples of processing tools for implementing the methods described herein. In other examples, one or more of the processes described herein may be performed using different tools.

[0100] The processing tool 1000 includes a processing chamber 1002 and a substrate support 1004 within the processing chamber. The substrate support 1004 is configured to support a substrate 1006 placed within the processing chamber 1002. The substrate support 1004 may include a base, such as an electrostatic chuck base or any other suitable structure. The substrate support 1004 may include a substrate heater 1008.

[0101] The processing tool 1000 further includes a nozzle 1010. In other examples, instead of or as a supplement to a nozzle, the processing tool may include a nozzle or other means for introducing gas into the processing chamber 1002. The processing tool 1000 further includes flow control hardware 1012. The flow control hardware 1012 connects a processing gas source to the processing chamber to allow the flow of each of one or more processing gases to be controlled. In the depicted example, the flow control hardware 1012 connects an inhibitor source 1014, a membrane precursor source 1016, a hydrogen fluoride source 1018, a hydroxyl-containing solvent source 1020, an organic base source 1022, and one or more inert gas sources 1024. The flow control hardware 1012 may include any suitable components. Examples include a mass flow controller, a valve, and a conduit.

[0102] Inhibitor source 1014 contains any suitable inhibitor that can be introduced into the processing chamber in the gas phase (including liquid or solid materials that can be vaporized to be introduced into the processing chamber) to selectively adsorb onto the substrate surface. Exemplary inhibitors include silicon-containing inhibitors, such as alkylsilane inhibitors and aminosilane inhibitors. Examples of silicon-containing inhibitors include n-octadecylsilane, tridecylsilane, dodecylsilane, undecylsilane, decylsilane, dec-4-ylsilane, nonylsilane, non-4-ylsilane, oct-2-ylsilane, octylsilane, heptylsilane, hept-4-ylsilane, (tetrazofluoro-1,1,2,2-tetrahydrooctyl)silane, or 10-undecenylsilane. Examples of aminosilane inhibitors include bis(diethylaminosilane), diisopropylaminosilane, bis(tert-butylamino)silane (BTBAS), disec-butylaminosilane, tris(dimethylamino)silane (3DMAS), dimethylaminotrimethylsilane, dimethylaminodimethylsilane, dimethylaminotriethylsilane, diethylaminotrimethylsilane, n-butyldimethyl(dimethylamino)silane, n-propyldimethyl(dimethylamino)silane, or triisopropyldimethylaminosilane. In some examples, inhibitor source 1014 contains an inhibitor in the condensed phase at standard pressure and temperature. In such examples, inhibitor source 1014 may comprise a flow-over-vapor delivery system, a vaporizer delivery system, a capacitive delivery system, a molar delivery device, or other suitable delivery system for volatilizing the condensed-phase inhibitor. This achieves gas-phase delivery of the inhibitor precursor.

[0103] The film precursor source 1016 contains a volatile or volatile dielectric film precursor, which can be adsorbed onto the substrate surface, for example, using atomic layer deposition and then chemically converted into a film. Exemplary dielectric films include alumina, silicon nitride, titanium oxide, zinc oxide, silicon dioxide (including doped silicon dioxide (e.g., fluorine-doped and carbon-doped silicon dioxide)), silicon carbide, silicon carbide, silicon oxynitride, silicon carbonitride, hafnium oxide, tantalum nitride, or titanium nitride. Exemplary dielectric film precursors include precursors containing Al, Si, Ti, Zn, Si, Hf, Sn, and Ta. Other materials, such as metals like W, Mo, Ta, Ru, Co, and Cu, can also be deposited after the substrate surface has been treated with an inhibitor, such as an aminosilane inhibitor. In some examples, the film precursor source 1016 contains a dielectric film precursor that is in a condensed phase at standard pressure and temperature. In such an example, the membrane precursor source 1016 may include a flow-through vapor delivery system, a vaporizer delivery system, a charge volume delivery system, a molar delivery device, or other suitable delivery system for evaporating the condensed dielectric membrane precursor. To form an alumina dielectric film, an exemplary dielectric film precursor may comprise one or more of the following: aluminum methylpropoxide, aluminum methylisopropoxide, aluminum methylbutoxide, aluminum methyl tert-butoxide, aluminum methylethanol, aluminum dimethylpropoxide, aluminum dimethylisopropoxide, aluminum dimethylbutoxide, aluminum dimethyl tert-butoxide, aluminum dimethylethanol, aluminum ethylpropoxide, aluminum ethylisopropoxide, aluminum ethylbutoxide, aluminum ethyl tert-butoxide, aluminum ethylethanol, aluminum diethylpropoxide, aluminum diethylisopropoxide, aluminum diethylbutoxide, aluminum diethyl tert-butoxide, aluminum diethylethanol, aluminum propylpropoxide, aluminum propylisopropoxide, aluminum propylbutoxide, aluminum propyl tert-butoxide, aluminum propylethanol, aluminum dipropylpropoxide, aluminum dipropylisopropoxide, aluminum dipropylbutoxide, aluminum dipropyl tert-butoxide, or aluminum dipropylethanol. For silicon dioxide or other silicon-containing oxides, such dielectric film precursors may include one or more of the following: triethoxysilane, tetraethyl orthosilicate, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, or tetravinyltetramethylcyclotetrasiloxane.For silicon nitride, such dielectric film precursors may comprise one or more of hexachlorodisilane, hydrazine, tetrachlorosilane, dichlorosilane, octachlorosilane, pentachlorodisilane, tris(dimethylamino)silane, bis(tert-butylamino)silane, di(sec-butylamino)silane, silica, trisilaneamine, allyltrimethoxysilane, butyldichlorosilane, chloropentamethyldisilane, dimethoxydimethylsilane, hexamethyldisilane, isobutyl(trimethoxy)silane, methyltrichlorosilane, pentamethyldisilane, isotetrasilane, neopentylsilane, trisilane, n-tetrasilane, chlorosilane, diiodosilane, triiodosilane, tetraiodosilane, tetrabromosilane, tetrachlorosilane, bis(diethylamino)silane, and / or any other suitable chlorosilane, organosilane, heterosilane, or alkylaminosilane.

[0104] Hydrogen fluoride source 1018 may contain hydrogen fluoride gas. Hydroxyl solvent source 1020 may contain any suitable hydroxyl solvent. Examples include water, butanol, ethanol, methanol, isopropanol, diethylene glycol, ethylene glycol, methyl tert-butyl ether, or phenol.

[0105] Organic base source 1022 may contain any suitable organic base. Examples include pyridine, imidazole, benzimidazole, histidine, guanidine, methylamine, aniline, dimethylamine, diphenylamine, aziridine, piperidine, 2-aminopentane, triethylamine, cyclodiphosphazane, hexachlorophosphazene, and polyphosphazene. In some examples, two or more organic base sources are included, each providing a different organic base.

[0106] Inert gas source 1024 may contain any suitable inert gas. Examples include helium, neon, argon, krypton, and xenon. In some applications, such as in processing steps that do not use plasma, nitrogen may be used as the inert gas. In some examples, one or more additional inert gas sources may be included, each providing a different inert gas.

[0107] The processing instrument 1000 further includes an exhaust system 1035. The exhaust system 1035 is configured to exhaust gas from the processing chamber 1002. The exhaust system 1035 may include any suitable hardware, including one or more low-vacuum pumps and one or more high-vacuum pumps.

[0108] The processing tool 1000 further includes a radio frequency power source 1036 configured to generate plasma. In the depicted example, the radio frequency power source 1036 is electrically connected to a substrate support 1004. A nozzle 1010 is electrically connected to ground as a counter electrode. In other examples, the radio frequency power source 1036 may be connected to the nozzle 1010 and the substrate support 1004 may be electrically connected to ground.

[0109] The processing tool 1000 further includes a matching network 1038 for impedance matching of the RF power source 1036. The RF power source 1036 can be configured to provide RF energy with any suitable frequency and power. Exemplary frequencies include 400 kHz, 13.56 MHz, 27 MHz, 60 MHz, and 90 MHz. In some examples, the RF power source 1036 is configured to operate at several different frequencies and / or powers. Examples of lower frequencies include frequencies of 3 MHz and lower. Lower frequency RF energy components can contain up to 6500 W of power. Examples of suitable high-frequency RF power include frequencies in the range of 3 MHz to 300 MHz. Higher frequency RF energy components can contain up to 6500 W of power. In other examples, the processing tool can provide other RF powers and / or frequencies.

[0110] Controller 1040 is operatively coupled to substrate heater 1008, flow control hardware 1012, exhaust system 1035, and RF power source 1036. Controller 1040 is configured to control various functions of processing tool 1000 to pretreat or selectively deposit films, such as dielectric films, on a substrate surface. For example, controller 1040 is configured to operate substrate heater 1008 to heat the substrate to a desired temperature. Controller 1040 is also configured to operate flow control hardware 1012 to control the flow rate of inhibitor flowing from inhibitor source 1014 into processing chamber 1002. Controller 1040 is further configured to operate flow control hardware 1012 to control the flow rate of film precursor from film precursor source 1016 to deposit a film onto the substrate surface after exposing the substrate surface to the aminosilane inhibitor. Controller 1040 may include any suitable computing system. References are provided below. Figure 11 Describe an exemplary computing system.

[0111] In the above description, several examples include HF as a halogen source for differentiated pretreatment. However, any suitable halogen source can be used. In several examples, the volume and mass percentages described for HF can be used for other halogen sources. In some examples, two or more halogen sources can be used. The halogen source can be any halogen-containing compound (e.g., containing X, where X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) that exists in the vapor phase at the treatment temperature. Examples include hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), fluorine (F2), chlorine (Cl2), bromine (Br2), chlorine trifluoride (ClF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCl3), and nitrogen tribromide (NBr3). In some implementations, the halogen source is an organohalide, examples of which include fluoroform (CHF3), chloroform (CHCl3), bromoform (CHBr3), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), carbon tetrabromide (CBr4), perfluorobutene (C4F8), and perchlorobutene (C4Cl8).

[0112] In some implementations, the halogen source is a silicon halide, examples of which include silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), silicon tetrabromide (SiBr4), and compounds including SiX6 (e.g., H2SiX6). In some implementations, the halogen source is a metal halide, examples of which include molybdenum hexafluoride (MoF6), molybdenum hexachloride (MoCl6), molybdenum hexabromide (MoBr6), tungsten hexafluoride (WF6), tungsten hexachloride (WCl6), tungsten hexabromide (WBr6), titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), zirconium fluoride (ZrF4), zirconium chloride (ZrCl4), and zirconium bromide (ZrBr4). In some examples, metal halides can be used for selective etching of metal oxides. In the above description, several examples include hydroxyl-containing solvents as organic solvents for differentiated pretreatment. However, any suitable organic solvent can be used. In several examples, the volume and mass percentages described for hydroxyl-containing solvents can be used for other organic solvents. In some examples, the organic solvent may include two or more of the organic solvents described herein or of the types of organic solvents. In some examples, water may be provided instead of the organic solvent, or water may be provided in addition to the organic solvent.

[0113] In some implementations, the organic solvent may be an alcohol. The alcohol may have the formula XC(R). n An alcohol of (OH)-Y, wherein: n =1; Each X and Y can be independently selected from hydrogen, -[C(R 1 )2] m -C(R 2)3 or OH, where each R 1 With R 2 Independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, wherein m The integer is from 0 to 10; and each R is independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic or any combination thereof.

[0114] In some examples, each R, R 1 and R 2 It is independently selected from alkyl, alkenyl, ynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, ynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In certain disclosed examples, the alcohol may be further substituted with one or more substituents, such as alkoxy, amide, amine, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halogenate, or any combination thereof.

[0115] In other examples, when at least one of X or Y = -[C(R 1 )2] m -C(R 2 )3 or R is hydrogen and m When the value is 1, the alcohol can be a C3 alcohol. For example, if at least one R... 1 And an R 2 If it does not exist, then the C3 alcohol can be a C3 enol (e.g., allyl alcohol). In another example, R with an R 2 If they can form a ring (e.g., cycloaliphatic), then the C3 alcohol can be cyclopropanol or 2-cyclopropenol.

[0116] In other examples, when at least one of X or Y = -[C(R 1 )2] m -C(R 2 )3 or R is hydrogen and m When the number is 2, the alcohol can be a C4 alcohol. For example, if at least one R 1 and an R2 If it does not exist, then the C4 alcohol can be a C4 enol (e.g., 2-buten-1-ol or 3-buten-1-ol). In another example, R is with an R 2 If X and Y can form a ring (e.g., cycloaliphatic), then the C4 alcohol can be a C4-cyclic alcohol (e.g., cyclobutanol or cyclopropylmethanol). In another example, if neither X nor Y is OH, then the C4 alcohol can be a C4-branched alcohol (e.g., 2-butanol, isobutanol, or tert-butanol).

[0117] In some instances, when X = OH and Y = -[C(R) 1 )2] m -C(R 2 When )3, the alcohol can be a diol. In other instances, when at least one X or Y = -[C(R 1 )2] m -C(R 2 )3 and at least one R 1 =OH or an R 2 When R = OH, or when R = OH, the alcohol can be a diol. Exemplary diols include, but are not limited to, 1,4-butanediol, propylene-1,3-diol, etc.

[0118] In other instances, the alcohol can be a triol when X = Y = OH. In still other instances, the alcohol can be a triol when X = R = OH. In some instances, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When R is OH, the alcohol can be a triol. In other examples, when R = OH and X = -[C(R)] 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When OH is present, the alcohol can be a triol. Exemplary triols include, but are not limited to, glycerol or its glycerol derivatives.

[0119] In certain examples, when R = cycloaliphatic, heterocyclic, heteroaryl, alkyl-heterocyclic, alkenyl-heterocyclic, alkynyl-heterocyclic, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, or heteroynyl-heterocyclic, the alcohol may be a heterocyclic alcohol (e.g., an optionally substituted heterocyclic group with more or fewer hydroxyl groups, such as furfuryl alcohol). In other examples, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2It can be a cycloaliphatic group, heterocyclic group, heteroaryl group, alkyl-heterocyclic group, alkenyl-heterocyclic group, alkynyl-heterocyclic group, heteroalkyl-heterocyclic group, heteroalkenyl-heterocyclic group, or heteroalkynyl-heterocyclic group, and the alcohol can be a heterocyclic alcohol.

[0120] In various examples, alcohols may have 1 to 10 carbon atoms. Alcohols may be primary, secondary, or tertiary alcohols. In some examples, alcohols may be selected from the group consisting of: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, and combinations thereof.

[0121] In these or other examples, organic solvents may include laboratory solvents such as acetonitrile, dichloromethane, carbon tetrachloride, or combinations thereof.

[0122] In some examples, the organic solvent may be a ketone. The organic solvent may also be an organic solvent having the formula X-[C(O)]. n -Y ketones, where: n Integers between 1 and 2; Each X and Y can be independently selected from -C(R) 1 3. -R 2 or -[C(R 3 )2] m -C(O)-R 4 , where each R 1 R 2 R 3 and R 4 It can be independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic or any combination thereof; Where R 3 and R 4 Together with the atoms they are attached to, they can optionally form cyclic aliphatic or cyclic heteroaliphatic ali ... m Integers between 0 and 10.

[0123] In some examples, each R 1 R 2 R 3 and R 4It is independently selected from alkyl, alkenyl, ynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, ynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In certain disclosed examples, the organic solvent may be further substituted with one or more substituents, such as aldehydes (-C(O)H), oxo (=O), alkoxy groups, amides, amines, hydroxyl groups, thioethers, thiols, acyloxy groups, silyl groups, cycloaliphatic groups, aryl groups, aldehydes, ketones, esters, carboxylic acids, acyl groups, acyl halides, cyano groups, halogens, sulfonates, nitro groups, nitroso groups, quaternary ammonium groups, pyridyl groups (or pyridyl groups in which the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halides, or any combination thereof. An exemplary ketone is acetone.

[0124] In some examples, the organic solvent may be a cyclic ketone when X and Y, together with their respective bonded atoms, form a cyclic aliphatic or cyclic heteroaliphatic group. Examples of cyclic ketones include cyclohexanone, cyclopentanone, etc.

[0125] In other examples, when at least one of X or Y = -[C(R 3 )2] m -C(O)-R 4 In this case, the organic solvent may be a diketone. Exemplary diketones include diacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, acetylacetone, acetone-acetone, and their halogenated forms, such as hexafluoroacetylacetone.

[0126] In a further example, when at least one of X or Y = -[C(R 3 )2] m -C(O)-R 4 When X and Y, together with their respective attached atoms, form a cyclic aliphatic or cyclic heteroaliphatic group, the organic solvent can be a cyclic diketone. Exemplary cyclic diketones include dimedone, 1,3-cyclohexanedione, etc.

[0127] In some instances, when X = -CH3, the organic solvent may have Y = -C(R) 1 )3, of which at least one R 1 C 2-10 Hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl propyl ketone, methyl butyl ketone, hydroxyacetone, etc.

[0128] In other instances, when X = -CH3, the organic solvent may have Y = -R. 2 , of which at least one R 2 C2 alkenyl, C 3-10 Aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, etc.

[0129] In other instances, the organic solvent may be an aromatic ketone when at least one of X or Y is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. Exemplary materials include acetophenone, benzophenone, benzylacetone, 1,3-diphenylacetone, cyclopentylphenyl ketone, etc.

[0130] In some instances where the organic solvent includes a ketone, the ketone may be selected from acetone and acetophenone. One or more additional ketones or other organic solvents described herein may also be provided.

[0131] In some examples, the organic solvent may be an alkane. In some examples, the alkane may be a hydrocarbon having the general formula C2. n H 2n+2 Noncyclic branched or unbranched hydrocarbons. Exemplary noncyclic alkanes include, but are not limited to, pentane, hexane, octane, and combinations thereof. In some other examples, the alkane may be a cyclic hydrocarbon. Exemplary cyclic hydrocarbons include, but are not limited to, cyclopentane, cyclohexane, and combinations thereof.

[0132] In some examples, the organic solvent may be an aromatic solvent. As used herein, "aromatic" means a cyclic conjugated group or portion having 5 to 15 (unless otherwise specified) ring atoms of a monocyclic (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized π-electron system. Typically, the number of out-of-plane π electrons corresponds to Hückel's rule (4n+2). The connection point with the parent structure is typically through the aromatic portion of the fused ring system. In some instances, the aromatic solvent may be selected from toluene and benzene.

[0133] In some examples, the organic solvent may be of the formula XOY or XO-[C(R)2]. n -OY ethers, wherein: n Integers from 1 to 4; Each X and Y can be independently selected from -[C(R 1 )2] m -C(R 2)3 or -R 3 or -[C(R 4 )2] p -O-[C(R 5 )2] m -C(R 6 )3, where each R 1 R 2 R 3 R 4 R 5 R 6 R can be independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and wherein m Integers from 0 to 10, and p Integers from 1 to 10; X and Y, along with the atoms they are attached to, may optionally form cyclic heteroaliphatic groups.

[0134] In some examples, each R, R 1 R 2 R 3 R 4 R 5 and R 6 It is independently selected from alkyl, alkenyl, ynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, ynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In a particular disclosed example, the ether may be further substituted with one or more substituents, such as alkoxy, amide, amine, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halogenate, or any combination thereof.

[0135] In some examples, when X and Y, together with their respective attached atoms, form a cyclic heteroaliphatic group, the organic solvent is a cyclic ether, such as acetal, dioxane, dioxolane, etc. In some examples, when n = 1 and each R = H, X and Y together form a six-, seven-, eight-, nine-, or ten-membered ring. Exemplary ethers include, but are not limited to, 1,3-dioxolane or its derivatives. In other examples, when n = 2 and R = H, X and Y form a seven-, eight-, nine-, or ten-membered ring. Exemplary ethers include, but are not limited to, 1,4-dioxane or its derivatives. In other examples, when n = 1 or n = 2, R is aliphatic, haloaliphatic, haloheteraliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 2-methyl-1,3-dioxolane, etc.

[0136] In other examples, the organic solvent may be an aromatic ether when at least one of X or Y is aromatic. Exemplary aromatic ethers include anisole, diphenyl ether, etc.

[0137] In some examples, the organic solvent may be a cycloalkyl ether when at least one of X or Y is cycloaliphatic. Exemplary cycloalkyl ethers include cyclopentylmethyl ether, cyclohexylmethyl ether, etc.

[0138] In other examples, when at least one of X or Y = -[C(R 4 )2-O] p -C(R 6 In case 3, the organic solvent may be a glycol-based ether. Exemplary glycol-based ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, etc., including methyl, ethyl, propyl, and butyl monoethers and diethers of ethylene glycol.

[0139] In some examples, the organic solvent is a nitrile having the formula RC≡N, wherein R represents aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic.

[0140] In some examples, R may optionally be hydroxylated (e.g., in one example, R may be CH3-CH(OH)-CH2- and the organic solvent will be CH3-CH(OH)-CH2-CN).

[0141] An example of a nitrile is acetonitrile as described above.

[0142] In the above description, several examples include organic bases as additives for differentiated pretreatment. However, any suitable additive can be used. In several examples, the volume and mass percentages described for the organic base can be used for other additives. In some examples, two or more additives can be used. In some examples, the additive can be used as a proton acceptor and to promote HF2. - The formation of HF2. In some such cases, HF2 - One or more materials, such as oxide materials or other materials, can be actively etched onto a substrate. The additive can be selected from several different types of additives. For example, in some examples, the additive can be a heterocyclic compound, a heterocyclic aromatic compound, a halogen-substituted heterocyclic aromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidant, a difluoride source, ammonia, an aldehyde, a carbene, or an organic acid. In some examples, more than one additive can be used. In some examples, the additive can be a boron-containing Lewis acid or a Lewis adduct. Boron trifluoride (BF3) is an example of a Lewis acid that forms the acid-base adduct BF4-. In some examples, the additive may belong to two or more of the categories listed above. In many examples, the additive is used to accelerate the reaction rate and enhance the reaction selectivity.

[0143] In some examples, the additive is a heterocyclic aromatic compound. The term "aromatic" is as defined above. A heterocyclic aromatic compound is an aromatic compound comprising a 5-, 6-, or 7-membered ring (unless otherwise specified) containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogens). Exemplary heterocyclic aromatic compounds that may be used include, but are not limited to, methylpyridine, pyridine, pyrrole, imidazole, thiophene, N-methylimidazolium, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolinic acid, 2,6-dimethylpyridine, 4-N,N-dimethylaminopyridine, and azulene. In some examples, the heterocyclic aromatic compound may be methylated. In some examples, the heterocyclic aromatic compound may follow the Hückel 4n+2 rule. In some examples, the additive is a halogen-substituted aromatic compound. Halogen-substituted aromatic compounds are aromatic compounds comprising at least one halogen bonded to an aromatic ring. As used herein, halogen or halo refers to F, Cl, Br, or I. Exemplary halogen-substituted aromatic compounds include, but are not limited to, 4-bromopyridine, chlorobenzene, 4-chlorotoluene, fluorobenzene, etc.

[0144] In some examples, the additive is a heterocyclic aliphatic compound. As used herein, "aliphatic" means having from at least one carbon atom to 50 carbon atoms (C60-200-3 ... 1-50Hydrocarbon groups, such as those with one to 25 carbon atoms (C 1-25 ), or one to ten carbon atoms (C 1-10 Heterocyclic aliphatic compounds include alkanes (or alkyl groups), alkenes (or alkenyl groups), alkynes (or alkynyl groups), including their cyclic forms, and further including straight-chain and branched arrangements, as well as all stereoisomers and positional isomers. Heterocyclic aliphatic compounds are aliphatic compounds comprising 5-, 6-, or 7-membered rings (unless otherwise specified) containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogens). Exemplary heterocyclic aliphatic compounds include pyrrolidine, piperidine, etc.

[0145] In some examples, the additive is of the formula NR. 1 R 2 R 3 amines, of which: R 1 R 2 and R 3 Each is independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; Where R 1 and R 2 Together with the atoms to which they are attached, they can optionally form cyclic heteroaliphatic groups; and Where R 1 R 2 and R 3 Together with the atoms they are attached to, they can optionally form cyclic heteroaliphatic groups.

[0146] In some examples, R 1 R 2 and R 3Each is independently selected from alkyl, alkenyl, ynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, ynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In a particular disclosed example, the amine may be further substituted with one or more substituents, such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halogenate, or any combination thereof.

[0147] In some examples, when R 1 R 2 and R 3 When at least one of the components is aliphatic, halogenated aliphatic, halogenated heteroaliphatic, or heteroaliphatic, the additive is an alkylamine. The alkylamine may include dialkylamines, trialkylamines, and their derivatives. Exemplary alkylamines include dimethylisopropylamine, N - Ethyl diisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, tert-butylamine, etc.

[0148] In other examples, when R 1 R 2 and R 3 When at least one of the components includes a hydroxyl group, the additive is an alcoholamine. In one example, R 1 R 2 and R 3 At least one of them is an aliphatic group substituted with one or more hydroxyl groups. Exemplary alcoholamines include 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(dipropylamino)ethanol, 2-(dibutylamino)ethanol, N-ethyldiethanolamine, N-tert-butyldiethanolamine, etc.

[0149] In some examples, when R 1 With R 2 When the additive, together with the atoms it is attached to, forms a cyclic heteroaliphatic compound, it can be a cyclic amine. Exemplary cyclic amines include piperidine, N -alkylpiperidine (e.g., N -Methylpiperidine, N propylpiperidine, etc.), pyrrolidine, N -alkylpyrrolidine (e.g., alkylpyrrolidine) N -Methylpyrrolidone,N -propylpyrrolidine, etc.), morpholine, N -alkylmorpholine (e.g., alkylmorpholine) N -Methylmorpholine, N -propylmorpholine, etc.), piperazine, N -alkylpiperazine, N,N -Dialkylpiperazine (e.g., 1,4-dimethylpiperazine), etc.

[0150] In other examples, when R 1 R 2 and R 3 When at least one of the components includes an aromatic compound, the additive is an aromatic amine. In some examples, R 1 R 2 and R 3 At least one of them is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. In other examples, R 1 and R 2 Including aromatics. In other examples, R 1 With R 2 And optional R 3 Together with the atoms they are attached to, they form aromatic cyclic heteroaliphatic amines. Exemplary aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and their derivatives.

[0151] In some examples, the additive may include amines selected from the group consisting of: methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1,2-ethylenediamine, aniline (and aniline derivatives such as N,N-dimethylaniline), N-ethyldiisopropylamine, tert-butylamine, and combinations thereof.

[0152] In some examples, the additive may include fluoroamines. Fluoroamines are amines having one or more fluorinated substituents. Exemplary fluoroamines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0153] In some examples, the additive may be a nitrogen-containing analogue of carbonic acid having the formula R 1 NC(NR 2 )-NR 3 Exemplary additives may include, but are not limited to, guanidine or its derivatives.

[0154] In some examples, the additive may be a relatively low molecular weight amine, for example, having a molecular weight of less than 200 g / mol or 100 g / mol in some examples. In some examples, higher molecular weight amines may be used, including those with long chains or heterocyclic compounds with aromatic rings.

[0155] In some examples, the additive may include amino acids. The amino acids may have the formula R-CH(NR՛2)-COOH, wherein: Each R and R՛ is independently hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0156] Exemplary amino acids that may be used include, but are not limited to, histidine, alanine, and their derivatives.

[0157] In some examples, the additive may include an organophosphorus compound. The organophosphorus compound may be a phosphate ester, phosphate amide, phosphonic acid, phosphinic acid, phosphonate, phosphinate, phosphine oxide, phosphine imide, or phosphonium salt. Exemplary organophosphorus compounds include phosphoric acid and trialkyl phosphate esters. In some examples, the organophosphorus compound is a phosphazene. A phosphazene is an organophosphorus compound containing phosphorus (V) and having a double bond between P and N. A phosphazene may have the formula RN=P(NR2)3 (where R and R2 are each independently selected from hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof). In some examples, a phosphazene has the formula [X2PN]. n (Where X is a halogen, alkoxide, or amide). Other types of phosphazenes may be used as needed.

[0158] In some examples, the additive includes an oxidizing agent. As used herein, an oxidizing agent is a material capable of oxidizing another substance (e.g., accepting electrons from it). Exemplary oxidizing agents that may be used include, but are not limited to, hydrogen peroxide, sodium hypochlorite, and tetramethylammonium hydroxide.

[0159] In some examples, the additive includes a difluoride source. The difluoride source is one that contains or produces difluoride (HF2). - Materials that may be used include, but are not limited to, ammonium fluoride, aqueous HF, gaseous HF, buffered oxide etching mixtures (e.g., mixtures of HF and buffers such as ammonium fluoride), and pyridine hydrogen fluoride. In some examples, the difluoride source (and / or one or more other additives listed herein) may react to form HF2 before or after delivery to the reaction chamber. - .

[0160] In some examples, the additive comprises an aldehyde having the formula X-[C(O)]-H, wherein: X can be selected from hydrogen, -R 1 -C(R) 2 )3 or -[C(R) 3 )2] m -C(O)H, where each R 1 R 2 and R 3 Independently selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and m Integers between 0 and 10.

[0161] In some examples, R 1 R 2 and R 3 Each of these elements independently comprises alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, alkynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In a particular disclosed example, the aldehyde or ketone may be further substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=O), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0162] In some examples, when X = aromatic, the additive may be an aromatic aldehyde. Exemplary aromatic aldehydes include benzaldehyde, 1-naphthal, benzodialdehyde, etc.

[0163] In other examples, when X = aliphatic, the additive may be an aliphatic aldehyde. Exemplary aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, etc.

[0164] In other examples, when X = -[C(R) 3 )2] m -C(O)H and mThe additive may be a dialdehyde when the value is 0 to 10 or when X = an aliphatic or heteroaliphatic aliphatic substance substituted with -C(O)H. Exemplary dialdehydes include glyoxal, phenylenedialdehyde, glutaraldehyde, malondialdehyde, butyraldehyde, etc.

[0165] In some instances, the aldehyde used as an additive may be selected from the group consisting of: acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other instances, the aldehyde used as an additive may be selected from the aldehydes discussed in this section and the aldehydes discussed in the section on organic solvents.

[0166] In some examples, the additive comprises carbene. The carbene may have the formula X-(C:)-Y, wherein: X and Y can each be independently selected from H, halogens, and -[C(R)]. 1 )2] m -C(R 2 3、-C(O)-R 1 or -C(=NR) 1 )-R 2 -NR 1 R 2 -OR 2 -SR 2 or -C(R) 2 )3, where R 1 With R 2 Each is independently selected from hydrogen, hydroxyl, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, wherein m Integers between 0 and 10; Where R 1 With R 2 Together with the atoms to which they are attached, they may optionally form cyclic heteroaliphatic groups; and X and Y, along with the atoms they are attached to, may optionally form cyclic aliphatic or cyclic heteroaliphatic groups.

[0167] In addition, the additive can be of the formula R 1 -C + (R)-R 2 The carbium cation, wherein R, R 1 With R 2 Each is independently selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0168] In some examples, each R, R 1 and R 2It is independently selected from alkyl, alkenyl, ynyl, heteroalkyl, heteroalkenyl, heteroynyl, haloalkyl, haloalkenyl, haloynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroynyl, aryl, heterocyclic, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-aryl, alkyl-heterocyclic, alkenyl-heterocyclic, ynyl-heterocyclic, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heterocyclic, heteroalkenyl-heterocyclic, heteroynyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heterocyclic, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In certain disclosed examples, the carbaene may be further substituted with one or more substituents, such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkyl halide, or any combination thereof. In any example of the carbaene, R 1 With R 2 Each person can choose independently.

[0169] In some examples, the additive may be a halocarne when at least one of X or Y is a halogen. Exemplary non-limiting halocarnes include dihalocarnes, such as dichlorocarnes, difluorocarnes, etc.

[0170] In some examples, when X=Y=-NR 1 R 2 In this case, the additive may be a diaminocarbamate. In one example, R... 1 With R 2 Each is independently aliphatic. Exemplary diaminocarbenes include bis(diisopropylamino)carbenes, etc.

[0171] In other examples, when at least one of X or Y = -NR 1 R 2 And R within X or Y 1 With R 2 When both, together with their respective attached nitrogen atoms, form a cyclic heteroaliphatic group, the additive can be a cyclic diaminocarbene. An exemplary cyclic diaminocarbene comprises bis( N -piperidinyl)carbene, bis( N -pyrrolidinyl) carbene, etc.

[0172] In one instance, when X=Y=-NR 1 R 2 And R from X 1 Group and R from Y 2 When the additive forms a cyclic heteroaliphatic group together with the nitrogen atom to which it is attached, the additive is N- Heterocyclic carbides. Exemplary examples N - Heterocyclic carbene contains imidazole-2-ylenes (e.g., 1,3-dimesitylimidazol-2-ylidene), 1,3-dimesitylimidazol-4,5-dichloroimidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylenes (e.g., 1,3-dimesitylimidazol-4,5-dichloroimidazol-2-ylidene), 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylenes (e.g., 1,3-dimesitylimidazol-4,5-dichloroimidazol-2-ylidene), 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylenes). (iisopropylphenyl)imidazol-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, etc.), imidazolidine-2-ylidene (e.g., 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene), triazole-5-ylidene (e.g., 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene), etc.

[0173] In some examples, when X = -NR 1 R 2 And Y = -SR 2 And R from X 1 Group and R from Y 2 When the group, together with the nitrogen atom to which it is attached, forms a cyclic heteroaliphatic group, the additive is a cyclic thioalkylamino carbene. Exemplary cyclic thioalkylamino carbenes include thiazole-2-carbenes (e.g., 3-(2,6-diisopropylphenyl)thiazole-2-carbenes, etc.).

[0174] In some examples, when X = -NR 1 R 2 And Y = -C(R) 2 )3 and R from X 1 Group and R from Y 2 When the groups together with the atoms to which they are attached form cyclic heteroaliphatic groups, the additive is an exemplary cyclic alkylamino carbene. Exemplary cyclic alkylamino carbenes include pyrrolidine-2-carbenes (e.g., 1,3,3,5,5-pentamethyl-pyrrolidine-2-carbenes, etc.) and piperidine-2-carbenes (e.g., 1,3,3,6,6-pentamethyl-piperidine-2-carbenes, etc.).

[0175] Further exemplary carbenes and their derivatives include compounds having a thiazole-2-carben moiety, a dihydroimidazolium-2-carben moiety, an imidazolium-2-carben moiety, a triazole-5-carben moiety, or a cyclopropene carben moiety. Other carbenes and carbene analogs include aminosulfonium carbenes, aminooxycarbenes, diaminocarbenes, heteroaminocarbenes, 1,3-dithionium carbenes, mesoionic carbenes (e.g., imidazoline-4-subunit compounds, 1,2,3-triazole subunit compounds, pyrazoline subunit compounds, tetrazolium-5-subunit compounds, isoxazolium-4-subunit compounds, thiazole-5-subunit compounds, etc.), cycloalkylaminocarbenes, boranylidene compounds, silylene compounds, stannylene compounds, nitrene compounds, phosphinidene compounds, foiled carbene compounds, etc. Further exemplary carbenes include dimethylimidazol-2-ylene, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylene, (phosphino)(trifluoromethyl)carbenes, bis(diisopropylamino)carbenes, bis(diisopropylamino)cyclopropene, 1,3-dimesityl-4,5-dichloroimidazol-2-ylene, 1,3-diadamantylimidazol-2-ylene, and 1,3,4,5-tetramethylimidazol-2-ylene. imidazol-2-ylidene, 1,3-dimesitylimidazol-2-ylidene, 1,3-dimesitylimidazol-2-ylidene, 1,3,5-triphenyltriazol-5-ylidene, bis(diisopropylamino)cyclopropenylidene, bis(9-anthrayl)carbene, norbornene-7-ylidene N (-7-ylidene), dihydroimidazol-2-ylidene, methylidenecarbene, etc.

[0176] In some examples, the additive comprises an organic acid. The organic acid may have the formula R-CO2H, wherein R is selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. In some examples, R is alkyl, alkenyl, ynylyl, heteroalkyl, heteroalkenyl, heteroynyl, halogenated alkyl, halogenated alkenyl, halogenated ynylyl, halogenated heteroalkyl, halogenated heteroalkenyl, halogenated heteroynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, ynyl-heteroaryl, alkyl-heteroaryl, alkenyl-heteroaryl, ynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroynyl-heteroaryl, or any combination thereof. In certain disclosed examples, R may be further substituted with one or more substituents, such as alkoxy, amide, amine, thioether, hydroxyl, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary ammonium, pyridyl (or a pyridyl group wherein the nitrogen atom is functionalized by an aliphatic or aryl group), alkylhalide, or any combination thereof. In some implementations, the organic acid may be selected from formic acid and acetic acid.

[0177] Any exemplary material described herein includes the unsubstituted and / or substituted forms of the compound. Non-limiting exemplary substituents include, for example, one, two, three, four, or more substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy groups (e.g., -OR, where R is C) 1-6 (2)C alkyl); 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C) 1-6 Alkyl); (3)C 1-6 Alkyl sulfonyl (e.g., -SO2-R, where R is C) 1-6 (4) Alkyl); (e.g., -C(O)NR 1 R 2 or -NHCOR 1 , where R 1 With R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein, or R. 1 With R 2 (5) aryl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryl acyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 (12) Cycloalkyl; (13) Halogen; (14) Heterocyclic group (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein); (15) Heterocyclic oxy group (e.g., -OR, where R is a heterocyclic group as defined herein); (16) Heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (17) Hydroxyl group (e.g., -OH); N - Protected amino group; (18) Nitro group (e.g., -NO2); (19) Oxyl group (e.g., =O); (20) C 1-6 Thioalkoxy groups (e.g., -SR, where R is C) 1-6 (21) Alkyl group; (22) Thiol group (e.g., -SH); (23) CO2R 1 , where R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (23)-C(O)NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (24)-SO2R 1 , where R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b)C 4-18 Aryl and (c)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (25)-SO2NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); and (26)-NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) N -Protective group, (c)C 1-6 Alkyl, (d)C 2-6 alkenyl, (e)C 2-6 alkynyl group, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C) 1-6 Alkyl group, R is C 4-18 Aryl), (h)C 3-8 cycloalkyl, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C) 1-6 Alkyl and R is C 3-8 (cycloalkyl), wherein in one example, neither of the two groups is bonded to the nitrogen atom via a carbonyl or sulfonyl group.

[0178] Figure 11 A non-limiting example of a computing system 1100 that can formulate one or more of the above-described methods and processes is shown schematically. The computing system 1100 is shown in a simplified form. The computing system 1100 may take the form of one or more personal computers, workstations, computers integrated with substrate processing tools, and / or network-accessible server computers.

[0179] The computing system 1100 includes a logic machine 1110 and a memory machine 1120. The computing system 1100 may optionally include a display subsystem 1130, an input subsystem 1140, a communication subsystem 1150, and / or a subsystem not displayed on... Figure 11 Other components. Figure 10 The controller 1040 is an example of the computing system 1100.

[0180] The logic machine 1110 includes one or more physical devices configured to execute instructions. For example, the logic machine may be configured to execute instructions belonging to one or more application programs, services, programs, routines, libraries, objects, components, data structures, or other logical structures. Such instructions may be implemented to perform work, implement data types, change the state of one or more components, achieve technical effects, or otherwise achieve desired results.

[0181] The logic machine may include one or more processors configured to execute software instructions. Additionally or alternatively, the logic machine may include one or more hardware or firmware logic machines configured to execute hardware or firmware instructions. The processor of the logic machine may be single-core or multi-core, and the instructions executed thereon may be configured for sequential, parallel, and / or distributed processing. Individual components of the logic machine may be distributed across two or more individual devices, which may be remotely set up and / or configured to perform coordinated processing. Aspects of the logic machine may be virtualized and executed via remotely accessible network computing devices configured in a cloud computing architecture.

[0182] Storage device 1120 includes one or more physical devices configured to accommodate instructions 1160, which can be executed by a logic machine to implement the methods and processes described herein. When such methods and processes are implemented, the state of storage device 1120 can be changed—for example, to accommodate different data.

[0183] Storage unit 1120 may include removable and / or built-in devices. Storage unit 1104 may include optical memory (e.g., CD, DVD, HD-DVD, Blu-ray disc, etc.), semiconductor memory (e.g., RAM, EPROM, EEPROM, etc.), and / or magnetic memory (e.g., hard disk drive, floppy disk drive, tape drive, MRAM, etc.). Storage unit 1120 may include volatile, non-volatile, dynamic, static, read / write, read-only, random access, sequential access, location-addressable, file-addressable, and / or content-addressable devices.

[0184] It should be understood that the memory 1120 includes one or more physical devices. However, aspects of the instructions described herein may alternatively be executed and propagated via a communication medium (e.g., electromagnetic signals, optical signals, etc.) that is not permanently retained by the physical devices.

[0185] The logic unit 1110 and the memory unit 1120 can be integrated into one or more hardware logic components. Such hardware logic components may include field-programmable gate arrays (FPGAs), application-specific integrated circuits (PASICs / ASICs), application-specific standard products (PSSPs / ASSPs), system-on-a-chip (SoCs), and complex programmable logic devices (CPLDs).

[0186] When included, the display subsystem 1130 can be used to present a visual representation of the data stored in the storage unit 1120. This visual representation may take the form of a graphical user interface (GUI). When the methods and processes described herein change the data stored in the storage unit, and thus change the state of the storage unit, the state of the display subsystem 1130 may also change to visually represent the potential data change. The display subsystem 1130 may include one or more display devices that virtually utilize any type of technology. Such display devices may be integrated with the logic unit 1110 and / or the storage unit 1120 in a shared enclosure, or such display devices may be peripheral display devices.

[0187] When included, the input subsystem 1140 may include or interact with one or more user input devices, such as a keyboard, mouse, or touchscreen. In some examples, the input subsystem may include or interact with selected Natural User Input (NUI) components. Such components may be integrated or peripheral, and the translation and / or processing of input actions may be performed on-board or off-board. Exemplary NUI components may include microphones for speech and / or voice recognition, and infrared, color, stereo, and / or depth cameras for machine vision and / or gesture recognition.

[0188] When included, the communication subsystem 1150 can be configured to communicatively couple the computing system 1100 to one or more other computing devices. The communication subsystem 1150 may include wired and / or wireless communication devices compatible with one or more different communication protocols. As a non-limiting example, the communication subsystem may be configured to perform communication using a wireless telephone network, or a wired or wireless local area network or wide area network. In some examples, the communication subsystem may allow the computing system 1100 to send messages to and / or receive messages from other devices via a network such as the Internet.

[0189] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific examples or illustrations should not be considered limiting, as many variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown and / or described may be performed in the order shown and / or described, in another order, in parallel, or omitted. Similarly, the order of the above processes may be changed.

[0190] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of various processes, systems and configurations, as well as other features, functions, behaviors and / or characteristics disclosed herein, and any and all equivalent schemes thereof.

Claims

1. A method for processing a substrate, the method comprising: A pretreatment is performed on the surface of a multi-region substrate comprising regions containing polycrystalline silicon semiconductors, silicon nitrides, or two or more of silicon oxides, each region having a surface containing a natural silicon oxide layer. The pretreatment includes a solvent-based vapor phase etching process, wherein at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base are flowed through the surface. Selective deposition of a first molecule on the pretreated surface is performed such that the first molecule is adsorbed onto one or more regions and not onto one or more other regions.

2. The method of claim 1, wherein the polysilicon-containing semiconductor comprises one or more of polysilicon or polysilicon germanium.

3. The method of claim 1, wherein the silicon-containing nitride comprises one or more of silicon nitride or silicon germanium nitride.

4. The method of claim 1, wherein the silicon-containing oxide comprises one or more of silicon oxide or silicon germanium oxide.

5. The method of claim 1, wherein the first molecular substance comprises a dielectric film precursor.

6. The method of claim 5, wherein the dielectric film precursor comprises one or more of aluminum oxide, titanium oxide, zinc oxide, silicon dioxide, silicon carbide, silicon carbide, silicon oxynitride, silicon carbonitride, hafnium oxide, tantalum nitride, titanium nitride, or silicon nitride.

7. The method of claim 1, wherein the first molecule comprises an inhibitor molecule.

8. The method of claim 7, wherein the inhibitor molecule comprises one or more of alkylsilane inhibitors or aminosilane inhibitors.

9. The method according to claim 1, wherein the organic base comprises one or more of imidazole, benzimidazole, histidine, guanidine, methylamine, aniline, dimethylamine, diphenylamine, aziridine, piperidine, pyridine, 2-aminopentane, triethylamine, cyclophosphonitrile, hexachlorophosphonitrile, or polyphosphazene.

10. The method of claim 1, wherein the hydroxyl-containing solvent comprises one or more of water, butanol, ethanol, methanol, isopropanol, diethylene glycol, ethylene glycol, methyl tert-butyl ether, or phenol.

11. The method of claim 1, further comprising: Selective deposition of a second molecule on the pretreated surface is performed, such that the second molecule is adsorbed onto one or more regions where the first molecule has not been adsorbed.

12. A processing tool comprising: Processing room; A substrate holder configured to hold a substrate positioned within the processing chamber; Flow control hardware, configured to control the flow rate of each of one or more processing chemicals into the processing chamber; as well as The controller is configured to control the processing tool to: A pretreatment comprising a solvent-based vapor phase etching process is performed by flowing at least hydrogen fluoride, a hydroxyl-containing solvent, and an organic base through the surface of the substrate. as well as After pretreating the surface, selective deposition of a first molecular substance is performed on the surface such that the first molecular substance is adsorbed onto one or more regions and not adsorbed onto one or more other regions.

13. The processing tool of claim 12, wherein the selective deposition is performed in a dry deposition manner.

14. The processing tool of claim 12, wherein the selective deposition is performed in a wet deposition manner.

15. The processing tool according to claim 12, wherein the flow control hardware is configured to co-vaporize the organic base and the hydroxyl-containing solvent.

16. The processing tool of claim 12, wherein the preprocessing is performed in a continuous flow manner.

17. The processing tool of claim 12, wherein the surface is not exposed to air between the performance of the pretreatment and the performance of the selective deposition.

18. The processing tool of claim 12, wherein the first molecular substance comprises a dielectric film precursor.

19. The processing tool of claim 12, wherein the first molecular substance comprises an inhibitor molecule.

20. A method for processing a substrate, the method comprising: A pretreatment is performed on the surface of a multi-region substrate comprising regions containing polycrystalline silicon semiconductors, silicon nitrides, or two or more of silicon oxides, each region having a surface containing a natural silicon oxide layer. The pretreatment includes a solvent-based vapor phase etching process, wherein at least a halogen source, an organic solvent, and an additive flow through the surface. Selective deposition of a first molecule onto the pretreated surface is performed such that the first molecule is adsorbed onto one or more regions and not onto one or more other regions.

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