Pretreating substrate for selective deposition

Abstract

One example provides a method for processing a substrate. The method comprises performing a pretreatment of a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon-containing semiconductor, a silicon-containing nitride, or a silicon-containing oxide. The surface comprises a native silicon oxide layer on each region. The pretreatment comprises a solvent-based vapor etch process wherein at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the surface. The method further comprises performing selective deposition of a first molecular species onto the pretreated surface, such that the first molecular species adsorbs to one or more regions, and does not adsorb to one or more other regions.

Description

PRETREATING SUBSTRATE FOR SELECTIVE DEPOSITIONBACKGROUND

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

[0002] Other methods can use chemical differences between substrate surface regions to selectively adsorb processing chemicals to some substrate areas but not others. The use of substrate surface characteristics for selective deposition can allow a material to be deposited in a pattern without using photolithography. Further, such methods also can facilitate accurate alignment of an edge of a deposited film with an edge of a selected substrate material region onto which the film is deposited.SUMMARY

[0003] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. Furthermore, the claimed subject matter is not limited to implementations that solve any or all disadvantages noted in any part of this disclosure.

[0004] One example provides a method for processing a substrate. The method comprises performing a pretreatment of a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon-containing semiconductor, a silicon- containing nitride, or a silicon-containing oxide. The surface comprises a native silicon oxide layer on each region. The pretreatment comprises a solvent-based vapor etch process wherein at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the surface. The method further comprises performingselective deposition of a first molecular species onto the pretreated surface, such that the first molecular species adsorbs to one or more regions and does not adsorb to one or more other regions.

[0005] In some such examples, the polycrystalline silicon-containing semiconductor comprises one or more of polycrystalline silicon or polycrystalline silicon-germanium.

[0006] In some such examples, the silicon-containing nitride comprises one or more of silicon nitride or silicon germanium nitride.

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

[0008] In some such examples, the first molecular species comprises a dielectric film precursor.

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

[0010] In some such examples, the first molecular species comprises an inhibitor molecule.

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

[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 comprises one or more of water, butanol, ethanol, methanol, isopropanol, diethylene glycol, ethylene glycol, methyl t-butyl ether, or phenol.

[0014] In some such examples, the method further comprises performing selective deposition of a second molecular species onto the pretreated surface, such that the second molecular species adsorbs to one or more regions to which the first molecular species did not adsorb.

[0015] Another example provides a processing tool. The processing tool comprises a processing chamber, a substrate holder configured to hold a substrate positioned within the processing chamber, flow control hardware configured to controla flow 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 etch pretreatment by flowing at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base over a surface of the substrate. The controller is further configured to control the processing tool to perform selective deposition of a first molecular species onto the surface after pretreating the surface, such that the first molecular species adsorbs to one or more regions and does not adsorb to one or more other regions.

[0016] In some such examples, the selective deposition is performed as a dry deposition.

[0017] In some such examples, the selective deposition is performed as a wet deposition.

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

[0019] In some such examples, the pretreatment is performed in a continuous flow.

[0020] In some such examples, the surface is not subject to an air break between performing the pretreatment and performing the selective deposition.

[0021] In some such examples, the first molecular species comprises a dielectric film precursor.

[0022] In some such examples, the first molecular species comprises an inhibitor molecule.

[0023] In yet another example, a method is provided for processing a substrate. The method comprises performing a pretreatment of a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon, silicon nitride, or silicon oxide. The surface comprises a native silicon oxide layer on each region. The pretreatment comprises a solvent-based vapor etch process wherein at least a halogen source, an organic solvent, and an additive are flowed over the surface. The method further comprises performing selective deposition of a first molecular species onto the surface after pretreating the surface, such that the first molecular species adsorbs to one or more regions and does not adsorb to one or more other regions.BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 A schematically shows an example multi-region substrate with a native oxide layer.

[0025] FIG. IB schematically shows a possible surface of the example multiregion substrate of FIG. 1A following an example differentiating pretreatment.

[0026] FIG. 1C schematically shows the example pretreated multi -region substrate of FIG. IB following selective deposition of an example first molecule.

[0027] FIG. ID schematically shows the example pretreated multi-region substrate of FIG. 1C following selective deposition of an example second molecule.

[0028] FIG. 2 is a flow diagram illustrating an example method of processing a substrate comprising performing a differentiating pretreatment.

[0029] FIG. 3 is a bar graph illustrating surface differentiation between polysilicon and silicon nitride following a range of pretreatments and inhibitor exposures.

[0030] FIG. 4 is a bar graph illustrating surface differentiation between polysilicon and silicon nitride following an example differentiating pretreatment.

[0031] FIG. 5 is a bar graph illustrating surface differentiation between polysilicon and silicon nitride following example differentiating pretreatments using different reaction conditions.

[0032] FIG. 6 is a bar graph illustrating surface differentiation between polysilicon and silicon nitride following example differentiating pretreatments and selective inhibitor treatments.

[0033] FIG. 7 is a bar graph illustrating surface stability of polysilicon and silicon nitride substrates over time following an example differentiating pretreatment.

[0034] FIG. 8 schematically shows the effect of an example differentiating pretreatment on aluminum oxide deposition compared to the omission of the differentiating pretreatment.

[0035] FIG. 9 schematically shows the effect of an example differentiating pretreatment on silicon nitride deposition compared to the omission of the differentiating pretreatment.

[0036] FIG. 10 shows an example of a processing tool that can be used to perform a differentiating pretreatment and selective deposition on a substrate.

[0037] FIG. 11 schematically shows an example computing system.DETAILED DESCRIPTION

[0038] The term “alcohol” generally represents hydrocarbon compounds comprising general formula R-OH, where R is an aryl or aliphatic group. Alcohols can have more than one OH (hydroxyl) group (polyols); For example, diols are polyols with two OH groups. Example alcohols comprise methanol, ethanol, and propanol.

[0039] The term “controller” generally represents a computing device that is configured to control one or more functions of another device, such as a processing tool.

[0040] The term “deposition” and variants thereof generally represent a process in which a film is formed on a substrate.

[0041] The term “dielectric film precursor” generally represents a chemical species that can be introduced into a processing chamber to form a dielectric film on the substrate.

[0042] The term “flow control hardware” generally represents components configured to place one or more chemical sources in fluid connection with a processing chamber. Flow control hardware can comprise one or more mass flow controllers and / or valves, for example.

[0043] The terms “inhibitor” and “inhibitor molecule” generally represent a compound that can be introduced into a processing chamber, that can adsorb on a substrate surface, and that can inhibit adsorption of other molecular species on a substrate when adsorbed on the substrate.

[0044] The term “native oxide” generally represents an oxidized surface layer that forms on a substrate when the substrate is exposed to air.

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

[0046] The term “pretreatment” generally represents subjecting a substrate to a process to modify a surface of the substrate before performing a deposition process.

[0047] The term “processing chamber” generally represents an enclosure in which chemical and / or physical processes are performed on substrates. The pressure, temperature and atmospheric composition within a processing chamber are controllable to perform chemical and / or physical processes.

[0048] The term “processing tool” generally represents a machine including a processing chamber and other hardware configured to enable processing to be carried out in the processing chamber.

[0049] The term “processing chemical” generally represents a chemical species used in the pretreatment and / or processing of a substrate in a processing chamber.

[0050] The term “region” generally represents a contiguous portion of a substrate having a same surface chemistry. The term “multi-region” generally represents a substrate having two or more regions, each having distinct surface chemistries.

[0051] The term “substrate” generally represents any object on which a film can be deposited.

[0052] The term “substrate holder” generally represents any structure configured to support a substrate in a processing chamber.

[0053] The term “surface” with reference to a substrate generally represents a portion of a substrate that is exposed to process conditions within a processing chamber.

[0054] The term “vapor etch process” generally represents a dry etching process that uses processing chemicals introduced into a processing chamber in a vapor phase to etch a substrate without a plasma. A vapor etch process can use a processing chemical that forms a liquid phase layer on a substrate surface.

[0055] Substrates in integrated circuit manufacturing processes can include multiple surface regions of differing materials. While having different compositions, the differing materials in different substrate surface regions can sometimes be indistinguishable to processing chemicals. As an example, a substrate can comprise regions of silicon, silicon oxide, and silicon nitride. All three of these bulk materials will grow a native oxide layer when exposed to air. As a result, each surface region behaves similarly with respect to many processing chemicals, such as film precursors and inhibitors. This makes region- selective deposition of films on substrates having regions of two or more of these materials difficult.

[0056] Current treatment techniques that remove the native oxide layer from such different regions result in similar surface terminations on the different regions. For example, dilute hydrofluoric acid etching can be used to remove a native oxide layer from a substrate having two or more of silicon, silicon oxide, or silicon nitride regions. However, dilute hydrofluoric etching leaves each substrate region with hydrogen and F fluorine terminations. Other types of etching leave the regions similarly indistinguishable to incoming processing chemicals. As a result, selective deposition is difficult.

[0057] Accordingly, examples are disclosed that relate to differentiating pretreatments that utilize a dry solvent-based vapor etching pretreatment. The disclosed differentiating pretreatments remove native oxides from different regions of a substrate, including from silicon, silicon nitride, and silicon oxide regions. The disclosed differentiating pretreatments further leave different surface terminations based on the chemistry of each underlying region. As an example, a substrate comprising regions of polysilicon (poly crystalline silicon), silicon nitride, and silicon oxide that is subjected to a differentiating pretreatment according to the present disclosure will yield surfaces that are hydrogen terminated (polysilicon), nitride terminated (silicon nitride), and oxide terminated (silicon oxide). This allows for selective adsorption of processing chemicals such as inhibitors and film precursors. As such, this allows for films to be selectively deposited on some surface regions, but not other surface regions.

[0058] FIG. 1A schematically shows an example multi-region substrate 100 with a native oxide layer 105. Multi -region substrate 100 comprises polysilicon region 110, silicon oxide region 112, and silicon nitride region 114. Native oxide layer 105 is located on surface 115 of substrate.

[0059] Due to native oxide layer 105 on surface 115, polysilicon region 110, silicon oxide region 112, and silicon nitride region 114 are not strongly differentiable to incoming processing chemicals. As such, each portion of native oxide layer 105 behaves similarly with respect to processing chemicals, such as film precursors and inhibitors.

[0060] Thus, a differentiating pretreatment can be applied to multi-region substrate 100 to remove a native oxide layer and differentiate the underlying regions. FIG. 2 shows a flow diagram illustrating an example method 200 for processing a substrate using a differentiating pretreatment. Method 200 can be performed by a processing tool controlled by a controller comprising one or more computing devices. Example processing tools are described in more detail below with regard to FIG. 10. Example computing devices are described herein and with regard to FIG. 11.

[0061] At 210, method 200 comprises performing a pretreatment on a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon-containing semiconductor, a silicon-containing nitride, or a silicon-containing oxide. The surface comprises a native silicon oxide layer on each region of the two or more regions.

[0062] The pretreatment is a process that comprises at least a solvent-based vapor etch process wherein at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the surface. When additionally or alternatively combined with the deposit of one or more inhibitors, the pretreatment can allow for three or more material surfaces to be distinguished. In addition to the above-described examples of silicon nitride, silicon oxide, and polysilicon surfaces, the disclosed example pretreatments also can allow other surfaces to be distinguished. Examples include polycrystalline silicon-germanium, silicon-germanium oxide, and silicongermanium nitride surfaces.

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

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

[0065] The solvent-based vapor phase etch process of method 200 removes the need for wet etching or wet processing. Various methods can be used to vaporize the hydroxyl containing solvent and organic base. Examples include feeding a solution of the hydroxyl containing solvent and organic base into a vaporizer prior to being introduced into the processing chamber. A flow-over vapor approach also can be used, in which a carrier gas is flowed over a heated solution of the hydroxyl containing solvent and organic base. In some examples, gas-phase hydrofluoric acid can be flowed to the processing chamber separately from the hydroxyl containing solvent and organic base. In other examples, hydrofluoric acid can be combined with the hydroxyl containing solvent and organic base before introduction into the processing chamber. Flows of the pretreatment processing chemicals can be continuous or pulsed. In some examples, a total chamber pressure can range from 0.1 Torr to 10 Torr during pretreatment. Further, in some examples, a substrate temperature can range from 60° C to 180° C during pretreatment. In other examples, pressures and / or temperatures outside of these ranges can be used.

[0066] The hydroxyl containing solvent creates a solvent layer at the surface of the substrate. This allows the hydrofluoric acid to dissolve into the solvent layer and perform the etching of the native oxide layer. The organic base acts as a catalyst that biases the etch towards the oxide or nitride layer. This allows for etching to be stopped or slowed on silicon and silicon nitride once the native oxide layer has been removed and the regions are terminated with hydrogen and amine, respectively. The concentration of the organic base in the hydroxyl containing solvent can be 1% or lower in some examples. In other examples, the concentration of the organic base in the hydroxyl containing solvent can be greater than 1%.

[0067] Example pretreatment processes according to method 200 favor silicon tetrafluoride (SiF4) formation at equilibrium. SiF4 is a gas, and thus volatilizes upon formation for removal from the substrate. The hydrogen from the hydrofluoric acid forms water from the oxygen of the native oxide layer. This water also can be removed by volatilization. Some wet etching processes, in contrast, can use ammonia and hydrofluoric acid. This can form SiFe2' anions with two ammonium cations (diammonium hexafluoride silicate). This compound is a solid. Thus, wet etching can leave behind a similar surface chemistry on different substrate regions.

[0068] FIG. IB shows the example multi-region substrate 100 of FIG. 1A following a differentiating pretreatment 120 according to the present disclosure. As shown at 122, polysilicon region 110 has become H terminated. As shown at 124, silicon oxide becomes OH terminated. As shown at 126, silicon nitride becomes NH2 terminated. This pretreatment thus differentiates the surfaces of the three substrate regions. These surfaces are then able to selectively react with the next incoming molecular species. For example, selective inhibition and / or film deposition is possible. It should be noted that other terminal groups are possible following such differentiating pretreatments, and that such differentiating pretreatments may not necessarily result in a surface with uniform terminal groups.

[0069] Returning to FIG. 2, at 220, method 200 comprises performing selective deposition of a first molecular species onto the pre-treated surface, such that the first molecular species adsorbs to one or more regions and does not adsorb to one or more other regions. For example, the first molecular species can comprise a dielectric film precursor. Example dielectric film precursors include precursors for one or more of aluminum oxide, titanium oxide, zinc oxide, silicon dioxide, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbon nitride, hafnium oxide, tantalum nitride,titanium nitride, or silicon nitride. The surface region differentiation that results from the disclosed example differentiating pretreatments can be used to selectively deposit a film on some surface regions but not others without the use of an inhibitor in some examples. In other examples, the first molecular species can comprise an inhibitor molecule. Examples of inhibitor molecules include alkylsilane inhibitors and an aminosilane inhibitors. Various examples of alkylsilane inhibitors and aminosilane inhibitors are listed herein below. An inhibitor can be used to inhibit the adsorption of a film precursor to a substrate surface. As such the selective adsorption of an inhibitor molecule to the substrate surface in some regions but not others can allow film deposition to occur on uninhibited surfaces but not inhibited surfaces. However, whether an inhibitor is used or whether a film precursor selectively adsorbs without the use of an inhibitor, region- selective deposition can be performed without the use of photolithographic patterning.

[0070] In some examples, the selective deposition of the first molecular species can be a wet or dry application. Some processing tools can perform this step without an air break (e.g., using load locks or transfer regions where the substrate is under inert gas or vacuum while awaiting a next stage of treatment). However, the pretreated surface can have inherent stability, and not re-oxidize instantaneously. As such, some air exposure can be tolerated. Thus, different processing tools also can be used for differentiating pretreatment, applying inhibitor, and deposition. Additionally or alternatively, a single tool with multiple modules and / or processing chambers can be used.

[0071] FIG. 1C schematically shows the example pretreated multi -region substrate of FIG. IB following selective deposition of a first molecular species 130. In this example, first molecular species 130 adsorbs selectively to silicon nitride region 114 to form a layer 132 of the first molecular species 130.

[0072] In some examples, layer 132 can be a layer of a film precursor. In such examples, the layer of film precursor can then be converted to a film layer, for example, by oxidation.

[0073] In other examples, layer 132 can be a layer of an inhibitor molecule. In such examples, layer 132 can inhibit the adsorption of a film precursor onto silicon nitride region 114. Thus, referring briefly back to FIG. 2, at 230 method 200 optionally comprises performing selective deposition of a second molecular species onto the pretreated surface. The second molecular species can be a film precursor, and can adsorbto one or more regions to which first molecular species 130 (an inhibitor in this example) did not adsorb.

[0074] FIG. ID shows the example pretreated multi -region substrate of FIG. 1C following selective deposition of a second molecular species 140 comprising a film precursor. In this example, layer 132 of the first molecular species (an inhibitor in this example) prevents the film precursor from adsorbing to the surface of the silicon nitride region 114. In this example, second molecular species 140 adsorbs selectively to silicon oxide region 112 in a layer 142. The layer 142 then can be converted to a film material, for example, by oxidation or other reaction. Further, in some examples, the hydrogen- terminated surface of poly silicon region 110 can prevent the film precursor (e.g., second molecular species 140) from adsorbing to the polysilicon region 110. In other examples, a film precursor may not show selectivity between poly silicon region 110 and silicon oxide region 112.

[0075] FIG. 3 shows a graph 300 comprising experimental data regarding enhancements in selectivity for a range of pretreatments and inhibitor exposures between polysilicon and silicon nitride substrates as determined by water contact angle (WCA). This measurement indicates a hydrophobicity of a surface, and thereby indicates likely deposition selectivity for these surfaces following each pretreatment. Substrates were subject to various treatment routines, none of which included exposure to a hydroxyl containing solvent, an organic base, and hydrofluoric acid.

[0076] The routines of FIG. 3 included no pretreatment, hydrogen (Fb) plasma pretreatment, ammonia (NH3) plasma pretreatment, exposure to a first aminosilane inhibitor (Inhl), H2 plasma pretreatment followed by exposure to the 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 the alkylsilane inhibitor.

[0077] Based on the WCA measurements, the polysilicon and silicon nitride surfaces display similar characteristics following each of the pretreatments and inhibitor exposures. Indeed, “no treatment” (“NONE”) resulted in a larger difference in WCA than any of the subject pretreatments or inhibitor exposures. A difference in inhibitor adsorption would presumably change the surface hydrophobicity of one material vs the other material. However, in all cases, the WCA of polysilicon and silicon nitride measured similarly. As such, selective inhibitor adsorption between polysilicon and silicon nitride is not feasible using these pretreatments.

[0078] FIG. 4 shows a graph 400 comprising experimental data regarding surface differentiation between polysilicon and silicon nitride substrates via an example differentiating pretreatment as determined by WCA. Substrates were subject to no treatment, differentiating pretreatment (e.g., a solvent-based vapor etch process wherein at least a vapor comprising hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the substrate), exposure to the third aminosilane inhibitor, and a differentiating pretreatment followed by exposure to the third aminosilane inhibitor. As described above, the differentiating pretreatment serves to remove native oxide from both polysilicon and silicon nitride surfaces.

[0079] Based on the WCA measurements, the example differentiating pretreatment alone was sufficient to increase the difference in WCA between silicon nitride and polysilicon by -10°. Inhibitor alone adsorbed to each surface, generating similar WCAs. When inhibitor was applied following differentiating pretreatment, the inhibitor adsorption was different on each surface, yielding a difference in WCA of -29°, favorably adsorbing to polysilicon instead of silicon nitride. As such, the application of inhibitor alone does not differentiate between silicon nitride and polysilicon, but differentiating pretreatment does enable selective inhibitor adsorption. This, in turn, can be further used for selective adsorption of film precursor molecules on polysilicon as opposed to silicon nitride.

[0080] FIG. 5 shows a graph 500 comprising experimental data regarding surface differentiation between polysilicon and silicon nitride substrates over differing durations of an example differentiating pretreatment as determined by WCA. Substrates were subject to no pretreatment, differentiating pretreatment (e.g., a solvent-based vapor etch process wherein at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the substrate) for 20 seconds, differentiating pretreatment for 30 seconds, differentiating pretreatment for 60 seconds, and differentiating pretreatment for 162 seconds. In these examples, differentiating pretreatment was performed at temperatures between 50° C and 150° C, and pressures of a few Torr.

[0081] Based on the WCA measurements, the differentiating pretreatment was sufficient to significantly increase the WCA for polysilicon as compared to silicon nitride within 20 seconds. Minimal change was observed with longer pretreatment times. Further, the WCA for polysilicon remained increased as compared to silicon nitride following longer pretreatment times. The higher temperature pretreatment alsodemonstrated differentiation between silicon nitride and polysilicon, showing that a variety of conditions can be used to effectively perform a differentiating pretreatment on substrates to differentiate surfaces.

[0082] In practice, lower temperature pretreatments can be compatible with more surface types. Etching rates can increase with increasing temperature. However, at higher temperatures, the solvent can boil off of the substrate, reducing the solvent thickness and reducing etching capabilities.

[0083] FIG. 6 shows a graph 600 comprising experimental data regarding surface differentiation between polysilicon and silicon nitride following example differentiating pretreatments and selective inhibitor treatments as determined by water contact angle. Substrates were subject to no treatment, differentiating treatment alone for 30 seconds, no treatment followed by exposure to the third aminosilane inhibitor, differentiating treatment for 30 seconds followed by exposure to the third aminosilane inhibitor, no treatment followed by exposure to the alkylsilane inhibitor, differentiating treatment for 20 seconds followed by exposure to the alkylsilane inhibitor, differentiating treatment for 30 seconds followed by exposure to the alkylsilane inhibitor, or differentiating treatment for 60 seconds followed by exposure to the alkylsilane inhibitor.

[0084] Based on the WCA measurements, differentiating pretreatment enhances inhibitor adsorption selectivity between polysilicon and silicon nitride for both the third aminosilane inhibitor and the alkylsilane inhibitor. In contrast, with inhibitor exposure alone, both the third aminosilane inhibitor and the alkylsilane inhibitor adsorbed similarly to polysilicon and silicon nitride. As such, differentiating pretreatment can enhance selectivity for multiple inhibitor molecules.

[0085] FIG. 7 shows a graph 700 comprising experimental data regarding surface stability of polysilicon and silicon nitride substrates over time following example differentiating pretreatments as determined by WCA. Substrates were subject to either differentiating pretreatment alone, or differentiating pretreatment followed by exposure to the third aminosilane inhibitor. Following pretreatment, substrates were subject to WCA measurements after 20 minutes, 3 hours, or 25 hours of air exposure time.

[0086] As shown, WCA on silicon nitride did not significantly change with air exposure time. WCA on polysilicon begins to decrease slightly after 3 hours of air exposure. Following inhibitor exposure, WCA on silicon nitride actually increases withair break time, while WCA on polysilicon begins to decrease slightly after 3 hours of air exposure.

[0087] This data indicates that differentiating pretreatment results in stable surface conditions for several hours. This can allow for the use of differentiating pretreatment with process tools that expose the substrate to a relatively brief air break prior to molecular deposition.

[0088] As described above, the combination of differentiating pretreatment and selective inhibitor exposure can enable selective deposition of dielectric film precursors. Example inhibitors include alkylsilane inhibitors and aminosilane inhibitors. Example dielectric film precursors include precursors for aluminum oxide and silicon nitride. FIG. 8 schematically shows the effect of differentiating pretreatment on aluminum oxide deposition. At 800, FIG. 8 shows an example multi-region substrate 801 with a native oxide layer 805. Multi-region substrate 801 comprises polysilicon region 810, silicon oxide region 812, and silicon nitride region 814. Native oxide layer 805 extends across each of poly silicon region 810, silicon oxide region 812, and silicon nitride region 814.

[0089] At 820, FIG. 8 shows multi -region substrate 801 following inhibitor application, but without differentiating pretreatment. In this example, the inhibitor deposits onto each region through reactions with native oxide layer 805. As such, selective adsorption of a film precursor is not possible in this example.

[0090] At 830, FIG. 8 shows multi-region substrate 801 following differentiating pretreatment. Native oxide layer 805 is removed. Polysilicon region 810 has become hydrogen terminated. Silicon oxide region 812 becomes hydroxyl terminated, and silicon nitride region 814 becomes amine terminated. However, in this example, aluminum oxide precursor is not selective to these surfaces. As such, at 840, FIG. 8 shows multi -region substrate 801 following differentiating pretreatment and adsorption of an aluminum oxide precursor (indicated schematically by Al). As shown, the aluminum oxide film precursor adsorbs onto each of regions 810, 812, and 814.

[0091] In view of the lack of selectivity of the aluminum oxide precursor to the different surface chemistries, an inhibitor can be selectively adsorbed to the surface to allow for selective adsorption of the aluminum oxide film precursor on uninhibited surface. At 850, FIG. 8 shows multi -region substrate 801 following differentiating pretreatment and following inhibitor application. Inhibitor molecules are indicated schematically by “X”. As shown, inhibitor adsorbs to polysilicon region 810 andsilicon oxide region 812. However, the inhibitor does not adsorb to silicon nitride region 814.

[0092] At 860, FIG. 8 shows multi-region substrate 801 following differentiating pretreatment and inhibitor exposure, and further following exposure to an aluminum oxide precursor (“Al”). In this example, aluminum oxide precursor selectively adsorbed to silicon nitride region 814. As such, the differentiating pretreatment allows the selective deposition of aluminum oxide onto silicon nitride at least by preventing the inhibitor from adsorbing to the silicon nitride surface, while the inhibitor adsorbs to polysilicon and silicon oxide.

[0093] FIG. 9 schematically shows the effect of differentiating pretreatment on an example silicon nitride deposition. At 900, FIG. 9 shows an example multi-region substrate 901 with a native oxide layer 905. Multi-region substrate 901 comprises polysilicon region 910, and silicon nitride region 814. Native oxide layer 905 extends across polysilicon region 910 and silicon nitride region 914.

[0094] At 920, FIG. 9 shows multi-region substrate 901 following exposure to a silicon nitride precursor, but without differentiating pretreatment. In this example, silicon nitride precursor (SiN) is deposited onto each region through reactions with native oxide layer 905. The silicon nitride film can be formed, for example, using atomic layer deposition (ALD). In a silicon nitride ALD deposition process, a silicon - containing precursor is adsorbed to the substrate. Then, the adsorbed precursor is chemically converted to silicon nitride. Chemical conversion can be performed using exposure to ammonia and nitrogen, for example.

[0095] At 930, FIG. 9 shows multi-region substrate 901 following differentiating pretreatment. Native oxide layer 905 is removed. Polysilicon region 910 has become H terminated. Silicon nitride region 914 becomes N terminated.

[0096] At 940, FIG. 9 shows multi-region substrate 901 following differentiating pretreatment and following exposure to a silicon nitride film precursor. Silicon nitride film can be deposited using any suitable precursors. For example, ALD deposition of silicon nitride can use a precursor such as an aminosilane precursor, a halogenated silane, and / or other silicon-containing precursors. The precursors can be converted to a silicon nitride layer thermally and / or using plasma. Silicon nitride also can be deposited by use of chemical vapor deposition (CVD) . As shown, silicon nitride selectively deposits on silicon nitride region 914 instead of poly silicon region 910, though some silicon nitride is shown deposited on polysilicon region 910.

[0097] At 950, FIG. 9 shows multi-region substrate 901 following differentiating pretreatment and following inhibitor application. As shown, inhibitor adsorbs to polysilicon region 810, but does not adsorb to silicon nitride region 814.

[0098] At 960, FIG. 9 shows multi-region substrate 901 following differentiating pretreatment and inhibitor application, and further following silicon nitride precursor adsorption. As shown, the silicon nitride precursor selectively adsorbs to silicon nitride region 914.

[0099] FIG. 10 shows an example of a processing tool 1000 that can be used to perform a differentiating pretreatment on a substrate. The processing tool also can be used to selectively adsorb inhibitors to the substrate, and / or selectively deposit a dielectric film precursor on a substrate. Processing tool 1000 is an example of a processing tool that can implement the methods described herein with reference to FIG. 2. In other examples, one or more of the processes described herein can be performed using a different tool.

[0100] Processing tool 1000 comprises a processing chamber 1002 and a substrate support 1004 within the processing chamber. Substrate support 1004 is configured to support a substrate 1006 disposed within processing chamber 1002. Substrate support 1004 can comprise a pedestal, such as an electrostatic chuck pedestal, or any other suitable structure. Substrate support 1004 can comprise a substrate heater 1008.

[0101] The processing tool 1000 further comprises a showerhead 1010. In other examples, a processing tool can comprise a nozzle or other apparatus for introducing gas into processing chamber 1002, as opposed to or in addition to a showerhead. The processing tool 1000 further comprises flow control hardware 1012. Flow control hardware 1012 connects processing gas source(s) to the processing chamber to allow a 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 film 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 source(s) 1024. The flow control hardware 1012 can include any suitable components. Examples include mass flow controllers, valves, and conduits.

[0102] The inhibitor source 1014 comprises any suitable inhibitor that can be introduced into a processing chamber in a gas phase (including liquid or solid materials that can be vaporized for introduction into the processing chamber) for selectivelyadsorbing to a substrate surface. Example inhibitors include silicon-containing inhibitors, such as alkylsilane inhibitors and aminosilane inhibitors. Examples of silicon-containing inhibitors include n-octadecylsilane, tridecylsilane, dodecylsilane, undecylsilane, decylsilane, decan-4-ylsilane, nonylsilane, nonan-4-ylsilane, octan-2- ylsilane, octylsilane, heptylsilane, heptan-4-ylsilane, (tri decafluoro- 1,1, 2, 2-tetra- hydrooctyl)silane, or 10-undecenylsilane. Examples of aminosilane inhibitors include bisdiethylaminosilane, diisopropylaminosilane, bis(t-butylamino) silane (BTBAS), di- sec-butylaminosilane, tris(dimethylamino)silane (3DMAS) dimethylamino trimethyl silane, dimethylamino dimethyl silane, dimethylamino triethyl silane, diethylamino trimethylsilane, n-butyldimethyl(dimethylamino)silane, n- propyldimethyl(dimethylamino)silane, or triisopropyldimethylaminosilane. In some examples, inhibitor source 1014 comprises an inhibitor that is in a condensed phase at standard pressure and temperature. In such examples, inhibitor source 1014 can comprise a flow-over-vapor delivery system, a vaporizer delivery system, charged volume delivery system, a mole delivery device, or other suitable delivery system to volatilize the condensed phase inhibitor. This enables the delivery of the inhibitor precursor in a vapor phase.

[0103] The film precursor source 1016 comprises a volatile or volatilizable dielectric film precursor that can adsorb to a substrate surface and then be chemically converted into a film, such as by using atomic layer deposition. Example dielectric films include aluminum oxide, silicon nitride, titanium oxide, zinc oxide, silicon dioxide, including doped silicon dioxide (e.g., fluorine-doped and carbon-doped silicon dioxide), silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbon nitride, hafnium oxide, tantalum nitride or titanium nitride. Example dielectric film precursors include precursors containing Al, Si, Ti, Zn, Si, Hf, Sn, and Ta. Other materials may also be deposited once the substrate surface has been treated with an inhibitor, such as an aminosilane inhibitor, or metals such as W, Mo, Ta, Ru, Co, and Cu among others using suitable precursors. 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 examples, film precursor source 1016 can comprise a flow-over vapor delivery system, a vaporizer delivery system, a charge volume delivery system, a mole delivery device, or other suitable delivery system to volatilize the condensed phase dielectric film precursor. For forming aluminum oxide dielectric films, example dielectric film precursors can comprise one or more of methyl aluminum propoxide,methyl aluminum isopropoxide, methyl aluminum butoxide, methyl aluminum t- butoxide, methyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum isopropoxide, dimethyl aluminum butoxide, dimethyl aluminum / -butoxide, dimethyl aluminum ethoxide, ethyl aluminum propoxide, ethyl aluminum isopropoxide, ethyl aluminum butoxide, ethyl aluminum / -butoxide, ethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum isopropoxide, diethyl aluminum butoxide, diethyl aluminum / -butoxide, diethyl aluminum ethoxide, propyl aluminum propoxide, propyl aluminum isopropoxide, propyl aluminum butoxide, propyl aluminum / -butoxide, propyl aluminum ethoxide, dipropyl aluminum propoxide, dipropyl aluminum isopropoxide, dipropyl aluminum butoxide, dipropyl aluminum / -butoxide, or dipropyl aluminum ethoxide. For silicon dioxide or other silicon-containing oxides, such dielectric film precursors can comprise one or more of triethoxysilane, tetraethyl orthosilicate, tetramethoxysilane, methyl triethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, bis-triethoxysilylethane, bis-triethoxysilylmethane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, or tetravinyltetram ethylcyclotetrasiloxane. For silicon nitride, such dielectric film precursors can comprise one or more of hexachlorodisilane, hydrazine, tetrachlorosilane, dichlorosilane, octachlorosilane, pentachlorodisilane, tris(dimethylamino) silane, bis(tert-butylamino)silane, di(sec-butylamino)silane, silica, trisilylamine, allyltrimethoxysilane, butyldichlorosilane, chloropentamethyldisilane, dimethoxydimethylsilane, hexamethyldisilane, isobutyl(trimethoxy)silane, methyltrichlorosilane, pentamethyldisilane, isotetrasilane, neopentasilane, trisilane, n-tetrasilane, chlorosilane, diiodosilane, triiodosilane, tetraiodosilane, tetrabromosilane, tetrachlorosilane, bis(diethylamino)silane, and / or any other suitable chlorosilanes, organosilanes, heterosilanes, or alkyl-aminosilanes.

[0104] Hydrogen fluoride source 1018 can comprise hydrogen fluoride gas. Hydroxyl containing solvent source 1020 can comprise any suitable hydroxyl containing solvent. Examples include water, butanol, ethanol, methanol, isopropanol, di ethylene glycol, ethylene glycol, methyl t-butyl ether, or phenol.

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

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

[0107] The processing tool 1000 further comprises an exhaust system 1035. The exhaust system 1035 is configured to exhaust gases from the processing chamber 1002. The exhaust system 1035 can comprise any suitable hardware, including one or more low vacuum pumps and one or more high vacuum pumps.

[0108] The processing tool 1000 further comprises a radiofrequency power source 1036 configured to generate a plasma. In the depicted example, the radiofrequency power source 1036 is electrically connected to the substrate support 1004. The showerhead 1010 is electrically connected to ground as a counter electrode. In other examples, the radiofrequency power source 1036 can be connected to showerhead 1010 and the substrate support 1004 can be electrically connected to ground.

[0109] The processing tool 1000 further includes a matching network 1038 for impedance matching of the radiofrequency power source 1036. The radiofrequency power source 1036 can be configured to provide RF energy of any suitable frequency and power. Example frequencies include 400 kHz, 13.56 MHz, 27 MHz, 60 MHz, and 90 MHz. In some examples, the radiofrequency power source 1036 is configured to operate at a plurality of different frequencies and / or powers. Examples of lower frequencies include frequencies of 3 MHz and below. The lower frequency radiofrequency energy component can comprise a power of up to 6500W. Examples of suitable high-frequency radiofrequency power includes frequencies within a range of 3 MHz to 300 MHz. The higher frequency radiofrequency energy component can comprise a power of up to 6500W. In other examples, a processing tool can provide for other radiofrequency powers and / or frequencies.

[0110] Controller 1040 is operatively coupled to the substrate heater 1008, flow control hardware 1012, exhaust system 1035, and radiofrequency power source 1036. Controller 1040 is configured to control various functions of the processing tool 1000 to pretreat and / or selectively deposit a film on a substrate surface, such as a dielectricfilm. For example, controller 1040 is configured to operate substrate heater 1008 to heat a substrate to a desired temperature. Controller 1040 is also configured to operate flow control hardware 1012 to control a flow of inhibitor from inhibitor source 1014 into processing chamber 1002. Controller 1040 is further configured to operate flow control hardware 1012 to control a flow of film precursor from film precursor source 1016 in order to deposit a film onto the substrate surface after exposing the substrate surface to the aminosilane inhibitor. Controller 1040 can comprise any suitable computing system. Example computing systems are described below with reference to FIG. 11.

[0111] In the description above, various examples include HF as a halogen source for the differentiating pretreatment. However, any suitable halogen source may be used. The volume and mass percentages described for HF may be used for other halogen sources in various examples. In some examples, two or more halogen sources may be used. The halogen source may be any halogen-containing (e.g., X-containing, where X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) compound that exists in vapor phase at the processing temperature. Examples include hydrogen fluoride (HF), hydrogen chloride (HC1), hydrogen bromide (HBr), fluorine (F2), chlorine (Ch), bromine (Bn), chlorine trifluoride (CIF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCI3), and nitrogen tribromide (NBn). In some implementations, the halogen source is an organohalide, with examples including fluoroform (CHF3), chloroform (CHCI3), bromoform (CHBn), carbon tetrafluoride (CF4), carbon tetrachloride (CCh), carbon tetrabromide (CBn), perfluorobutene (C4F8), and perchlorobutene (C4CI8).

[0112] In some implementations, the halogen source is a silicon halide, with examples including silicon tetrafluoride (SiF4), silicon tetrachloride (SiCh), silicon tetrabromide (Si Bn), and compounds that include SiXe such as H2SiXe. In some implementations, the halogen source is a metal halide with examples including molybdenum hexafluoride (MoFe), molybdenum hexachloride (MoCk), molybdenum hexabromide (MoBre), tungsten hexafluoride (WFe), tungsten hexachloride (WCk), tungsten hexabromide (WBre), titanium tetrafluoride (TiF4), titanium tetrachloride (TiCh), titanium tetrabromide (TiBn), zirconium fluoride (ZrF4), zirconium chloride (ZrCh), and zirconium bromide (ZrBn). Metal halides may be used in some examples to selectively etch metal oxides. In the description above, various examples include a hydroxyl containing solvent as an organic solvent for the differentiating pretreatment. However, any organic solvent may be used. The volume and mass percentagesdescribed for the hydroxyl containing solvent may be used for other organic solvents in various examples. In some examples, the organic solvent may include two or more of the organic solvents or types of organic solvents described herein. In some examples, water may be provided instead of, or in addition to, the organic solvent.

[0113] In certain implementations, the organic solvent may be an alcohol. The alcohol can be an alcohol having a formula of X-C(R)„(OH)-Y, where: n is 1; each X and Y can be independently selected from hydrogen, -[C(R1)2]m- C(R2)3, or OH, wherein each R1and R2is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10; and each R independently is selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof.

[0114] In some examples, each R, R1and R2independently is selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the alcohol may further be 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 amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0115] In other examples, when at least one of X or Y = -[C(R1)2]m-C(R2)3 or R is a hydrogen and m is 1, the alcohol can be a C3 alcohol. For instance, if at least one R1and one R2is absent, then the C3 alcohol can be a C3 alkenol (e.g., allyl alcohol). In another instance, R and one R2together can form a ring(such as, cycloaliphatic), then the C3 alcohol can be a cyclopropanol or 2-cyclopropenol.

[0116] In yet other examples, when at least one of X or Y = -[C(R1)2]m-C(R2)3 or R is a hydrogen and m is 2, the alcohol can be a C4 alcohol. For instance, if at least one R1and one R2is absent, then the C4 alcohol can be a C4 alkenol (e.g., 2-buten-l- ol or 3-buten-l-ol). In another instance, R and one R2together can form a ring (such as, cycloaliphatic), then the C4 alcohol can be a C4-cyclic alcohol (e.g., cyclobutanol or a cyclopropylmethanol). In yet another instance, if both X and Y are not 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(R1)2]m-C(R2)3, the alcohol can be a diol. In other instances, when at least one X or Y= -[C(R1)2]m-C(R2)3 and at least one R1= OH or one R2= OH, or when R= OH, the alcohol can be a diol. Example diols include, but are not limited to, 1,4-butane diol, propylene- 1,3 -diol, and the like.

[0118] In other instances, when X = Y = OH, the alcohol can be a triol. In yet other instances, when X = R = OH, the alcohol can be a triol. In some instances, when at least one of X or Y is -[C(R1)2]m-C(R2)3 and one R1and at least one R2is OH, the alcohol can be triol. In other instances, when R = OH and X = -[C(R1)2]m-C(R2)3 and one R1and at least one R2is OH, the alcohol can be triol. Example triols include, but are not limited to, glycerol or glycerine derivatives thereof.

[0119] In particular examples, when R = cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl- heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol can be a heterocyclyl alcohol (e.g., an optionally substituted heterocyclyl substituted with or more hydroxyls, such as furfuryl alcohol). In other examples, when at least one of X or Y is -[C(R1)2]m-C(R2)3 and one R1and at least one R2is cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl- heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl- heterocyclyl, the alcohol can be a heterocyclyl alcohol.

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

[0121] In these or other cases, the organic solvent may include a laboratorytype solvent such as acetonitrile, dichloromethane, carbon tetrachloride, or a combination thereof.

[0122] In some examples, the organic solvent may be a ketone. The organic solvent can also be a ketone having a formula of X-[C(O)]„-Y, where: n is an integer from 1 to 2; each X and Y can be independently selected from-C(R1)3, -R2, or -[C(R3)2]m- C(O)-R4, wherein each R1, R2, R3and R4can be independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof; in which R3and R4, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic, and in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic; and m is an integer from 0 to 10.

[0123] In some examples, each R1, R2, R3and R4, independently, are alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl- heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl- heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl- heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkylheteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the organic solvent may further be substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=0), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof. One example ketone is acetone.

[0124] In some examples, when X and Y, taken together with the atom to which each are attached, forms a cycloaliphatic or cycloheteroaliphatic, the organic solvent can be a cyclic ketone. Example cyclic ketones include cyclohexanone, cyclopentanone, and the like.

[0125] In other examples, when at least one of X or Y = -[C(R3)2]m-C(O)-R4, the organic solvent can be a diketone. Example diketones include diacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, acetylacetone, acetonyl acetone, and the like, as well as halogenated forms thereof, such as hexafluoroacetyl acetone.

[0126] In further examples, when at least one of X or Y = -[C(R3)2]m-C(O)-R4and X and Y, taken together with the atom to which each are attached, forms a cycloaliphatic or cycloheteroaliphatic, the organic solvent can be a cyclic diketone. Example cyclic diketones include dimedone, 1,3-cyclohexanedione, and the like.

[0127] In some instances, when X = -CH3, the organic solvent can have Y = - C(RX)3, in which at least one R1is C2-10 hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof. Example materials can include methyl propyl ketone, methyl butyl ketone, hydroxy acetone, and the like.

[0128] In other instances, when X = -CH3, the organic solvent can have Y = - R2, in which at least one R2is C2 alkenyl, C3-10 aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof. Example materials can include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, and the like.

[0129] In yet other instances, when at least one of X or Y = aromatic, or aliphatic-aromatic, or heteroaliphatic-aromatic, the organic solvent can be an aromatic ketone. Example materials include acetophenone, benzophenone, benzyl acetone, 1,3- diphenylacetone, cyclopentyl phenyl ketone, and the like.

[0130] In certain examples where the organic solvent includes a ketone, the ketone may be selected from acetone and acetophenone. One or more additional ketones and / or other organic solvents described herein may be provided, as well.

[0131] In some examples, the organic solvent may be an alkane. In certain examples, the alkane may be an acyclic branched or unbranched hydrocarbon having the general formula CnH2n+2. Example acyclic alkanes include, but are not limited to, pentane, hexane, octane, and combinations thereof. In certain other examples, the alkane may be a cyclic hydrocarbon. Example 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 moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings,have a continuous, delocalized 7t-electron system. Typically, the number of out of plane ^-electrons corresponds to the Hiickel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system. In some cases, an aromatic solvent may be selected from toluene and benzene.

[0133] In some examples, the organic solvent may be an ether having a formula of X-O-Y or X-O-[C(R)2]n-O-Y, where: n is an integer from 1 to 4; each X and Y can be independently selected from -[C(R1)2]m-C(R2)3 or -R3or -[C(R4)2]P-O-[C(R5)2]m-C(R6)3, wherein each of R1, R2, R3, R4, R5, R6and R is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10 and p is an integer from 1 to 10; in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic group.

[0134] In some examples, each R, R1, R2, R3, R4, R5and R6independently are selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl -heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl -heterocyclyl , heteroalkyl -heteroaryl , heteroalkenyl -heteroaryl , heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the ether may further be 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 amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0135] In some examples, when X and Y are taken together with the atom to which each are attached in order form a cycloheteroaliphatic 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 taken together form a six, seven, eight, nine, or ten-membered ring. Example ethers include, but are not limited to, 1,3-dioxolane, or derivatives thereof. In other examples, when n = 2 and R = H, X and Y form a seven, eight, nine, or ten-membered ring. Example ethers include, but are not limited to, 1,4- dioxane, or derivatives thereof. In yet other examples, when n = 1 or n = 2, then R is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic- aromatic, heteroaliphatic-aromatic, or any combinations thereof. Example cyclic ethers include tetrahydrofuran, 2-m ethyltetrahydrofuran, 2-m ethyl- 1,3 -di oxolane, and the like.

[0136] In other examples, when at least one of X or Y = aromatic, the organic solvent can be an aromatic ether. Example aromatic ethers include anisole, diphenyl ether, and the like.

[0137] In some examples, when at least one of X or Y = cycloaliphatic, the organic solvent can be a cycloalkyl ether. Example cycloalkyl ethers include cyclopentyl methyl ether, cyclohexyl methyl ether, and the like.

[0138] In other examples, when at least one of X or Y = -[C(R4)2-O]P-C(R6)3, the organic solvent can be a glycol based ether. Example glycol based ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, etc., including methyl, ethyl, propyl, and butyl mono- and diethers of ethylene glycol, and the like.

[0139] In some cases, the organic solvent is a nitrile having a formula R-C=N, whereR is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic.

[0140] In certain examples, R can be optionally substituted with a hydroxyl group (e.g., in one example R can be CH3-CH(OH)-CH2-, and the organic solvent will be CH3-CH(OH)-CH2-CN).

[0141] One example nitrile is acetonitrile, mentioned above.

[0142] In the description above, various examples include an organic base as an additive for the differentiating pretreatment. However, any suitable additive may be used. The volume and mass percentages for the organic base may be used for other additives in various examples. In some examples, two or more additives may be used. In certain examples, the additive may act as a proton acceptor and promote formation of HF . In some such cases, the EHY may actively etch one or more materials on the substrate such as an oxide material or another material. The additive may be selectedfrom a number of different types of additives. For instance, in some cases the additive may be a heterocycle compound, a heterocyclic aromatic compound, a halogensubstituted heterocyclic aromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidizer, a bifluoride source, ammonia, an aldehyde, a carbene, or an organic acid. In some cases, more than one additive may be used. In some examples, the additive may be a boron- containing Lewis acid or Lewis adduct. Boron trifluoride (BF3) is an example of a Lewis acid that forms the acid-base adduct BFF. In some cases, the additive may fall into two or more of the categories listed above. In various examples, the additive serves the purposes of accelerating the reaction rate and enhancing the reaction selectivity.

[0143] In certain examples, the additive is a heterocyclic aromatic compound. The term “aromatic” is defined above. A heterocyclic aromatic compound is an aromatic compound that includes 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, phosphorous, sulfur, or halo). Example heterocyclic aromatic compounds that may be used include, but are not limited to, picoline, pyridine, pyrrole, imidazole, thiophene, N- methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolonic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, and azulene. In some cases, a heterocyclic aromatic compound may be methylated. In some cases, a heterocyclic aromatic compound may follow the Hiickel 4 / / + 2 rule. In some cases, the additive is a halogen-substituted aromatic compound. A halogen- substituted aromatic compound is an aromatic compound that includes at least one halogen bonded to the aromatic ring. As used herein, halogen or halo refers to F, Cl, Br, or I. Example 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 a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (Ci- 10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. A heterocyclic aliphatic compound is an aliphatic compound that includes 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, phosphorous, sulfur, or halo). Example heterocyclic aliphatic compounds include pyrrolidine, piperidine, etc.

[0145] In some examples, the additive is an amine having a formula of NRJR2R3, where: each of R1, R2, and R3is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic- aromatic, heteroaliphatic-aromatic, or any combinations thereof; in which R1and R2, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic; and in which R1, R2, and R3, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic.

[0146] In some examples, each of R1, R2, and R3is independently selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the amine may further be 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 amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0147] In some examples, when at least one of R1, R2, and R3is aliphatic, haloaliphatic, haloheteroaliphatic, or heteroaliphatic, the additive is an alkyl amine. The alkyl amine can include dialkylamines, trialkyl amines, and derivatives thereof. Example alkyl amines include dimethylisopropylamine, 7V-ethyldiisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, t-butyl amine, and the like.

[0148] In other examples, when at least one of R1, R2, and R3includes a hydroxyl, the additive is an alcohol amine. In one instance, at least one of R1, R2, andR3is an aliphatic group substituted with one or more hydroxyls. Example alcohol amines include 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2- (dipropylamino)ethanol, 2-(dibutylamino)ethanol, 7V-ethyldiethanolamine, N- tertbutyldiethanolamine, and the like.

[0149] In some examples, when R1and R2, taken together with the atom to which each are attached, form a cycloheteroaliphatic, the additive can be a cyclic amine. Example cyclic amines include piperidine, A -alkyl piperidine (e.g., N-m ethyl piperidine, A-propyl piperidine, etc.), pyrrolidine, A -alkyl pyrrolidine (e.g., / f-m ethyl pyrrolidine, A-propyl pyrrolidine, etc.), morpholine, A-alkyl morpholine (e.g., N- methyl morpholine, A-propyl morpholine, etc.), piperazine, A -alkyl piperazine, N,N- dialkyl piperazine (e.g., 1,4-dimethylpiperazine), and the like.

[0150] In other examples, when at least one of R1, R2, and R3includes an aromatic, the additive is an aromatic amine. In some examples, at least one of R1, R2, and R3is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. In other examples, both R1and R2includes an aromatic. In yet other examples, R1and R2and optionally R3, taken together with the atom to which each are attached, from a cycloheteroaliphatic that is an aromatic. Example aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and the derivatives thereof.

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

[0152] In some examples, the additive may include a fluoramine. A fluoramine is an amine having one or more fluorinated substituents. Example fluoroamines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0153] In some examples, the additive can be a nitrogenous analogue of a carbonic acid, having a formula R1N-C(NR2)-NR3. Example additives can include, but are not limited to, guanidine or derivatives thereof.

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

[0155] In some examples, the additive may include an amino acid. The amino acid may have a formula of R-CH(NR'2)-COOH, where: each R and R' independently are hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combination thereof.

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

[0157] In some examples, the additive may include an organophosphorus compound. The organophosphorus compound may be a phosphate ester, a phosphate amide, a phosphonic acid, a phosphinic acid, a phosphonate, a phosphinate, a phosphine oxide, a phosphine imide, or a phosphonium salt. Example organophosphorus compounds include phosphoric acid and trialkylphosphate. In some cases, the organophosphorous compound is a phosphazene. A phosphazene is an organophosphorus compound that includes phosphorus (V) with a double bond between P and N. The phosphazene may have a formula of RN=P(NR2)3 (where each of R and R2 are independently selected from hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combination thereof). In some cases, the phosphazene may have a formula of [X2PN]n(where X is a halide, alkoxide, or amide). Other types of phosphazenes may be used as desired.

[0158] In some examples, the additive includes an oxidizer. As used herein, an oxidizer is a material that has the ability to oxidize (e.g., accept electrons from) another substance. Example oxidizers that may be used include, but are not limited to, hydrogen peroxide, sodium hypochlorate, and tetramethyl ammonium hydroxide.

[0159] In some examples, the additive includes a bifluoride source. A bifluoride source is a material that includes or produces bifluoride (HF2‘). Example bifluoride sources that may be used include, but are not limited to, ammonium fluoride, aqueous HF, gaseous HF, buffered oxide etch mixture (e.g., a mixture of HF and a buffering agent such as ammonium fluoride), and hydrogen fluoride pyridine. In some examples, the bifluoride source (and / or one or more of the other additives listed herein) may react to form HF2' before or after delivery to the reaction chamber.

[0160] In some examples, the additive includes an aldehyde having a formula of X-[C(O)]-H, where:X can be selected from hydrogen, -R1, -C(R2)3 or -[C(R3)2]m-C(O)H, whereineach R1, R2and R3independently are selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof, and m is an integer from 0 to 10.

[0161] In some examples, each of R1, R2, and R3is, independently, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl- heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl- heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl- heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkylheteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the aldehyde or ketone may further be substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=0), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0162] In some examples, when X = aromatic, the additive can be an aromatic aldehyde. Example aromatic aldehydes include benzaldehyde, 1 -naphthaldehyde, phthalaldehyde, and the like.

[0163] In other examples, when X = aliphatic, the additive can be an aliphatic aldehyde. Example aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovalerylaldehyde, and the like.

[0164] In yet other examples, when X = -[C(R3)2]m-C(O)H and m is 0 to 10 or when X = aliphatic or heteroaliphatic substituted with -C(O)H, the additive can be a dialdehyde. Example dialdehydes include glyoxal, phthalaldehyde, glutaraldehyde, malondialdehyde, succinaldehyde, and the like.

[0165] In some examples, an 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 cases, an aldehyde used as an additive may be selected from the aldehydes discussed in this section and the aldehydes discussed in the organic solvent section.

[0166] In some examples, the additive includes a carbene. The carbene may have a formula of X-(C:)-Y, where: each of X and Y can be independently selected from H, halo, -[C(R1)2]m- C(R2)3, -C(O)-RJ, or -C(=NR1)-R2, -NR1R2, -OR2, -SR2, or -C(R2)3, wherein each of R1and R2is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10; in which R1and R2, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic group; and in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic group.

[0167] Furthermore, the additive can be a carbenium cation having a formula R1-C+(R)-R2, wherein each of R, R1, and R2is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic- aromatic, heteroaliphatic-aromatic, or any combinations thereof.

[0168] In some examples, each R, R1, and R2independently is selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed examples, the carbene may further be 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 amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof. In any example of a carbene, each of R1and R2can be independently selected.

[0169] In some examples, when at least one of X or Y is halo, the additive can be a halocarbene. Example, non-limiting halocarbenes include dihalocarbene, such as di chlorocarbene, difluorocarbene, and the like.

[0170] In some examples, when both X = Y = -NRJR2, the additive can be a diaminocarbene. In one instance, each of R1and R2is independently aliphatic. Example diaminocarbenes include bis(diisopropylamino) carbene, and the like.

[0171] In other examples, when both at least one of X or Y = -NR'R2and both R1and R2within X or within Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive can be a cyclic diaminocarbene. Example cyclic diamino carbenes include bis(7V-piperidyl) carbene, bis(7V- pyrrolidinyl) carbene, and the like.

[0172] In one instance, when both X = Y = -NR'R2and an R1group from X and an R2group from Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive is an Y-heterocyclic carbene. Example N-heterocyclic carbenes include imidazol-2-ylidenes (e.g., 1,3- dimesitylimidazol-2-ylidene, l,3-dimesityl-4,5-dichloroimidazol-2-ylidene, 1,3- bis(2,6-diisopropylphenyl)imidazol-2-ylidene, l,3-di-tert-butylimidazol-2-ylidene, etc.), imidazolidin-2-ylidenes (e.g., l,3-bis(2,6-diisopropylphenyl)imidazolidin-2- ylidene), triazol-5-ylidenes (e.g., l,3,4-triphenyl-4,5-dihydro-lH-l,2,4-triazol-5- ylidene), and the like.

[0173] In some examples, when X = -NR'R2and Y = -SR2and an R1group from X and an R2group from Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive is acyclic thioalkyl amino carbene. Example cyclic thioalkyl amino carbenes include thiazol-2-ylidenes (e.g., 3-(2,6-diisopropylphenyl)thiazol-2-ylidene and the like).

[0174] In some examples, when X = -NR'R2and Y = -C(R2)3 and an R1group from X and an R2group from Y are taken together, with the atom to which each are attached, to form a cycloheteroaliphatic group, the additive is an cyclic alkyl amino carbene. Example cyclic alkyl amino carbenes include pyrrolidine-2-ylidenes (e.g.,1.3.3.5.5-pentamethyl-pyrrolidin-2-ylidene and the like) and piperidin-2-ylidenes (e.g.,1.3.3.6.6-pentamethyl-piperidin-2-ylidene and the like).

[0175] Further example carbenes and derivatives thereof include compounds having a thiazol-2-ylidene moiety, a dihydroimidazol-2-ylidene moiety, an imidazoleylidene moiety, a triazol-5-ylidene moiety, or a cyclopropenylidene moiety. Yet other carbenes and carbene analogs include an aminothiocarbene compound, an aminooxycarbene compound, a diaminocarbene compound, a heteroamino carbene compound, a 1,3-dithiolium carbene compound, a mesoionic carbene compound (e.g.,an imidazolin-4-ylidene compound, a 1,2,3-triazolylidene compound, a pyrazolinylidene compound, a tetrazol-5-ylidene compound, an isoxazol-4-ylidene compound, a thiazol-5-ylidene compound, etc.), a cyclic alkyl amino carbene compound, a boranylidene compound, a silylene compound, a stannylene compound, a nitrene compound, a phosphinidene compound, a foiled carbene compound, etc. Further example carbenes include dimethyl imidazol-2-ylidene, l,3-bis(2,4,6- trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, (phosphanyl)(trifluoromethyl)carbene, bis(diisopropylamino) carbene, bis(diisopropylamino) cyclopropenylidene, l,3-dimesityl-4,5-dichloroimidazol-2- ylidene, l,3-diadamantylimidazol-2-ylidene, l,3,4,5-tetramethylimidazol-2-ylidene, l,3-dimesitylimidazol-2-ylidene, l,3-dimesitylimidazol-2-ylidene, 1,3,5- triphenyltriazol-5-ylidene, bis(diisopropylamino) cyclopropenylidene, bis(9- anthryl)carbene, norbomen-7-ylidene, dihydroimidazol-2-ylidene, methylidenecarbene, etc.

[0176] In some examples, the additive includes an organic acid. The organic acid may have a formula of R-CO2H, wherein R is selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic or any combinations thereof. In certain examples, R is alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl- heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkylheteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl or any combinations thereof. In particular disclosed examples, R may further be 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 amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide or any combinations thereof. In certain implementations, the organic acid may be selected from formic acid and acetic acid.

[0177] Any of the example materials described herein include unsubstituted and / or substituted forms of the compound. Non-limiting example substituents include, e.g., one, two, three, four, or more substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1-6 alkylsulfinyl(e.g., -S(O)-R, in which R is Ci-6 alkyl); (3) Ci-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (e.g., -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)- R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N- protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (20) C1-6 thioalkoxy (e.g., -S-R, in which R is C1-6 alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) - C(O)NR'R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl- C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) -SO2NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) -NR'R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one example no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group.

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

[0179] Computing system 1100 includes a logic machine 1110 and a storage machine 1120. Computing system 1100 can optionally include a display subsystem 1130, input subsystem 1140, communication subsystem 1150, and / or other components not shown in FIG. 11. Controller 1040 of FIG. 10 is an example of computing system 1100.

[0180] Logic machine 1110 includes one or more physical devices configured to execute instructions. For example, the logic machine can be configured to execute instructions that are part of one or more applications, services, programs, routines, libraries, objects, components, data structures, or other logical constructs. Such instructions can be implemented to perform a task, implement a data type, transform the state of one or more components, achieve a technical effect, or otherwise arrive at a desired result.

[0181] The logic machine can include one or more processors configured to execute software instructions. Additionally or alternatively, the logic machine can include one or more hardware or firmware logic machines configured to execute hardware or firmware instructions. Processors of the logic machine can be single-core or multi-core, and the instructions executed thereon can be configured for sequential, parallel, and / or distributed processing. Individual components of the logic machine optionally can be distributed among two or more separate devices, which can be remotely located and / or configured for coordinated processing. Aspects of the logic machine can be virtualized and executed by remotely accessible, networked computing devices configured in a cloud-computing configuration.

[0182] Storage machine 1120 includes one or more physical devices configured to hold instructions 1160 executable by the logic machine to implement the methods and processes described herein. When such methods and processes are implemented, the state of storage machine 1120 can be transformed — e.g., to hold different data.

[0183] Storage machine 1120 can include removable and / or built-in devices. Storage machine 1120 can 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.), among others. Storage machine 1120 can include volatile, nonvolatile, dynamic, static,read / write, read-only, random-access, sequential-access, location-addressable, file- addressable, and / or content-addressable devices.

[0184] It will be appreciated that storage machine 1120 includes one or more physical devices. However, aspects of the instructions described herein alternatively can be propagated by a communication medium (e.g., an electromagnetic signal, an optical signal, etc.) that is not held by a physical device for a finite duration.

[0185] Aspects of logic machine 1110 and storage machine 1120 can be integrated together into one or more hardware-logic components. Such hardware-logic components can include field-programmable gate arrays (FPGAs), program- and application-specific integrated circuits (PASIC / ASICs), program- and applicationspecific standard products (PSSP / ASSPs), system-on-a-chip (SOC), and complex programmable logic devices (CPLDs), for example.

[0186] When included, display subsystem 1130 can be used to present a visual representation of data held by storage machine 1120. This visual representation can take the form of a graphical user interface (GUI). As the herein described methods and processes change the data held by the storage machine, and thus transform the state of the storage machine, the state of display subsystem 1130 can likewise be transformed to visually represent changes in the underlying data. Display subsystem 1130 can include one or more display devices utilizing virtually any type of technology. Such display devices can be combined with logic machine 1110 and / or storage machine 1120 in a shared enclosure, or such display devices can be peripheral display devices.

[0187] When included, input subsystem 1140 can comprise or interface with one or more user-input devices such as a keyboard, mouse, or touch screen. In some examples, the input subsystem can comprise or interface with selected natural user input (NUI) componentry. Such componentry can be integrated or peripheral, and the transduction and / or processing of input actions can be handled on- or off- board. Example NUI componentry can include a microphone for speech and / or voice recognition, and an infrared, color, stereoscopic, and / or depth camera for machine vision and / or gesture recognition.

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

[0189] It will be understood that the configurations and / or approaches described herein are exemplary in nature, and that these specific examples or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein can represent one or more of any number of processing strategies. As such, various acts illustrated and / or described can be performed in the sequence illustrated and / or described, in other sequences, in parallel, or omitted. Likewise, the order of the above-described processes can be changed.

[0190] The subject matter of the present disclosure includes all novel and non- obvious combinations and sub-combinations of the various processes, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

Claims

CLAIMS:

1. A method for processing a substrate, the method comprising: performing a pretreatment of a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon-containing semiconductor, a silicon- containing nitride, or a silicon-containing oxide, the surface comprising a native silicon oxide layer on each region, the pretreatment comprising a solvent-based vapor etch process wherein at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base are flowed over the surface; and performing selective deposition of a first molecular species onto the pretreated surface, such that the first molecular species adsorbs to one or more regions, and does not adsorb to one or more other regions.

2. The method of claim 1, wherein the poly crystalline silicon-containing semiconductor comprises one or more of polycrystalline silicon or polycrystalline silicon-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 species comprises a dielectric film precursor.

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

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

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

9. The method of 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, cyclodiphosphazane, hexachlorophosphazene, 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 t-butyl ether, or phenol.

11. The method of claim 1, further comprising: performing selective deposition of a second molecular species onto the pretreated surface, such that the second molecular species adsorbs to one or more regions to which the first molecular species did not adsorb.

12. A processing tool, comprising: a processing chamber; a substrate holder configured to hold a substrate positioned within the processing chamber; flow control hardware configured to control a flow of each of one or more processing chemicals into the processing chamber; and a controller configured to control the processing tool to: perform a pretreatment comprising a solvent-based vapor etch process by flowing at least hydrogen fluoride, a hydroxyl containing solvent, and an organic base over a surface of the substrate; and perform selective deposition of a first molecular species onto the surface after pretreating the surface, such that the first molecular species adsorbs to one or more regions, and does not adsorb to one or more other regions.

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

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

15. The processing tool of 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 pretreatment is performed in a continuous flow.

17. The processing tool of claim 12, wherein the surface is not subject to an air break between performing the pretreatment and performing the selective deposition.

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

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

20. A method for processing a substrate, the method comprising: performing a pretreatment of a surface of a multi-region substrate comprising regions of two or more of a polycrystalline silicon-containing semiconductor, a silicon- containing nitride, or a silicon-containing oxide, the surface comprising a native silicon oxide layer on each region, the pretreatment comprising a solvent-based vapor etch process wherein at least a halogen source, an organic solvent, and an additive are flowed over the surface; and performing selective deposition of a first molecular species onto the pretreated surface, such that the first molecular species adsorbs to one or more regions, and does not adsorb to one or more other regions.

Images