In situ de-blocking in plasma etch

Abstract

In semiconductor processing, plasma etching of a material (e.g., carbon or silicon material) due to unwanted deposition of a blocking material (e.g., silicon oxide) from a mask to form vertical high aspect ratio recessed features may result in blocking inside the recessed features. This can be addressed by de-blocking that includes etching the blocking material by contacting the substrate with a halogen source, preferably in the same processing chamber. After the deblocking step, plasma etching is further performed. The de-blocking and plasma etching steps may be repeated multiple times as desired to etch recessed features of a desired depth.

Description

Incorporated by Reference

[0001] The PCT application form is filed concurrently with this specification as a part of this application. Each application identified in the concurrently filed PCT application form from which this application claims the benefit or priority is incorporated herein by reference in its entirety and for all purposes. Technical Field

[0002] The present invention relates to methods and apparatus for semiconductor device fabrication. In particular, embodiments of the present invention relate to methods and apparatus for declogging recessed features during plasma etching in semiconductor processing. Background Art

[0003] In semiconductor device manufacturing, deposition and etching techniques are used to pattern materials, such as metal lines embedded in dielectric layers. Deposition techniques include atomic layer deposition (ALD), chemical vapor deposition (CVD), and physical vapor deposition (PVD). Etching techniques include wet etching methods and dry etching methods (e.g., plasma etching).

[0004] Etching methods can be isotropic and anisotropic. Isotropic etching is characterized by etching in multiple directions (both vertical and horizontal) on the substrate, where the etching rate in different directions is approximately the same. For example, horizontal etching requires isotropic etching. Anisotropic etching is characterized by etching primarily in one direction (e.g., the vertical direction) and is often used to form recessed features (e.g., through-holes) on the substrate. Anisotropic etching is also called "directional etching."

[0005] Directional plasma etching is often used to form recessed features in a target material layer beneath a patterned mask layer. The chemistry of the directional plasma etch is typically selected so that the target material is etched at a higher etch rate than the mask material.

[0006] The background description provided here is for the purpose of generally presenting the context of the present disclosure. It is neither explicitly nor implicitly admitted that the work of the presently designated inventors is prior art to the extent described in this background section and to any aspects of the specification that were not determined to be prior art at the time the application was filed. Summary of the Invention

[0007] Methods and apparatus for plasma etching of materials in semiconductor device fabrication are presented. In some embodiments, the method allows for efficient directional etching and formation of high aspect ratio recessed features, such as recessed features having an aspect ratio of at least about 5:1 (e.g., 5:1-500:1). The method can be used, for example, in the fabrication of 3D NAND devices, dynamic random access memory (DRAM) devices, and high aspect ratio (HAR) logic devices. In some embodiments, the method utilizes alternating plasma etching and declogging steps, wherein the declogging step at least partially removes blocking material that would narrow the recessed features and interfere with the plasma etching.

[0008] One aspect of the present disclosure relates to a method of etching material on a semiconductor substrate, the method comprising: (a) providing a semiconductor substrate having an exposed layer of a mask material, a recessed feature, and a layer of a target material below the layer of the mask material, wherein the target material is exposed at a bottom of the recessed feature; (b) etching the target material using a plasma and thereby increasing the depth of the recessed feature, wherein the etching of the target material causes narrowing or blocking of the recessed feature at least in one location due to deposition of blocking material; and (c) etching the blocking material by contacting the semiconductor substrate with a halogen source without contacting the substrate with an organic solvent and without contacting the substrate with water.

[0009] In some embodiments, the halogen source is provided to a processing chamber containing the substrate with a carrier gas. In some embodiments, the halogen source is provided to the processing chamber containing the substrate without a carrier gas. In some embodiments, the etching of the target material (b) and the etching of the blocking material (c) are performed in a single processing chamber. In some such embodiments, transitioning from (b) to (c) comprises increasing the chamber pressure of the processing chamber.

[0010] In some embodiments, (c) comprises activating the halogen source in a plasma. In some such embodiments, (c) is performed without applying an external bias to the substrate, and in some such embodiments, the plasma in (c) is a transformer-coupled plasma. In some such embodiments, the plasma power in (c) is no greater than 500 W. In some such embodiments, the chamber pressure of the chamber containing the substrate during (c) is between 100 mTorr and 1 Torr. In some embodiments, the chamber pressure of the chamber containing the substrate during (a) is less than 100 mTorr. In some embodiments, the plasma in (c) is pulsed.

[0011] In some embodiments, the blocking material comprises silicon oxide. In some embodiments, the target material is selected from the group consisting of carbon and silicon. In some embodiments, the mask material is selected from the group consisting of silicon oxynitride, silicon nitride, silicon oxide, silicon oxycarbide, silicon boride, boron-doped carbon, tungsten, tungsten-doped carbon, and boron-doped carbon. In some embodiments, the etching of the blocking material has an etch selectivity greater than 1 to both the mask material and the target material.

[0012] In some embodiments, (c) is performed in the absence of a plasma. In some such embodiments, the chamber pressure of the chamber containing the substrate during (c) is between 100 mTorr and 100 Torr.

[0013] In some implementations, the substrate temperature is maintained during the processing.

[0014] Another aspect of the present disclosure relates to a method of etching material on a semiconductor substrate, the method comprising: (a) providing a semiconductor substrate having an exposed layer of a mask material, a recessed feature, and a layer of a target material below the layer of the mask material, wherein the target material is exposed at a bottom of the recessed feature; (b) etching the target material using a plasma and thereby increasing the depth of the recessed feature, wherein the etching of the target material causes narrowing or blocking of the recessed feature at least in one location due to deposition of blocking material; and (c) etching the blocking material by contacting the semiconductor substrate with a plasma generated by a gas-phase halogen source.

[0015] In some embodiments, the etching of the target material (b) and the etching of the blocking material (c) are performed in one process chamber. In some such embodiments, transitioning from (b) to (c) comprises increasing the chamber pressure of the process chamber.

[0016] In some embodiments, the blocking material comprises silicon oxide. In some embodiments, the target material is selected from the group consisting of carbon and silicon. In some embodiments, the mask material is selected from the group consisting of silicon oxynitride, silicon nitride, silicon oxide, silicon oxycarbide, silicon boride, boron-doped carbon, tungsten, tungsten-doped carbon, and boron-doped carbon. In some embodiments, the etching of the blocking material has an etch selectivity greater than 1 to both the mask material and the target material.

[0017] In some embodiments, (c) is performed without applying an external bias to the semiconductor substrate.

[0018] In some embodiments, the method further comprises: repeating steps (b)-(c).

[0019] In some embodiments, the etching of the blocking material comprises contacting the semiconductor substrate with a plasma generated by the halogen source and a vapor of a liquid selected from the group consisting of an organic solvent and water.

[0020] In some embodiments, the plasma in (c) is pulsed.

[0021] In some embodiments, the etching of the blocking material comprises sequentially contacting the semiconductor substrate with the halogen source and a vapor of a liquid selected from the group consisting of an organic solvent and water.

[0022] In some embodiments, (c) further comprises: contacting the semiconductor substrate with an additive selected from the group consisting of amines, heterocyclic compounds, and bifluoride sources.

[0023] In some embodiments, the etching of the blocking material is performed at a pressure between about 0.01 Torr - 1 Torr and a temperature between about -60°C - 250°C.

[0024] In some implementations, the recessed features of the semiconductor substrate provided in (a) have a width of approximately 5 nm - 300 nm.

[0025] In some embodiments, the semiconductor substrate comprises a device selected from the group consisting of a partially fabricated 3D NAND device, a DRAM device, and a logic device. In some embodiments, after the etching is completed, the aspect ratio of the recessed feature is at least about 5:1.

[0026] In some embodiments, the halogen source is selected from the group consisting of nitrogen tribromide (NBr3), nitrogen trichloride (NCl3), chlorine trifluoride (ClF3), hydrogen fluoride (HF), hydrogen chloride (HCl), and hydrogen bromide (HBr).

[0027] In some embodiments, the plasma etching in (b) includes contacting the substrate with an oxygen-containing reactant.

[0028] These and other aspects of the implementation of the objects described in this specification will be explained in the accompanying drawings and the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figures 1A-1D Schematic cross-sectional views of a portion of a substrate undergoing processing are provided according to embodiments presented herein.

[0030] Figure 2 is a process flow diagram for etching deblocking according to embodiments presented herein.

[0031] Figure 3A is a flow chart of a process for deblocking according to embodiments presented herein.

[0032] Figure 3B is a flow chart of a process for deblocking according to embodiments presented herein.

[0033] Figure 4 is a schematic diagram of an apparatus suitable for plasma etching and deblocking according to embodiments presented herein.

[0034] Figure 5 is a diagram illustrating vapor delivery to a process chamber according to embodiments presented herein.

[0035] Figure 6 is a schematic diagram of a system that is suitable for implementing the method proposed in this article. DETAILED DESCRIPTION

[0036] Methods and apparatus for etching are presented. The proposed methods can be used in a variety of applications, but are particularly suitable for directional plasma etching of materials to form high aspect ratio recessed features on semiconductor substrates. For example, the proposed methods can be used to form recessed features having a width between about 5-300 nm (e.g., 10-200 nm) and an aspect ratio of at least about 5:1 (e.g., between about 5:1-500:1), such as an aspect ratio of at least about 10:1, at least about 50:1, or at least 100:1. The methods can be used, for example, in the manufacture of 3D NAND devices, DRAM devices, and high aspect ratio (HAR) logic devices. In some embodiments, the methods are used to form recessed features having a width between about 5 nm and 30 nm in the manufacture of DRAM devices and HAR logic devices.

[0037] Plasma etching for forming high-aspect-ratio recessed features in semiconductor device manufacturing is often hampered by unintentional deposition of blocking materials in the recessed features. Blockage can slow the plasma etch process and may lead to increased non-uniformity. The proposed method allows for rapid in situ deblocking with minimal changes to the critical dimensions of the recessed features.

[0038] As used herein, deposition of a blocking material may include, but is not limited to, redistribution of material from other portions of the substrate (e.g., by sputtering) into the recessed feature, chemical modification of any substrate material to form the blocking material, and a combination of redistribution and chemical modification. For example, the blocking material may be derived from the mask material and / or the target layer material. In some embodiments, the blocking material has a similar composition to the material of the substrate (e.g., the mask material), but is more porous. For example, in some embodiments, a silicon oxide mask material may be sputtered and redistributed during plasma etching and form a more porous silicon oxide blocking material within the recessed feature.

[0039] As used herein, "blocking" means that a recessed feature is narrowed or blocked at any location (e.g., near the opening of the recessed feature) due to the deposition of a blocking material. For example, the diameter of the recessed feature may be reduced by at least about 10%, such as at least about 20%, at the location of the blockage. In some embodiments, the blocking material is selected from the group consisting of oxides (e.g., silicon oxide, tin oxide, etc.), nitrides (e.g., silicon nitride, tantalum nitride, titanium nitride, etc.), carbides (e.g., silicon carbide, etc.), carbonitrides (e.g., silicon carbonitride, etc.), oxycarbides (e.g., silicon oxycarbide, etc.), and the like. In some embodiments, the blocking material is a silicon-containing material, such as a material comprising silicon (Si) and oxygen (O). In some embodiments, the blocking material is silicon oxide (SiO). Other silicon-containing materials containing silicon and oxygen are silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbonitride (SiOCN), and the like.

[0040] In the description of material layers (e.g., SiO, SiON, Si, C, etc.), the chemical formula does not indicate stoichiometry, which may vary. These materials contain the elements listed in their respective chemical formulas, and optionally hydrogen (H). Other elements may be present as dopants in small concentrations, typically not exceeding 20 atomic % (excluding hydrogen), for example, not exceeding 10 atomic % (excluding hydrogen), or not exceeding 5 atomic % (excluding hydrogen).

[0041] In some embodiments, the blocking material is formed from any material of the semiconductor substrate (e.g., the mask material and / or the target material), with or without chemical modification. For example, the blocking material can be formed from a silicon-containing material, such as silicon (Si), silicon oxide (SiO), silicon nitride (SiN), silicon oxynitride (SiON), silicon carbide (SiC), and silicon oxycarbide (SiOC). In some embodiments, the blocking material is an oxygen-containing material and is formed when the semiconductor substrate is exposed to an oxygen-containing reactant (e.g., O2, O3, CO2, CO, COS, and H2O), where the oxygen-containing reactant can be activated in a plasma. For example, an oxygen-containing blocking material (e.g., silicon oxide) may be formed from silicon oxynitride or silicon oxycarbide when these materials are exposed to a plasma etching chemistry that includes an oxygen-containing reactant. For example, when a silicon-containing mask material is used on a substrate and a plasma etch is performed using an oxygen-containing reactant, a silicon oxide blocking material may be formed due to redistribution and / or chemical modification of the mask material.

[0042] As used herein, the term "semiconductor substrate" refers to a substrate at any stage of semiconductor device fabrication, containing semiconductor material anywhere within its structure. It should be understood that the semiconductor material in the semiconductor substrate need not be exposed. A semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material is an example of a semiconductor substrate. The following detailed description assumes that the disclosed implementation is implemented on a semiconductor wafer (e.g., on a 200 mm, 300 mm, or 450 mm semiconductor wafer). However, the disclosed implementation is not limited to this. The semiconductor wafer can have a variety of shapes, sizes, and materials. In addition to semiconductor wafers, the disclosed implementation can be used in other types of objects, including various objects such as printed circuit boards.

[0043] When used in reference to numerical values, the term "about" includes a range of ±20% from the recited value unless otherwise indicated.

[0044] “A” is used herein to designate “one or more.” For example, “a recessed feature” should be interpreted as “one or more recessed features.”

[0045] The proposed method employs one or more deblocking steps alternating with plasma etching steps, wherein the deblocking is preferably performed in the same process chamber as the plasma etching step (in-situ deblocking). Because the substrate does not need to be moved to a different process chamber for deblocking, the entire etching process can be performed in a fast and efficient manner. Another advantage of the proposed method is that no external electrical biasing of the substrate is required during the deblocking step, as the proposed deblocking chemistry can be used to etch blocking materials without an external bias and even in the absence of plasma activation. Deblocking without applying a bias to the substrate can advantageously result in reduced substrate damage and smaller variations in the critical dimensions of recessed features.

[0046] According to some embodiments, deblocking during plasma etching is depicted in Figures 1A-1D and Figure 2 According to the implementation scheme proposed in this article, Figures 1A-1D A schematic cross-sectional view of a portion of a semiconductor substrate during processing is shown. It should be noted that Figures 1A-1D A portion of a substrate is depicted and shows a recessed feature, but it is understood that the substrate may include multiple recessed features and multiple underlying layers (not shown). Figure 2 is a processing flow that depicts the Figures 1A-1D The processing method of the embodiment shown in FIG. 1 is performed by providing a substrate having a target layer below a patterned mask layer, wherein the substrate has at least one recessed feature and wherein the target layer is exposed at the bottom of the recessed feature. An example of such a substrate is shown in FIG. Figure 1A , wherein a patterned mask layer 101 is over a target layer 103, which in turn is over an etch stop layer 105. The substrate includes a recessed feature 107, wherein a target material of the target layer 107 is exposed at the bottom of the recessed feature 107. In some embodiments, the width of the recessed feature 107 is between about 5 nm and 300 nm, such as between about 10 nm and 100 nm. In some embodiments (e.g., in DRAM device manufacturing or in HAR logic device manufacturing), the width of the recessed feature is between about 5 nm and 30 nm.

[0047] The materials of mask layer 101 and target layer 103 are preferably selected so that, for etching the target material, the etch selectivity relative to the mask material in the desired etching direction is greater than 1, for example, greater than 2. The material of etch stop layer 105 is preferably selected so that, for etching the target material, the etch selectivity relative to the etch stop material is greater than 1, for example, greater than 2. Examples of target materials include, but are not limited to, carbon (e.g., amorphous carbon), silicon (e.g., polycrystalline silicon, amorphous silicon, and doped silicon), and other silicon-containing materials. Examples of mask materials include, but are not limited to, silicon-containing materials such as silicon nitride (SiN), silicon oxynitride (SiON), silicon oxide (SiO), silicon carbide (SiC), silicon oxycarbide (SiOC), and silicon boride (SiB); tungsten-containing materials such as tungsten (W); and carbon-containing materials such as tungsten-doped carbon (WC) and boron-doped carbon (BC). The thickness of mask layer 101 is typically less than the thickness of target layer 103. In some embodiments, the thickness of the mask layer 101 is between about 10 nm and 1500 nm, and the thickness of the target layer 103 is between about 50 nm and 1000 nm.

[0048] The material of the target layer 103 on the proposed substrate is exposed so that the gaseous reactants can access it. The substrate is processed in any suitable apparatus having a process chamber equipped with a substrate holder (e.g., a susceptor) and an inlet for introducing reactants, wherein the apparatus is configured to generate a plasma directly in the process chamber or remotely. Figure 2 The process then etches the target layer 103 using plasma etching in step 203, wherein during the etching, blocking material is unintentionally deposited such that it narrows or blocks the recessed features. The resulting substrate is shown in FIG. Figure 1B 1, wherein during plasma etching of the target layer 103, blocking material 109 is deposited on the sidewalls of a recessed feature 107. In the depicted example, the blocking material narrows the recessed feature 107 at the feature opening because it is primarily deposited on the mask layer 101, but in other cases, the blocking material may be deposited deeper within the recessed feature 107. The unintentionally deposited blocking material 109, if not removed, can prevent the plasma etching chemistry from contacting the target layer 103 at the bottom of the recessed feature 107, which in turn may result in slower (or even stopped) etching and lower etch uniformity. For example, if the blocking material is allowed to remain in the recessed feature, the circular hole may have a deviation from roundness and a lower local critical dimension uniformity (LCDU).

[0049] After this treatment, in step 205, the blocking material is etched using a deblocking etchant in the same process chamber as the plasma etch of the target layer. In some embodiments, the deblocking etchant includes a halogen source. For example, the halogen source can be provided in a gas phase without a plasma, or as a plasma generated from a gas. In some embodiments, the halogen source is provided alone or only with a carrier gas (e.g., nitrogen, argon, or helium). In alternative embodiments, the halogen source is provided using an organic solvent and / or water, as further described below. In some embodiments, the first deblocking step begins after at least about 5% (e.g., at least about 10%, at least about 20%, at least about 30%, at least about 40%) of the target depth of the recessed features has been etched by plasma etching. The etching of the blocking material can be partial or complete. The structure obtained after complete removal of the blocking material is depicted in FIG. Figure 1C , which shows that the blocking material 109 is absent and the width of the recessed feature 107 is restored. It should be understood that in some embodiments, the blocking material need not be completely removed and only a portion of the blocking material may be etched to widen the recessed feature. In some embodiments, the deblocking etch chemistry is selective to both the mask material and the target material (i.e., etches the blocking material at a higher rate than both the mask material and the target material). In some embodiments, the etch selectivity is at least about 2 relative to both the mask material and the target material.

[0050] Next, in step 207, the plasma etching of the target material and the etching of the blocking material are optionally repeated as many times as needed to form a recessed feature having a desired depth. For example, the etching process may include 2-21 cycles, such as 2-10 cycles, wherein each cycle includes a target material etching step and a deblocking step. In some implementations, each target material etching step removes between about 10nm and 300nm of target material. By the proposed method, recessed features having a depth between about 100nm and 2000nm and a high aspect ratio of at least about 5:1 can be formed in the target material without changing the processing chamber. In some embodiments, the deblocking material is etched in the absence of plasma (thermal deblocking). In other embodiments, the process is plasma assisted. In some embodiments, the etching of the blocking material is performed without applying an external bias to the semiconductor substrate in order to reduce the possibility of substrate damage due to interaction of ions with the substrate. Reference Figure 1DAfter etching the target layer 103, the substrate has a recessed feature 107 extending to the etch stop layer 105, which is exposed at the bottom of the feature. Depending on the desired size of the recessed feature and the nature of the blocking, etching can be completed in a single etching cycle (with a single target material etching step followed by a deblocking step) or in several cycles of alternating steps. If desired, the process chamber can be purged between the target material etching step and the deblocking step. In some embodiments, the entire etching process is carried out at a single temperature and / or pressure. In other embodiments, the temperature and / or pressure of the target material etching step is different from the temperature and / or pressure of the deblocking step. In some embodiments, the process temperature for both steps is between approximately -60°C and 250°C, for example, between approximately 0°C and 175°C. In some embodiments, the pressure for both steps is between approximately 0.01 and 10 Torr. Constant temperature and constant pressure refer to temperatures within 1°C and 1 mTorr, respectively.

[0051] In some embodiments, the plasma etching step includes introducing an etching process gas into a processing chamber that houses the substrate, wherein the process gas includes a reactant gas (e.g., an oxygen-containing reactant gas and / or a halogen-containing reactant gas) and, optionally, a carrier gas (e.g., nitrogen, helium, argon, etc.), and forming a plasma to activate the reactants in the plasma while also providing an external bias to the substrate to achieve directional etching of the target material. Next, the flow of the reactant gas is stopped, the external bias to the substrate is turned off, and a deblocking composition is introduced into the processing chamber without breaking the vacuum. In some embodiments, the plasma is maintained and the deblocking step is plasma-assisted. In some embodiments, the plasma is generated by the deblocking composition. In some embodiments, the plasma is turned off to perform the deblocking step, and the deblocking step is performed thermally.

[0052] In some embodiments, plasma-assisted deblocking can be used to increase throughput. In embodiments where plasma-assisted deblocking is performed, it can be performed with or without the use of organic solvents or water. In some embodiments, one or more parameters are set to improve selectivity. These include relatively low plasma power. For example, a transformer-coupled plasma (TCP) source power of 500W or less can be used. A relatively high chamber pressure can be used, for example, between 100mTorr and 1Torr. The deblocking plasma can be in continuous mode or pulsed. One or both of the plasma power and the chamber pressure can be changed from the plasma etching step 203. For example, a chamber pressure of less than 100mTorr can be used for the plasma etching in step 203. The transition from step 203 to 205 can involve increasing the chamber pressure. As described above, step 205 can be performed without applying a bias voltage to the substrate.

[0053] Figure 3A and 3B An example of operation 205 is shown. Figure 3A In operation 301, the substrate is exposed to a halogen source. This can be a non-plasma or plasma operation. Figure 3A In an example of , the halogen source is provided in a deblocking gas that contains the halogen source but does not contain a solvent. In some embodiments, the deblocking gas may consist essentially of the halogen source. In some embodiments, the deblocking gas may consist essentially of the halogen source and one or more inert carrier gases (e.g., argon (Ar)). It should be understood that some trace amounts of water or other impurities may be present due to ambient humidity or other environmental conditions. In some embodiments, the substrate is exposed to HF or other halogen-containing gas. In some embodiments, this step may be performed at the same temperature as the etching in operation 203.

[0054] In some embodiments, operation 301 is a non-plasma operation. In such embodiments, the deblocking gas containing the halogen source can be introduced into the chamber in a pulsed flow sequence or as a continuous flow. If pulsed, an inert gas purge operation can be used between pulses. Exemplary chamber pressures for non-plasma operations range from 0.01 Torr to 10 Torr. Exemplary durations for non-plasma operations range from 3 seconds to 120 seconds.

[0055] In other embodiments, operation 301 is a plasma-assisted operation. In some embodiments, plasma-assisted deblocking can be used to increase production capacity. A solvent-free deblocking gas can be provided to the plasma generator and activated in the plasma. In some embodiments, one or more plasma parameters are set to improve selectivity. These include relatively low plasma power (e.g., 500W TCP source power) and / or relatively high chamber pressure (e.g., between 100mTorr and 1Torr). The deblocking plasma can be in continuous mode or pulsed. As described above, operation 303 can be performed without applying a bias voltage to the substrate. An exemplary duration of plasma-activated deblocking is 3 seconds to 120 seconds.

[0056] Examples of halogen sources that may be used in operation 301 are provided below.

[0057] In operation 305, operation 301 may be repeated until the desired amount of obstructing material is removed. In some embodiments, one iteration of operation 301 is sufficient. In other embodiments, there may be multiple cycles of operation 301, where each cycle includes a pulse of a halogen source gas (with or without plasma activation) and a sweep gas.

[0058] Figure 3BA process flow diagram is shown in which a deblocking operation is performed by exposing a substrate to a deblocking gas comprising a halogen source and organic solvent vapor (and / or water vapor). The deblocking gas may also include a carrier gas. In some embodiments, the deblocking gas includes an additive for improving etch selectivity.

[0059] In some embodiments, the halogen source and the organic solvent vapor (and / or water vapor) are sequentially introduced into the process chamber. When used, the additive is typically introduced together with the organic solvent vapor (and / or water vapor). A carrier gas may also be included. Figure 3B These embodiments are illustrated in the process flow diagram of . In step 311, the substrate in the deblocking step is exposed to vapor of an organic solvent and / or water (optionally, with additives) for a period of time in the absence of a halogen source. Next, after a layer of solvent and / or water (e.g., an adsorbed layer) is formed on the substrate, the substrate is exposed to the halogen source in step 313 and allowed to deblock etching. In some embodiments, exposing the substrate to the halogen source is accompanied by activation of the halogen source in a plasma, while exposing the substrate to the solvent and / or water is performed in the absence of a plasma. Next, referring to step 315, the exposure to the solvent and / or water and the exposure to the halogen source are optionally repeated as many times as needed to remove the desired amount of blocking material and complete the deblocking step. For example, each deblocking step may include 2-20 cycles, where each cycle includes solvent and / or water exposure and halogen source exposure.

[0060] exist Figure 3A and 3B In an illustrative embodiment of the method, reference is made to Figure 1A, the target layer 103 is a carbon layer (e.g., an amorphous carbon layer), and the mask layer 101 is a silicon-containing layer, such as a silicon oxynitride (SiON) layer. The etch stop layer 105 can also be a silicon-containing layer, such as a silicon oxide layer. In one example, the thickness of the mask layer 101 is about 300 nm, the thickness of the target layer is about 3000 nm, and the thickness of the etch stop layer is about 200 nm. The process first plasma etches the carbon-containing target layer using a plasma etching chemical that is selective to both the mask material and the etch stop material. For example, the substrate can be exposed to an oxygen-containing reactant that is activated in the plasma. Examples of suitable oxygen-containing reactants include O2, COS, SO2, and any combination thereof. In addition to the oxygen-containing reactant, the plasma etching process gas may include additives and a carrier gas. In some embodiments, the plasma is formed using an inductively coupled plasma (ICP) source. The plasma density is controlled by the plasma source power. Because anisotropic vertical etching is required, the etching in this example also uses a bias voltage provided to the substrate. Examples of frequencies used for the ICP source are 2 MHz, 13 MHz, 27 MHz, and 60 MHz. Examples of frequencies used for the bias voltage are 400 KHz, 1 MHz, 2 MHz, 13 MHz, 27 MHz, and 60 MHz.

[0061] As the target material is etched (e.g., after etching 200 nm to 2000 nm), the silicon-containing mask material will be sputtered away and redeposited on the sidewalls of the recessed features to form a blocking material. In some cases, the material may be chemically modified. For example, when a silicon oxynitride mask is used, the redeposited silicon oxynitride material may react with an oxygen-containing reactant to form a porous silicon oxide blocking material at the opening of the recessed feature, such as Figure 1B Next, without breaking the vacuum, the porous silicon oxide blocking material is etched by exposing the substrate to a halogen source without applying an external bias to the substrate, as described above with reference to Figure 3A or as described in 3B. Optionally, vapor of an organic solvent (and / or water vapor), and optional additives (e.g., amines, heterocyclic compounds, or bifluoride sources) may be used. In some embodiments, the blocking material is etched in the absence of a plasma. In other embodiments, deblocking is plasma-assisted. Following deblocking, the oxygen-containing plasma etch of the carbon-containing target layer may continue in the same process chamber without breaking vacuum and may continue until the blocking material is re-formed, so that the plasma etching and deblocking steps may be repeated as many times as desired in an alternating manner.

[0062] In another illustrative embodiment, the target layer 103 is silicon (e.g., polycrystalline silicon, amorphous silicon, or doped silicon), and the mask material is a silicon-containing mask, such as silicon oxide, silicon oxynitride, silicon nitride, silicon carbide, or the like. The silicon target material is anisotropically etched using a plasma formed in a process gas comprising a halogen source (e.g., Cl2, HBr, a fluorocarbon, or a combination thereof) and an oxygen source (e.g., O2), wherein the oxygen source is used to control the etch profile. In this case, etching of the silicon target material results in the deposition of a silicon oxide blocking material and narrowing of the recessed features, wherein the blocking material originates from the mask material (e.g., by redistribution and / or chemical modification using O2). The blocking material is then etched using a deblocking chemistry as described herein, with or without plasma activation.

[0063] In both examples, the deblocking etch is selective to the blocking material (relative to both the mask material and the target material). In some embodiments, the target material has an etch selectivity greater than 1.5, such as greater than 2, in the desired direction relative to both the mask material and the target material. For example, a silicon oxide blocking material is selectively etched in the desired direction (relative to both the carbon target layer and the silicon oxynitride mask layer). It should be noted that when both the blocking material and the mask material are silicon oxide, deblocking can still be performed selectively because the blocking silicon oxide material is generally more porous and more easily etched than the silicon oxide of the mask material (e.g., CVD deposited silicon oxide). In another example, the silicon oxide blocking material is selectively etched in the desired direction (relative to the silicon target material and to the silicon oxide or silicon oxynitride mask material). Declogging chemicals

[0064] Deblocking is usually performed in the same processing chamber as plasma etching, and includes exposing the substrate to a gas phase halogen source to etch the blocking material. Optionally, steam and / or water vapor of an organic solvent are used. Additives (e.g., amines, heterocyclic compounds, or bifluoride sources) can be added to improve the etching selectivity of the blocking material. An inert carrier gas may also be included. When the reactant is in the gas phase, it is provided to the reaction chamber and exposed to the substrate. Remote or in-situ plasma can be generated by the reactant, or reactants can be provided in thermal deblocking without plasma. Appropriate hardware can be provided to ensure that the reactant is fully gasified before and during being transported to the reaction chamber. Two or more reactants can be mixed before being transported to the reaction chamber. In other embodiments, each reactant can be transported to the reaction chamber separately, for example, in a separate pipeline or at a separate time. Halogen source

[0065] The halogen source can be any halogen-containing compound (e.g., containing X, where X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) that exists in the gas phase at the processing temperature. Examples include hydrogen bromide (HBr), hydrogen chloride (HCl), hydrogen fluoride (HF), fluorine (F2), chlorine (Cl2), bromine (Br2), chlorine trifluoride (ClF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCl3), and nitrogen tribromide (NBr3). In some implementations, the halogen source is an organic halide, such as fluoroform (CHF3), chloroform (CHCl3), bromoform (CHBr3), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), carbon tetrabromide (CBr4), perfluorobutene (C4F8)), and perchlorobutene (C4Cl8). In some implementations, the halogen source is a silicon halide, examples of which include silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), silicon tetrabromide (SiBr4), and compounds including SiX6, such as H2SiX6. In some implementations, the halogen source is a metal halide, examples of which include molybdenum hexafluoride (MoF6), molybdenum hexachloride (MoCl6), molybdenum hexabromide (MoBr6), tungsten hexafluoride (WF6), tungsten hexachloride (WCl6), tungsten hexabromide (WBr6), titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), zirconium fluoride (ZrF4), zirconium chloride (ZrCl4), and zirconium bromide (ZrBr4). Metal halides can be used in some embodiments to selectively etch metal oxides.

[0066] In the following description, various examples include HF as a halogen source. However, any suitable halogen source may be used. The volume and mass percentages described for HF may be used for other halogen sources. In some embodiments, two or more halogen sources may be used. organic solvents In some embodiments, organic solvents are used, examples of which are provided below. Alkanes:

[0067] In some embodiments, the organic solvent may be an alkane. In certain embodiments, the alkane may be an alkane having the general formula C n H 2n+2 Examples of non-cyclic branched or unbranched hydrocarbons include, but are not limited to, pentane, hexane, octane, and combinations thereof. In certain other embodiments, the alkane may be a cyclic hydrocarbon. Examples of cyclic hydrocarbons include, but are not limited to, cyclopentane, cyclohexane, and combinations thereof. Aromatic solvents:

[0068] In some embodiments, the organic solvent may be an aromatic solvent. As used herein, "aromatic" means a cyclic conjugated group or moiety having 5 to 15 (unless otherwise specified) ring atoms of a monocyclic ring (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized π electron system. Typically, the number of out-of-plane π electrons corresponds to the Hückel rule (4n+2). The point of connection to the parent structure is typically through the aromatic portion of the fused ring system. In some cases, the aromatic solvent may be selected from toluene and benzene. alcohol:

[0069] In certain embodiments, the organic solvent may be an alcohol. The alcohol may be a compound having the formula XC(R) n (OH)-Y alcohol, wherein:

[0070] n is 1;

[0071] Each X and Y may be independently selected from hydrogen, -[C(R 1 )2] m -C(R 2 )3 or OH, wherein each R 1 and R 2 R is independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and wherein m is an integer from 0 to 10; and each R is independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0072] In some embodiments, each R, R 1 and R 2independently 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 combination thereof. In certain disclosed embodiments, the alcohol can be further substituted with one or more substituents, such as alkoxy, amide, amine, thioether, thiol, acyloxy, silanyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkylhalide, or any combination thereof.

[0073] In some embodiments, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 ) 3 or R is hydrogen and m is 1, the alcohol may be a C3 alcohol. For example, if at least one R 1 One R 2 In another example, R is present with one R 2 Together they may form a ring (eg, cycloaliphatic), and the C3 alcohol may be cyclopropanol or 2-cyclopropenol.

[0074] In yet other embodiments, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3- or R is hydrogen and m is 2, the alcohol may be a C4 alcohol. For example, if at least one R 1 and an R 2 In another example, R is not present, the C4 alcohol may be a C4 alkenol (e.g., 2-butene-1-ol or 3-butene-1-ol). 2 Together, X and Y can form a ring (e.g., cycloaliphatic), the C4 alcohol can be a C4-cyclic alcohol (e.g., cyclobutanol or cyclopropylmethanol). In another example, if both X and Y are not OH, the C4 alcohol can be a C4-branched alcohol (e.g., 2-butanol, isobutanol, or tert-butanol).

[0075] In some instances, when X=OH and Y=-[C(R 1 )2] m -C(R 2)3-, the alcohol may be a diol. In other examples, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3, and at least one R 1 =OH or an R 2 =OH, the alcohol may be a diol. Exemplary diols include, but are not limited to, 1,4-butanediol, propylene-1,3-diol, and the like.

[0076] In other examples, when X=Y=OH, the alcohol may be a triol. In still other examples, when X=R=OH, the alcohol may be a triol. In some examples, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When R=OH, the alcohol may be a triol. In other examples, when R=OH and X=-[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When is OH, the alcohol may be a triol. Exemplary triols include, but are not limited to, glycerol or a glycerol derivative thereof.

[0077] In certain embodiments, when R = cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol can be a heterocyclic alcohol (e.g., an optionally substituted heterocyclyl substituted with one or more hydroxy groups, such as furanmethanol). In other embodiments, when at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3 and one R 1 At least one R 2 When the group is a cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl or heteroalkynyl-heterocyclyl, the alcohol may be a heterocyclic alcohol.

[0078] In various embodiments, the alcohol can have 1-10 carbon atoms. The alcohol can be a primary alcohol, a secondary alcohol, or a tertiary alcohol. In some cases, the alcohol can be selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, and combinations thereof. Laboratory solvents:

[0079] In these or other cases, the organic solvent can include laboratory solvents such as acetonitrile, dichloromethane, carbon tetrachloride, or combinations thereof. ketone:

[0080] In some embodiments, the organic solvent may be a ketone.

[0081] The organic solvent may also be a solvent having the formula X-[C(O)] n -Y ketone, wherein:

[0082] n is an integer from 1 to 2;

[0083] Each X and Y can be independently selected from -C(R 1 )3. -R 2 , or -[C(R 3 )2] m -C(O)-R 4 , where R 1 、R 2 、R 3 and R 4 may be independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof;

[0084] where R 3 With R 4 together with the atoms to which they are attached, may optionally form a cycloaliphatic or cycloheteroaliphatic, and wherein X and Y together with the atoms to which they are attached, may optionally form a cycloaliphatic or cycloheteroaliphatic; and

[0085] m is an integer from 0 to 10.

[0086] In some embodiments, each R 1 、R 2 、R 3 and R 4and alkyl, alkyl, alkyl- ... In certain disclosed embodiments, the organic solvent can be further substituted with one or more substituents, such as an aldehyde (—C(O)H), an oxo (═O), an alkoxy, an amide, an amine, a hydroxyl, a thiol, an acyloxy, a silane, a cycloaliphatic, an aryl, an aldehyde, a ketone, an ester, a carboxylic acid, an acyl, an acyl halide, a cyano, a halogen, a sulfonate, a nitro, a nitroso, a quaternary amine, a pyridyl (or a pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), a halogenated alkyl, or any combination thereof. An exemplary ketone is acetone.

[0087] In some embodiments, when X and Y together with the atoms to which they are attached form a cycloaliphatic or cycloheteroaliphatic group, the organic solvent may be a cyclic ketone. Exemplary cyclic ketones include cyclohexanone, cyclopentanone, and the like.

[0088] In other embodiments, when at least one of X or Y is -[C(R 3 )2] m -C(O)-R 4 When the organic solvent is a diketone, exemplary diketones include biacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, acetylacetone, acetonylacetone, and the like, as well as halogenated forms thereof, such as hexafluoroacetylacetone.

[0089] In further embodiments, when at least one of X or Y is -[C(R 3 )2] m -C(O)-R 4 and X or Y together with the atoms to which they are attached form a cycloaliphatic or cycloheteroaliphatic group, the organic solvent may be a cyclic dione. Exemplary cyclic diones include dimedone, 1,3-cyclohexanedione, and the like.

[0090] In some examples, when X = -CH3, the organic solvent may have Y = -C(R 1 )3, where at least one R 1 C 2-10 Hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl propyl ketone, methyl butyl ketone, hydroxyacetone, and the like.

[0091] In other examples, when X = -CH3, the organic solvent may have Y = -R 2 , where at least one R 2 C2 alkenyl, C 3-10 Aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, and the like.

[0092] In yet other examples, when at least one of X or Y is aromatic or aliphatic-aromatic or heteroaliphatic-aromatic, the organic solvent may be an aromatic ketone. Exemplary materials include acetophenone, benzophenone, benzyl acetone, 1,3-diphenyl acetone, cyclopentyl phenyl ketone, and the like.

[0093] In certain embodiments where the organic solvent comprises a ketone, the ketone may be selected from acetone and acetophenone.One or more additional ketones and / or other organic solvents described herein may also be provided. ether:

[0094] In some embodiments, the organic solvent may be a compound having the formula XOY or XO-[C(R)2] n -OY ethers, wherein:

[0095] n is an integer from 1 to 4;

[0096] Each X and Y can be independently selected from -[C(R 1 )2] m -C(R 2 )3 or -R 3 or -[C(R 4 )2] p -O-[C(R 5 )2] m -C(R 6 )3, where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R are each independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and wherein m is an integer from 0 to 10 and p is an integer from 1 to 10;

[0097] wherein X and Y together with the atoms to which they are attached may optionally form a cycloheteroaliphatic group.

[0098] In some embodiments, each R1 、R 2 、R 3 、R 4 、R 5 and R 6 independently selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkyl-alkynyl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, alkyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. In the specific disclosed embodiments, the ether can be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, thiol, acyloxy, silanyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0099] In some embodiments, when X and Y, together with the atoms to which they are attached, form a cyclic heteroaliphatic group, the organic solvent is a cyclic ether, such as an acetal, dioxane, dioxolane, or the like. In some embodiments, when n=1 and each R=H, X and Y together form a six-, seven-, eight-, nine-, or ten-membered ring. Exemplary ethers include, but are not limited to, 1,3-dioxolane or its derivatives. In other embodiments, when n=2 and R=H, X and Y form a seven-, eight-, nine-, or ten-membered ring. Exemplary ethers include, but are not limited to, 1,4-dioxane or its derivatives. In yet other embodiments, when n=1 or n=2, R is aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 2-methyl-1,3-dioxolane, and the like.

[0100] In other embodiments, when at least one of X or Y is aromatic, the organic solvent may be an aromatic ether. Exemplary aromatic ethers include anisole, diphenyl ether, and the like.

[0101] In some embodiments, when at least one of X or Y is cycloaliphatic, the organic solvent may be a cycloalkyl ether. Exemplary cycloalkyl ethers include cyclopentyl methyl ether, cyclohexyl methyl ether, and the like.

[0102] In other embodiments, when at least one of X or Y is -[C(R4 )2-O] p -C(R 6 )3, the organic solvent may be a glycol-based ether. Exemplary glycol-based ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, and the like, including methyl, ethyl, propyl, and butyl monoethers and diethers of ethylene glycol, and the like. Nitrile:

[0103] In some cases, the organic solvent is a nitrile having the formula RC≡N, wherein

[0104] R is aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic or heteroaliphatic-aromatic.

[0105] In certain embodiments, R may be optionally substituted with hydroxy (e.g., in one example, R may be CH3-CH(OH)-CH2-, and the organic solvent would be CH3-CH(OH)-CH2-CN).

[0106] An exemplary nitrile is acetonitrile, as described above.

[0107] In some embodiments, the organic solvent can include two or more organic solvents or types of organic solvents described herein. In some embodiments, water can be provided in place of or in addition to the organic solvent. carrier gas

[0108] If used, the carrier gas can be an inert gas. In some cases, the carrier gas is an inert gas. In certain embodiments, the carrier gas can be selected from the group consisting of N2, He, Ne, Ar, Kr, and Xe. In some such embodiments, the carrier gas can be selected from the group consisting of N2, He, and Ar. additive

[0109] If used, the additive can be selected from a variety of different types of additives. For example, in some cases, the additive can be a heterocyclic compound, a heterocyclic aromatic compound, a halogen-substituted heterocyclic aromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidant, a bifluoride source, ammonia, an aldehyde, a carbene, or an organic acid. In some cases, more than one additive can be used. In some embodiments, the additive can be a boron-containing Lewis acid or Lewis adduct. Boron trifluoride (BF3) is a boron-containing Lewis acid or Lewis adduct that forms an acid-base adduct BF4. - Examples of Lewis acids. In some cases, the additive may belong to two or more of the categories listed above. In various embodiments, the additive is used to accelerate the reaction rate and improve the reaction selectivity. Heterocyclic aromatic compounds:

[0110] In certain embodiments, the additive is a heterocyclic aromatic compound. The term "aromatic" is as defined above. A heterocyclic aromatic compound is an aromatic compound comprising a 5-, 6-, or 7-membered ring (unless otherwise specified) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogen). Exemplary heterocyclic aromatic compounds that can be used include, but are not limited to, methylpyridine, pyridine, pyrrole, imidazole, thiophene, N-methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolinic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, and azulene. In some cases, the heterocyclic aromatic compound may be methylated. In some cases, the heterocyclic aromatic compound may follow the Hückel 4n+2 rule. In some cases, the additive is a halogen-substituted aromatic compound. Halogen-substituted aromatic compounds are aromatic compounds that include at least one halogen bonded to an aromatic ring. As used herein, halogen or halo refers to F, Cl, Br, or I. Exemplary halogen-substituted aromatic compounds include, but are not limited to, 4-bromopyridine, chlorobenzene, 4-chlorotoluene, fluorobenzene, and the like. Heterocyclic aliphatic compounds:

[0111] In some embodiments, the additive is a heterocyclic aliphatic compound. As used herein, "aliphatic" means a compound having at least one carbon atom to 50 carbon atoms (C 1-50 ) of a hydrocarbon group, for example, 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), and includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and further including linear and branched arrangements, as well as all stereo and positional isomers. Heterocyclic aliphatics are aliphatic compounds comprising 5-, 6-, or 7-membered rings (unless otherwise specified) that contain 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halogen). Exemplary heterocyclic aliphatics include pyrrolidine, piperidine, and the like. amine:

[0112] In some embodiments, the additive is of formula NR 1 R 2 R 3 Amines, wherein:

[0113] R 1 、R 2 and R 3are each independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof;

[0114] where R 1 With R 2 together with the atoms to which they are attached, may optionally form a cycloheteroaliphatic; and

[0115] where R 1 、R 2 With R 3 Together with the atoms to which they are attached they may optionally form a cycloheteroaliphatic.

[0116] In some embodiments, R 1 、R 2 and R 3 Each is 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 combination thereof. In particularly disclosed embodiments, the amine can be further substituted with one or more substituents, such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silanyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0117] In some embodiments, when R 1 、R 2 and R 3 When at least one of the alkylamines is aliphatic, halogenated aliphatic, halogenated heteroaliphatic, or heteroaliphatic, the additive is an alkylamine. The alkylamine may include dialkylamine, trialkylamine, and derivatives thereof. Exemplary alkylamines include dimethylisopropylamine, N-ethyldiisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, tert-butylamine, and the like.

[0118] In other embodiments, when R 1 、R 2 and R 3 When at least one of the R comprises a hydroxyl group, the additive is an alcohol amine. 1 、R 2 and R 3At least one of the alcohol amines is an aliphatic group substituted with one or more hydroxyl groups. Exemplary alcohol amines include 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(dipropylamino)ethanol, 2-(dibutylamino)ethanol, N-ethyldiethanolamine, N-tert-butyldiethanolamine, and the like.

[0119] In some embodiments, when R 1 With R 2 When the additive forms a cyclic heteroaliphatic group together with the atoms to which it is attached, the additive can be a cyclic amine. Exemplary cyclic amines include piperidine, N-alkylpiperidines (e.g., N-methylpiperidine, N-propylpiperidine, etc.), pyrrolidine, N-alkylpyrrolidines (e.g., N-methylpyrrolidine, N-propylpyrrolidine, etc.), morpholine, N-alkylmorpholines (e.g., N-methylmorpholine, N-propylmorpholine, etc.), piperazine, N-alkylpiperazine, N,N-dialkylpiperazine (e.g., 1,4-dimethylpiperazine), and the like.

[0120] In other embodiments, when R 1 、R 2 and R 3 When at least one of the additives comprises an aromatic group, the additive is an aromatic amine. 1 、R 2 and R 3 At least one of is aromatic, aliphatic-aromatic or heteroaliphatic-aromatic. In other embodiments, R 1 and R 2 In yet other embodiments, R 1 With R 2 and optional R 3 Together with the atoms to which they are attached, they form an aromatic cycloheteroaliphatic. Exemplary aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and derivatives thereof.

[0121] In some embodiments, the additive may include an amine selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1,2-ethylenediamine, aniline (and aniline derivatives such as N,N-dimethylaniline), N-ethyldiisopropylamine, tert-butylamine, and combinations thereof.

[0122] In some embodiments, the additive may include a fluoroamine. A fluoroamine is an amine having one or more fluorinated substituents. Exemplary fluoroamines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0123] In some embodiments, the additive may be a nitrogen-containing analog of carbonic acid having the formula R 1 NC(NR 2 )-NR 3Exemplary additives may include, but are not limited to, guanidine or its derivatives.

[0124] In some embodiments, the additive can be a relatively low molecular weight amine, for example, having a molecular weight of less than 200 g / mol or 100 g / mol in certain embodiments. In some embodiments, higher molecular weight amines can be used, including those with long chains and / or heterocyclic compounds with aromatic rings. Amino acids:

[0125] In some embodiments, the additive may include an amino acid. The amino acid may have the formula R-CH(NR'2)-COOH, wherein:

[0126] Each R and R' is independently hydroxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0127] Exemplary amino acids that can be used include, but are not limited to, histidine, alanine, and their derivatives. Organophosphorus compounds:

[0128] In some embodiments, 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. Exemplary organophosphorus compounds include phosphoric acid and trialkyl phosphates. In some cases, the organophosphorus compound is a phosphazene. A phosphazene is an organophosphorus compound containing phosphorus (V) having a double bond between P and N. The phosphazene may have the formula RN=P(NR2)3 (wherein R and R 2 are each independently selected from hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof). In some cases, the phosphazene has the formula [X2PN] n (wherein X is a halide, an alkoxide, or an amide.) Other types of phosphazenes may be used as desired. Oxidants:

[0129] In some embodiments, the additive includes an oxidant. As used herein, an oxidant is a material that has the ability to oxidize another substance (e.g., accept electrons from another substance). Exemplary oxidants that can be used include, but are not limited to, hydrogen peroxide, sodium hypochlorite, and tetramethylammonium hydroxide. Difluoride source:

[0130] In some embodiments, the additive includes a bifluoride source. The bifluoride source is a material containing or generating bifluoride (HF2 - ) materials. Exemplary bifluoride sources that may be used include, but are not limited to, ammonium fluoride, aqueous HF, gaseous HF, buffered oxide etching mixtures (e.g., a mixture of HF and a buffer such as ammonium fluoride), and hydrogen fluoride pyridine. In some embodiments, the bifluoride source (and / or one or more other additives listed herein) may be reacted to form HF2 before or after delivery to the reaction chamber. - . aldehyde:

[0131] In some embodiments, the additive includes an aldehyde having the formula X-[C(O)]-H, wherein:

[0132] X can be selected from hydrogen, -R 1 、-C(R 2 )3 or -[C(R 3 )2] m -C(O)H, where each R 1 、R 2 and R 3 are independently selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and m is an integer from 0 to 10.

[0133] In some embodiments, R 1 、R 2 and R 3Each is 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, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. In certain disclosed embodiments, the aldehyde or ketone can be further substituted with one or more substituents, such as aldehyde (—C(O)H), oxo (═O), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silanyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0134] In some embodiments, when X=aromatic, the additive may be an aromatic aldehyde. Exemplary aromatic aldehydes include benzaldehyde, 1-naphthaldehyde, phthalaldehyde, and the like.

[0135] In other embodiments, when X=aliphatic, the additive may be an aliphatic aldehyde. Exemplary aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and the like.

[0136] In yet other embodiments, when X=-[C(R 3 )2] m When -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. Exemplary dialdehydes include glyoxal, phthalaldehyde, glutaraldehyde, malondialdehyde, succinaldehyde, and the like.

[0137] In some examples, the aldehyde used as an additive can be selected from the group consisting of acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other cases, the aldehyde used as an additive can be selected from the aldehydes discussed in this section and the aldehydes discussed in the organic solvent section. Carbene:

[0138] In some embodiments, the additive includes a carbene. The carbene may have the formula X-(C:)-Y, wherein:

[0139] X and Y can each be independently selected from H, halogen, -[C(R 1 )2] m -C(R 2 )3. -C(O)-R 1 or -C(=NR1 )-R 2 、-NR 1 R 2 、-OR 2 、-SR 2 or -C(R 2 )3, where R 1 With R 2 are each independently selected from hydrogen, hydroxy, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, wherein m is an integer from 0 to 10;

[0140] where R 1 With R 2 together with the atoms to which they are attached, may optionally form a cycloheteroaliphatic group; and

[0141] wherein X and Y together with the atoms to which they are attached may optionally form a cycloaliphatic or cycloheteroaliphatic group.

[0142] In addition, the additive may be of formula R 1 -C + (R)-R 2 carbonium cation, where R, R 1 With R 2 Each is independently selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0143] In some embodiments, each R, R 1 and R 2 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 combination thereof. In particularly disclosed embodiments, the carbene may be further substituted with one or more substituents such as alkoxy, amide, amine, hydroxy, thioether, thiol, acyloxy, silane, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof. In any embodiment of the carbene, R 1 With R 2Each can be selected independently.

[0144] In some embodiments, when at least one of X or Y is a halogen, the additive can be a halocarbene. Exemplary non-limiting halocarbenes include dihalocarbenes, such as dichlorocarbene, difluorocarbene, and the like.

[0145] In some embodiments, when X=Y=-NR 1 R 2 When the additive can be diaminocarbene. In one embodiment, R 1 With R 2 and each is independently aliphatic. Exemplary diaminocarbene includes bis(diisopropylamino)carbene and the like.

[0146] In other embodiments, when at least one of X or Y = -NR 1 R 2 And R in X or Y 1 With R 2 When the two, together with the nitrogen atoms to which they are attached, form a cyclic heteroaliphatic group, the additive can be a cyclic diaminocarbene. Exemplary cyclic diaminocarbenes include bis(N-piperidinyl)carbene, bis(N-pyrrolidinyl)carbene, and the like.

[0147] In one example, when X=Y=-NR 1 R 2 And R from X 1 Group and R from Y 2 When the groups together with the nitrogen atoms to which they are attached form a cycloheteroaliphatic group, the additive is an N-heterocyclic carbene. Exemplary N-heterocyclic carbenes include imidazol-2-ylidene (e.g., 1,3-dimesitylimidazol-2-ylidene), 1,3-dimesityl-4,5-dichloroimidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, imidazol-2-ylidene (e.g., 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), 1,3-di-tert-butylimidazol-2-ylidene, etc.), imidazolidin-2-ylidene (e.g., 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), triazole-5-ylidene (e.g., 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene), and the like.

[0148] In some embodiments, when X=-NR1 R 2 And Y=-SR 2 and R from X 1 Group and R from Y 2 When the groups, together with the nitrogen atoms to which they are attached, form a cyclic heteroaliphatic group, the additive is a cyclic sulfanylaminocarbene. Exemplary cyclic sulfanylaminocarbenes include thiazole-2-carbene (e.g., 3-(2,6-diisopropylphenyl)thiazole-2-carbene and the like).

[0149] In some embodiments, when X=-NR 1 R 2 And Y=-C(R 2 )3 and R from X 1 Group and R from Y 2 When the groups together with the atoms to which they are attached form a cycloheteroaliphatic group, the additive is an exemplary cyclic alkylaminocarbene.

[0150] Exemplary cyclic alkylaminocarbenes include pyrrolidine-2-carbene (e.g., 1,3,3,5,5-pentamethyl-pyrrolidine-2-carbene, etc.) and piperidine-2-carbene (e.g., 1,3,3,6,6-pentamethyl-piperidine-2-carbene and the like).

[0151] Further exemplary carbenes and their derivatives include compounds having a thiazole-2-carbene moiety, a dihydroimidazole-2-carbene moiety, an imidazole-2-carbene moiety, a triazole-5-carbene moiety, or a cyclopropene-carbene moiety. Still other carbenes and carbene analogs include aminosulfur carbene compounds, aminooxy carbene compounds, diamino carbene compounds, heteroamino carbene compounds, 1,3-disulfonium carbene compounds, mesoionic carbene compounds (e.g., imidazolin-4-ylidene compounds, 1,2,3-triazoleylidene compounds, pyrazolinylidene compounds, tetrazole-5-ylidene compounds, isoxazole-4-ylidene compounds, thiazole-5-ylidene compounds, etc.), cycloalkylamino carbene compounds, boranylidene compounds, silylene compounds, stannylene compounds, nitrene compounds, phosphinidene compounds, foiled carbene compounds, etc. Further exemplary carbenes include dimethylimidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, (phosphino)(trifluoromethyl)carbene, bis(diisopropylamino)carbene, bis(diisopropylamino)cyclopropene, 1,3-dimesityl-4,5-dichloroimidazol-2-ylidene, 1,3-diadamantylimidazol-2-ylidene, 1,3,4,5-tetramethylimidazol-2-ylidene, 1,3-dimesityl-4,5-dichloroimidazol-2-ylidene, ,3-dimesitylimidazol-2-ylidene), 1,3-dimesitylimidazol-2-ylidene, 1,3,5-triphenyltriazol-5-ylidene, bis(diisopropylamino)cyclopropenylidene, bis(9-anthryl)carbene, norbornene-7-ylidene, dihydroimidazol-2-ylidene, methylidenecarbene, etc. Organic acids:

[0152] In some embodiments, the additive includes an organic acid. The organic acid can have a formula R-CO2H, wherein R is selected from hydrogen, aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic or any combination thereof. In certain embodiments, R is alkyl, alkenyl, alkynyl, assorted alkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-heteroaryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, assorted alkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, assorted alkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl or any combination thereof. In certain disclosed embodiments, R can be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, hydroxy, thiol, acyloxy, silanyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridyl (or pyridyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof. In certain embodiments, the organic acid can be selected from formic acid and acetic acid. replace:

[0153] Any exemplary materials described herein include compounds in unsubstituted and / or substituted forms. Non-limiting exemplary substituents include, for example, one, two, three, four or more substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 alkyl); (2) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl); (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl); (4) amine (e.g., -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2together with the nitrogen atom to which they are attached to form a heterocyclic group as defined herein); (5) aryl; (6) aralkyloxy (e.g., -OLR, wherein L is alkyl and R is aryl); (7) aroyl (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 Cycloalkyl; (12) halogen; (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., -OR, wherein R is a heterocyclyl as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is a heterocyclyl as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkoxy (e.g., -SR, where R is C 1-6 alkyl); (21) thiol (e.g. -SH); (22) -CO2R 1 , where R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (23)-C(O)NR 1 R 2 , where R 1 With R 2 Each of which is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b)C 4-18 Aryl and (c)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR1 R 2 , where R 1 With R 2 Each of which is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl, R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 cycloalkyl), wherein in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl or sulfonyl group.

[0154] In certain embodiments, the additive may act as a proton acceptor and promote HF2 - In some such cases, HF2 - One or more materials on the substrate, such as an oxide material or another material, may be actively etched. Etching

[0155] The gaseous phase material that is transported to the reaction chamber can be collectively referred to as gas mixture.The non-inert material (for example, the reactant of non-carrier gas) that is transported to the reaction chamber can be collectively referred to as reactant mixture.Gas mixture includes reaction mixture and carrier gas.In some cases, reaction mixture and / or gas mixture can have specific composition.For example, halogen source can be provided in the reaction mixture at a concentration between about 20-100% (volume) or between about 20-99% (volume).In these or other cases, halogen source can be provided in the gas mixture at a concentration between about 0.5-20% (volume).Organic solvent and / or water can be provided in the reactant mixture at a concentration between about 10-100% (volume) or between about 10-99% (volume).In these or other cases, organic solvent and / or water can be provided in the gas mixture at a concentration between about 0-10% (volume), for example, between about 1-10% (volume).Additive can be provided in the reactant mixture at a concentration between about 0.2-5% (volume). In these or other cases, the additive can be provided to the gas mixture at a concentration between about 0-0.2% or between about 0.0001-0.2% by volume.The carrier gas can be provided to the gas mixture at a concentration between about 0-99% by volume.

[0156] In some embodiments, the additive and the organic solvent and / or water are mixed such that the additive is between about 0.1% and 5% by weight of the additive / organic solvent and / or water mixture. Regardless of the order of mixing, the reactant mixture can be characterized in that the additive is between about 0.1% and 5% by weight of the total amount of the additive and the organic solvent and / or water.

[0157] In the same or alternative embodiments, the reactant mixture can be characterized by a halogen source:additive ratio (by volume). As further described below, in some embodiments, selectivity can be adjusted by the halogen source:additive volume ratio, with selectivity increasing as the amount of additive increases (and thus the ratio decreases). In some embodiments, the halogen source:additive ratio is less than or equal to 10. In some embodiments, the halogen source:additive ratio is greater than 10.

[0158] According to various embodiments, the reactant mixture may include a halogen source, an alcohol, and an amine, wherein the amine is between 0.1 and 5 weight percent of the total amount of the alcohol and the amine. In some embodiments, the halogen source:amine volume ratio does not exceed 10. In other embodiments, the halogen source:amine volume ratio is 10 or higher.

[0159] As described above, according to various implementations, the etch can be selective to one material on the substrate relative to another material. In other implementations, the etch can be non-selective to multiple materials on the substrate. Other definitions

[0160] This section presents additional definitions that may be used herein. Some of the material described in this section may overlap with material presented elsewhere in this application.

[0161] The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to a radical of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms, or hydrogen, in a linear, branched, cyclic configuration, saturated, unsaturated, and aromatic, and combinations thereof, attached to the parent molecular moiety through a carbonyl group, as defined herein. Examples of such radicals include formyl, acetyl, propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl radical is -C(O)-R, wherein R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0162] "Acyl halide" means -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0163] "Aldehyde" means a -C(O)H group.

[0164] "Aliphatic" means a hydrocarbon group having at least one carbon atom and up to 50 carbon atoms (C1-50), for example, 1 to 25 carbon atoms (C1-50). 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), and includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and further includes straight chain and branched arrangements, as well as all stereo and positional isomers.

[0165] "Alkyl-aryl," "alkenyl-aryl," and "alkynyl-aryl" mean an aryl group, as defined herein, coupled or coupleable (or linked) to a parent molecular group through an alkyl, alkenyl, or alkynyl group, as defined herein. Alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups can be substituted with one or more substituents, as described herein for alkyl, alkenyl, alkynyl, and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkyl-aryl), and those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbon atoms (C 7-16alkenyl-aryl), and those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkynyl-aryl), and those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, alkyl-aryl is -LR, wherein L is alkyl as defined herein and R is aryl as defined herein. In some embodiments, alkenyl-aryl is -LR, wherein L is alkenyl as defined herein and R is aryl as defined herein. In some embodiments, alkynyl-aryl is -LR, wherein L is alkynyl as defined herein and R is aryl as defined herein.

[0166] "Alkenyl" means an alkenyl group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ) (e.g., two to 25 carbon atoms (C 2-25 ), or two to ten carbon atoms (C 2-10 )) and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from a parent olefin by removing a hydrogen atom from a carbon atom. The alkenyl group can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 Alkyl. An alkenyl group can be monovalent or multivalent (e.g., divalent) by removing one or more hydrogens to form a suitable linkage to the parent molecular group or between the parent molecular group and another substituent. An alkenyl group can also be substituted or unsubstituted. For example, an alkenyl group can be substituted with one or more substituents, as described herein for an alkyl group.

[0167] "Alkyl-heteroaryl" means a heteroaryl, as defined herein, attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, alkyl-heteroaryl is -LR, wherein L is alkyl, as defined herein, and R is heteroaryl, as defined herein.

[0168] "Alkyl-heterocyclyl," "alkenyl-heterocyclyl," and "alkynyl-heterocyclyl" mean a heterocyclyl group, as defined herein, coupled or coupleable (or linked) to a parent molecule through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. Alkyl-heterocyclyl, alkenyl-heterocyclyl, and / or alkynyl-heterocyclyl groups may be substituted or unsubstituted. For example, an alkyl-heterocyclyl, alkenyl-heterocyclyl, and / or alkynyl-heterocyclyl group may be substituted with one or more substituents, as described herein for alkyl, alkenyl, alkynyl, and / or heterocyclyl groups. Exemplary unsubstituted alkyl-heterocyclyl groups have from 2 to 16 carbon atoms (C 2-16 alkyl-heterocyclyl), and those having an alkyl group with 1 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C 1-6 Alkyl-C 1-18 Heterocyclyl). Exemplary unsubstituted alkenyl-heterocyclyl groups have 3 to 16 carbons (C 3-16 alkenyl-heterocyclyl), and those having an alkenyl group with 2 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C 2-6 Alkenyl-C 1-18 Heterocyclyl). Exemplary unsubstituted alkynyl-heterocyclyl groups have 3 to 16 carbons (C 3-16 alkynyl-heterocyclyl), and those having an alkynyl group with 2 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C 2-6 Alkynyl-C 1-18 In some embodiments, alkyl-heterocyclyl is -LR, wherein L is alkyl as defined herein and R is heterocyclyl as defined herein. In some embodiments, alkenyl-heterocyclyl is -LR, wherein L is alkenyl as defined herein and R is heterocyclyl as defined herein. In some embodiments, alkynyl-heterocyclyl is -LR, wherein L is alkynyl as defined herein and R is heterocyclyl as defined herein.

[0169] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy groups such as trifluoromethoxy, and the like. Alkoxy groups may be substituted or unsubstituted. For example, alkoxy groups may be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 、C 1-6 、C 1-12 、C 1-16 、C 1-18 、C 1-20 , or C1-24 Alkoxy.

[0170] "Alkyl" means a group having at least one carbon atom to 50 carbon atoms (C 1-50 )(e.g. 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be derived from a parent compound (e.g., an alkane) by removing one hydrogen atom from one carbon atom. The alkyl group can be branched, straight chain, or cyclic (e.g., a cycloalkyl group). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group may be substituted with one, two, three, or (in the case of an alkyl group having two or more carbons) four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g. -OR, where R is C 1-6 alkyl); (2) C 1-6 Alkylsulfinyl (e.g. -S(O)-R, where R is C 1-6 alkyl); (3) C 1-6 Alkylsulfonyl (e.g. -SO2-R, where R is C 1-6 alkyl); (4) amine (e.g., -C(O)NR 1 R 2 or-NHCOR 1 , wherein each of R1 and R2 is independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 With R 2 together with the nitrogen atom to which they are attached to form a heterocyclic group as defined herein); (5) aryl; (6) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl); (7) aroyl (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8Cycloalkyl; (12) halogen; (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., -OR, wherein R is a heterocyclyl as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is a heterocyclyl as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkoxy (e.g., -SR, where R is an alkyl group); (21) thiol (e.g., -SH); (22) -CO2R 1 , where R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (23)-C(O)NR 1 R 2 , wherein each of R1 and R2 is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b)C 4-18 Aryl and (c)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR 1 R 2 , where R 1 With R 2 Each of which is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl and (d)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl, R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 In one embodiment, no two groups are bound to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C 1-3 、C 1-6 、C 1-12 、C 1-16 、C 1-18 、C 1-20 or C 1-24 alkyl.

[0171] "Alkylsulfinyl" means an alkyl group, as defined herein, attached to the parent molecular group through a -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 In other embodiments, alkylsulfinyl is -S(O)-R, wherein R is alkyl as defined herein.

[0172] "Alkylsulfonyl" means an alkyl group, as defined herein, attached to the parent molecular group through a -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is C 1-6 or C 1-12 In other embodiments, alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., as described herein, comprising optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0173] "Alkynyl" means a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ) (e.g., two to 25 carbon atoms (C 2-25 ), or two to ten carbon atoms (C 2-10 )) and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from the removal of a hydrogen atom from a carbon atom of a parent alkyne. Alkynyl groups can be branched, straight chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include optionally substituted C 2-24 Alkyl groups. Alkyl groups can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. Alkyl groups can be monovalent or multivalent (e.g., divalent), formed by removing one or more hydrogen atoms to form a suitable linkage to the parent molecular group or between the parent molecular group and another substituent. Alkyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl groups.

[0174] "Amide" refers to -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein, or wherein R 1 With R 2 Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0175] "Amine" means -NR 1 R 2 , where R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or wherein R 1 With R 2 Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0176] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminoalkyl is -L-NR 1 R 2 , wherein L is alkyl as defined herein, and R 1 With R 2are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. In other embodiments, aminoalkyl is -LC(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond or an alkyl group as defined herein; R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 together with the nitrogen atom to which they are attached, form a heterocyclic group as defined herein; and R 3 With R 4 Each is independently H or alkyl as defined herein.

[0177] "Aromatic" means a cyclic conjugated group or moiety having from 5 to 15 (unless otherwise specified) ring atoms in a single ring (e.g., phenyl) or multiple fused rings, wherein at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized π-electron system. Typically, the number of out-of-plane π electrons corresponds to Huckel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system.

[0178] "Aryl" means a group containing at least 5 carbon atoms and up to 15 carbon atoms (C 5-15 ) (e.g. five to ten carbon atoms (C 5-10)) is an aromatic carbocyclic group having a single ring or multiple fused rings, the fused rings of which may or may not be aromatic, provided that the point of attachment to the rest of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen (e.g., aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof). Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, also included in the term aryl, defines a group containing an aromatic group and no heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five substituents, the substituents being independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g. -C(O)-R, where R is C 1-6 alkyl); (2) C 1-6 Alkyl; (3)C 1-6 Alkoxy (e.g. -OR, where R is C 1-6 alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, where L and R are each independently C 1-6 alkyl); (5) C 1-6 Alkylsulfinyl (e.g. -S(O)-R, where R is C 1-6 alkyl); (6)C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g. -LS(O)-R, where L and R are each independently C 1-6 Alkyl); (7) C 1-6 Alkylsulfonyl (such as -SO2-R, where R is C 1-6 alkyl); (8)C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g. -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amine (e.g., -NR 1 R 2 , where R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 together with the nitrogen atom to which they are attached, to form a heterocyclic group as defined herein); (11) C 1-6 Aminoalkyl (e.g., -L1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 C 1-6 Alkyl; L 2 Covalent bond or C 1-6 Alkyl; R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 With R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; R 3 With R 4 Each independently is H or C 1-6 alkyl); (12) heteroaryl; (13) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (14) aroyl (e.g., -C(O)-R, wherein R is an aryl group); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehyde (e.g., C(O)H); (19) aldehyde-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 alkyl); (20)C 3-8 Cycloalkyl; (21)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 Cycloalkyl); (22) halogen; (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 C 1-6 Alkyl; L 2 Covalent bond or C 1-6 Alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 With R 2 Each independently is H or C1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocycloxy (e.g., -OR, wherein R is a heterocyclyl as defined herein); (26) heterocyclyl (e.g., -C(O)-R, wherein R is a heterocyclyl as defined herein); (27) hydroxy (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 With R 2 are each independently H or C as defined herein 1-6 alkyl); (29) nitro; (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R, where L 1 C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 With R 2 are each independently H or C as defined herein 1-6 alkyl); (31) N-protected amino; (32) N-protected amino-C 1-6 Alkyl; (33) Oxo (eg, =O); (34) C 1-6 Thioalkoxy (e.g., -SR, where R is C 1-6 alkyl); (35)thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, where L and R are each independently C 1-6 alkyl); (36)-(CH2) r CO2R 1 , wherein r is an integer from 0 to 4, and R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (37)-(CH2) rCONR 1 R 2 , wherein r is an integer from 0 to 4, and wherein R 1 With R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (38)-(CH2) r SO2R 1 , wherein r is an integer from 0 to 4, and wherein R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b)C 4-18 Aryl, and (c) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (39)-(CH2) r SO2NR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 With R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (40)-(CH2) r NR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 With R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, wherein n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, wherein n is an integer from 0 to 10); (44) aryloxy (e.g., -OR, wherein R is aryl); (45) cycloalkoxy (e.g., -OR, wherein R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, wherein L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl is C 4-18 、C 4-14 、C 4-12 、C 4-10 、C 6-18 、C 6-14 、C 6-12 , or C 6-10 Aryl.

[0179] "Arylalkoxy" means an alkyl-aryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, arylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is aryl, as defined herein.

[0180] "Aryloxy" means -OR, wherein R is an optionally substituted aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C 4-18 or C 6-18 Aryloxy.

[0181] "Aroyl" means an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aryloyl is C 7-11 Aroyl or C 5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

[0182] "Azido" means a -N3 group.

[0183] "Azidoalkyl" means an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, wherein L is an alkyl group, as defined herein. "Azo" means a -N=N- group.

[0184] "Carbene" means H2C: and its derivatives having carbon or (C:) with two non-bonding electrons. In some embodiments, the carbene is R 1 R 2 (C:), where R 1 With R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 With R 2 Together with the atoms to which they are attached, they form a cycloaliphatic group as defined herein.

[0185] "Carbenium cation" means H3C + and carbon or C with a +1 formal charge + In some embodiments, the carbonium cation is R 1 -C+(R)-R 2 , where R, R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 With R 2 and optional R together with the atoms to which they are attached form a cycloaliphatic group as defined herein.

[0186] "Carbonyl" means a -C(O)- group, which may also be represented as >C=O.

[0187] "Carboxyl" means a -CO2H group or its anion.

[0188] "Cyano" means a -CN group.

[0189] "Cycloaliphatic" means a cyclic aliphatic group as defined herein.

[0190] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, cycloalkoxy is -OR, wherein R is a cycloalkyl group, as defined herein.

[0191] "Cycloalkylalkoxy" means an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, cycloalkylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is cycloalkyl, as defined herein.

[0192] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbon atoms (unless otherwise specified), exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyl groups may also be substituted or unsubstituted. For example, a cycloalkyl group may be substituted with one or more groups, including those described herein for alkyl groups.

[0193] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group as defined herein.

[0194] "Ester" means -C(O)OR or -OC(O)R, wherein R is selected from aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0195] "Halo" means F, Cl, Br or I.

[0196] "Haloaliphatic" means an aliphatic group as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0197] "Haloalkyl" means an alkyl group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (e.g., fluorine, bromine, chlorine, or iodine). In an independent embodiment, a haloalkyl group may be a -CX3 group, wherein each X is independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, a haloalkyl group is -LX, wherein L is an alkyl group as defined herein and X is fluorine, bromine, chlorine, or iodine. In other embodiments, a haloalkyl group is -LC(X)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine or iodine; and R 1 With R 2 Each is independently H or alkyl as defined herein.

[0198] "Haloheteroaliphatic" means a heteroaliphatic as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0199] "Heteroaliphatic" means an aliphatic group as defined herein containing from at least one heteroatom to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which heteroatoms may be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0200] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" mean an alkyl, alkenyl, or alkynyl group (which may be branched, straight chain, or cyclic) as defined herein, respectively, containing from at least one heteroatom to 20 heteroatoms (e.g., 1 to 15 heteroatoms or 1 to 5 heteroatoms), which heteroatoms may be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0201] "Heteroalkyl-aryl," "heteroalkenyl-aryl," and "heteroalkynyl-aryl" mean an aryl group, as defined herein, coupled or coupleable to a compound disclosed herein, wherein the aryl group is coupled or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, heteroalkyl-aryl is -LR, wherein L is heteroalkyl, as defined herein, and R is aryl, as defined herein. In some embodiments, heteroalkenyl-aryl is -LR, wherein L is heteroalkenyl, as defined herein, and R is aryl, as defined herein. In some embodiments, heteroalkynyl-aryl is -LR, wherein L is heteroalkynyl, as defined herein, and R is aryl, as defined herein.

[0202] “Heteroalkyl-heteroaryl,” “heteroalkenyl-heteroaryl,” and “heteroalkynyl-heteroaryl” mean a heteroaryl group, as defined herein, coupled or coupleable to a compound disclosed herein, wherein the heteroaryl group is coupled or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, heteroalkyl-heteroaryl is -LR, wherein L is heteroalkyl, as defined herein, and R is heteroaryl, as defined herein. In some embodiments, heteroalkenyl-heteroaryl is -LR, wherein L is heteroalkenyl, as defined herein, and R is heteroaryl, as defined herein. In some embodiments, heteroalkynyl-heteroaryl is -LR, wherein L is heteroalkynyl, as defined herein, and R is heteroaryl, as defined herein.

[0203] "Heteroaryl" means an aromatic group containing at least one heteroatom to six heteroatoms (e.g., one to four heteroatoms), which heteroatoms may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the ring. Such heteroaryl groups may have a single ring or multiple fused rings, wherein the fused rings may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. The heteroaryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n+2 pi electrons within a single or multiple ring system.

[0204] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, heteroatoms do not include halogen atoms, for example, when valence restrictions do not permit.

[0205] "Heterocyclyl" means a 5-, 6-, or 7-membered ring (unless otherwise specified) containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, or halogen). Five-membered rings have zero to two double bonds, while six- and seven-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle (e.g., indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothiophenyl, and the like). Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, homopiperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, piperazinyl), pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl,thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydro isoquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0206] "Heterocyclyloxy" means a heterocyclyl, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -OR, wherein R is a heterocyclyl, as defined herein.

[0207] "Heterocyclyloyl" means a heterocyclyl, as defined herein, attached to the parent molecular moiety through a carbonyl group. In some embodiments, heterocyclyl is -C(O)-R, wherein R is a heterocyclyl, as defined herein.

[0208] "Hydroxy" means -OH.

[0209] "Hydroxyalkyl" means an alkyl group as defined herein substituted with one to three hydroxy groups, provided that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group, exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, hydroxyalkyl is -L-OH, where L is an alkyl group as defined herein. In other embodiments, hydroxyalkyl is -LC(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 With R 2 Each is independently H or alkyl as defined herein.

[0210] "Ketone" means -C(O)R, wherein R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein.

[0211] "Nitro" means a -NO2 group.

[0212] "Nitroalkyl" means an alkyl group, as defined herein, substituted with one to three nitro groups. In some embodiments, nitroalkyl is -L-NO, wherein L is an alkyl group, as defined herein. In other embodiments, nitroalkyl is -LC(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 With R 2 Each is independently H or alkyl as defined herein.

[0213] "Oxo" means a =0 group.

[0214] "Oxy" means -O-.

[0215] "Perfluoroalkyl" means an alkyl group as defined herein in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, wherein n is an integer from 0 to 10.

[0216] "Perfluoroalkoxy" means an alkoxy group, as defined herein, with each hydrogen atom replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, wherein R is a perfluoroalkyl group, as defined herein.

[0217] "Salt" means an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that contains a cationic or anionic compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge SM et al., "Pharmaceutical salts," J. Pharm. Sci. 1977 January; 66(1): 1-19; and in "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. PHS Tahl and The salts can be prepared in situ during the final isolation and purification of the compounds of the present disclosure, or separately by reacting the free base groups with suitable organic acids (thus producing anionic salts) or by reacting the acid groups with suitable metal or organic salts (thus producing cationic salts). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride. chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride,hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts, for example, alkali metal salts or alkaline earth metal salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; and non-toxic ammonium, quaternary ammonium, and amine cations, including but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine,Pyridinium and the like. Other cationic salts include organic salts such as chloroprocain, choline, benzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium ium), optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium,optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinoline quinolizinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium.

[0218] "Sulfo" means a -S(O)2OH group.

[0219] "Sulfonyl" or "sulfonate" means a -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0220] "Thioalkoxy" means an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkoxy groups include C 1-6 In some embodiments, thioalkoxy is -SR, wherein R is alkyl as defined herein.

[0221] "Thiol" means a -SH group.

[0222] Those skilled in the art will appreciate that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with five different groups, and the like). Such impermissible substitution patterns are readily apparent to those skilled in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise indicated therein. Device

[0223] The etching methods described herein can be performed in a variety of apparatuses. Suitable apparatuses include a processing chamber, a substrate holder configured to hold the substrate in position during etching within the processing chamber, an inlet to the processing chamber for introducing one or more reactants, and a plasma generating mechanism configured to generate a plasma to activate the one or more reactants in the process gas. In some cases, the etching apparatus also has the capability to perform deposition.

[0224] Examples of suitable apparatus include, but are not limited to, inductively coupled plasma (ICP) reactors. Although ICP reactors are described in detail herein, it should be understood that capacitively coupled plasma reactors may also be used.

[0225] FIG. 1 schematically illustrates a cross-sectional view of an inductively coupled plasma integrated etching apparatus suitable for implementing the etching methods described herein, an example of which is manufactured by Lam Research Corp. (Fremont, CA). Reactor. The apparatus includes a chamber 132, which includes a cavity 114, a chuck 116, and a dielectric window 106. The chamber 132 includes a processing region, and the dielectric window 106 is disposed above the processing region. The chuck 116 can be an electrostatic chuck for supporting the substrate 112 and is disposed below the processing region in the chamber. In some embodiments, an internal Faraday shield (not shown) is disposed within the chamber 100 and below the dielectric window 106. A transformer coupled plasma (TCP) coil 134 is disposed above the dielectric window 106 and is connected to the matching circuit 102.

[0226] The system includes a bias RF generator 120, which can be defined by one or more generators. If multiple generators are provided, different frequencies can be used to achieve various tuning characteristics. A bias match 118 is coupled between the RF generator 120 and the conductive plates that define the assembly of the chuck 116. The chuck 116 also includes electrostatic electrodes to allow for clamping and unclamping of the wafer. Generally, filters and a DC clamping power supply can be provided. Other control systems for lifting the wafer from the chuck 116 can also be provided.

[0227] In various embodiments, the bias voltage of the electrostatic chuck can be set to about 50 Vb, or can be set to a different bias voltage, depending on the process performed according to the disclosed embodiments. For example, the bias voltage during plasma etching can be between about 20 Vb and about 100 Vb, or between about 30 Vb and about 150 Vb.

[0228] The first gas injector 104 provides two different channels for injecting two independent streams of process gas or liquid precursor (in vapor form) into the chamber from the top of the chamber. It should be understood that multiple gas supplies can be provided to supply different gases to the chamber for various types of operations, such as on-wafer processing operations, waferless autoclean (WAC) operations, and other operations. The second gas injector 110 provides another gas flow that enters the chamber through the side rather than from the top.

[0229] In one embodiment, the delivery system 128 includes an etching gas delivery system 127 and a liquid delivery system 129. The manifold 122 is used to select, switch, and / or mix the outputs from the respective delivery systems. As described in more detail below, the etching gas delivery system is configured to output an etchant gas that is optimized to etch one or more material layers of the substrate. In response to control from the controller 108, the manifold 122 is further optimized to perform plasma etching and deblocking operations.

[0230] exist Figure 4 In one embodiment, independent gas streams can be delivered to the chamber. One gas stream can be injected through the center of injector 104. A second gas stream can also be injected through injector 104, but through a different path around the center of injector 104. A third gas stream can be injected into the side of the chamber through side injectors 110. In one embodiment, gas injectors 104 also provide optical access into the processing chamber, for example, along an axial path from a diagnostic endpoint outside the processing chamber through an optical access window.

[0231] A variety of ways of injecting gases into the chamber have been described to illustrate that etching gases and / or liquid precursors can be provided to the chamber from a variety of positions. In some cases, only the injector 104 is used. In other cases, only the side injector 110 is used. In other cases, both the injector 104 and the side injector 110 can be used. In one configuration, the manifold 122 controls which gas is supplied to each of the three different gas lines. The manifold 122 allows any type of gas to be provided to any of the three different gas lines. The gas can be delivered to the chamber without mixing or mixing with other gases before being introduced into the chamber. In some embodiments, the halogen source and the vaporized organic solvent are delivered to the processing chamber through corresponding inlets. In other embodiments, they can be delivered through one inlet.

[0232] Return Reference Figure 4 A vacuum pump 130 is connected to the chamber 132 to enable vacuum pressure control and removal of gaseous byproducts from the chamber during plasma processing. A valve 126 is provided between the exhaust 124 and the vacuum pump 130 to control the amount of vacuum applied to the chamber.

[0233] The dielectric window 106 may comprise a ceramic material or a ceramic-like material. Other dielectric materials are also possible, as long as they can withstand the conditions of the semiconductor etching chamber. Typically, the chamber operates at a temperature ranging between -60 degrees Celsius and approximately 250 degrees Celsius. The apparatus also typically includes a heater and a temperature control mechanism. The temperature will depend on the etching process operation and the specific recipe. The chamber 132 will also operate under vacuum conditions in a range between about 1 millitorr (mT) and about 10 Torr.

[0234] Although not specifically shown in full, when installed in a cleanroom or processing facility, chamber 132 is typically coupled to a number of facilities. These facilities include piping systems that provide process gases, vacuum, temperature control, and environmental particle control, among others. When chamber 132 is installed in the target processing facility, these facilities are coupled to chamber 132. Furthermore, chamber 132 may be coupled to a transfer chamber that allows a robot to transfer semiconductor wafers into and out of chamber 132 using automated processes.

[0235] A programmable controller 108 is provided for controlling the operation of the chamber 132 and its associated components. Broadly speaking, the controller 108 can be programmed to perform chamber operations defined by a recipe. A given recipe can specify various parameters for the operation, such as the application of power to the TCP coil, the flow of gas into the chamber, and the application of vacuum. It should be understood that the timing, duration, magnitude, or any other adjustable parameter or controllable feature can be defined by a recipe and implemented by the controller to control the operation of the chamber 132 and its associated components. In addition, a series of recipes can be programmed into the controller 108. In one embodiment, the recipe is used to process the etching operation and includes program instructions for performing any of the methods presented herein.

[0236] In some embodiments, a system controller 108 (which may include one or more physical or logical controllers) controls some or all operations of the process chamber. The system controller 108 may include one or more memory devices and one or more processors. In some embodiments, the apparatus includes a switching system for controlling the flow rate of the process gas. In some embodiments, the controller 108 includes program instructions for causing the steps of any of the methods provided herein.

[0237] In some implementations, the system controller is part of a system, which can be part of the examples described above. Such a system can include semiconductor processing equipment, which includes one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronics for controlling their operation before, during, and after processing of semiconductor wafers or substrates. The electronics can be integrated into the system controller 108, which can control various components or subcomponents of one or more systems. Depending on the processing parameters and / or system type, the system controller can be programmed to control any of the processes disclosed herein, including the delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer into and out of tools connected or docked with a specific system and other transfer tools and / or load locks.

[0238] In general, the system controller 108 can be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits can include chips in the form of firmware that stores program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions can be instructions sent to the controller in the form of various individual settings (or program files) that define operating parameters for performing specific processes on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer to complete one or more process steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0239] In some implementations, the system controller 108 can be part of or coupled to a computer that is integrated with the system, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller can be in the "cloud" or all or part of a wafer fab host system that can allow remote access to wafer processing. The computer can enable remote access to the system to monitor the current progress of manufacturing operations, review the history of past manufacturing operations, review trends or performance metrics across multiple manufacturing operations, change parameters of the current process, set processing steps to follow the current process, or start a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system via a network (which can include a local network or the Internet). The remote computer can include a user interface that enables the input or programming of parameters and / or settings, which are then sent from the remote computer to the system. In some examples, the system controller 430 receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters can be specific to the type of process to be performed and the type of tool the controller is configured to interface with or control. Thus, as described above, the system controller 108 can be distributed, for example, by including one or more discrete controllers networked together and working toward a common purpose (e.g., processing and control as described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber communicating with one or more integrated circuits remotely (e.g., at a platform level or as part of a remote computer), which combine to control processing on the chamber.

[0240] Exemplary systems may include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, bevel edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, ALD chambers or modules, ALE chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the manufacture and / or preparation of semiconductor wafers.

[0241] As described above, depending on one or more processing steps to be performed by the tool, the controller can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in the material transport of wafer containers to and from tool locations and / or load ports in a semiconductor manufacturing facility.

[0242] In some embodiments, the controller includes program instructions for: (i) etching a target material using plasma etching on a semiconductor substrate having an exposed mask material layer, a recessed feature, and a target material layer below the mask material layer, wherein the target material is exposed at the bottom of the recessed feature, thereby increasing the depth of the recessed feature; and (ii) etching blocking material deposited during the plasma etching and narrowing or blocking the recessed feature by contacting the semiconductor substrate with a halogen source and a vapor of a liquid selected from the group consisting of an organic solvent and water.

[0243] Figure 5 FIG is a schematic diagram illustrating additional details of a liquid delivery system according to one embodiment. The liquid delivery system allows for the delivery of organic solvents and / or water in a gas phase to the processing chamber. Figure 5 As shown in , the liquid delivery system 129 includes a liquid (e.g., solvent or water) source 308, a liquid flow controller 310, and a vaporizer 312. The liquid source 308 can be coupled in flow communication to a facility that provides a suitable liquid solvent or water. As described above, various organic solvents, such as alkanes, ketones, and alcohols, can be used. The liquid organic solvent or water flows from the source 308 to the liquid flow controller 310, which regulates the flow rate based on instructions received from the controller 108. The liquid flows from the liquid flow controller 310 to the vaporizer 312, which converts the liquid solvent or water from a liquid state to a gaseous state. The vaporized precursor flows to the manifold 122, which, based on control received from the controller 108, supplies the vaporized solvent or water to the gas injector 104 (see, for example, Figure 4 The vaporized solvent or water flows through the gas injector 104 into the chamber 132 defined by the cavity 114 (see, for example, Figure 4 In some embodiments, the vaporized solvent or water is delivered to the process chamber through a first inlet, while the halogen source is delivered through a different inlet. In other embodiments, all components of the deblocking mixture are delivered to the process chamber through a shared inlet.

[0244] Figure 6A semiconductor processing cluster architecture is depicted having multiple modules that interface with a vacuum transfer module 1038 (VTM). A configuration of multiple modules that "transfer" wafers between multiple storage facilities and processing modules may be referred to as a "cluster tool architecture" system. An airlock 1030 (also known as a load lock or transfer module) interfaces with the VTM 1038, which interfaces with four processing modules 1020a-1020d, each of which may be individually optimized to perform various manufacturing processes. For example, the processing modules 1020a-1020d may be implemented to perform substrate etching, deposition, ion implantation, wafer cleaning, sputtering, and / or other semiconductor processing. In some embodiments, plasma etching of a target layer and patterning of a mask layer are performed in the same module. In some embodiments, plasma etching of a target layer and patterning of a mask layer are performed in different modules of the same tool. One or more of the substrate etch processing modules (any one of 1020a-1020d) can be implemented as disclosed herein, for example, for plasma etching of a target layer, and other suitable functions according to the disclosed embodiments. The airlock 1030 and the processing modules 1020a-1020d can be referred to as "stations." Each station has a facet 1036 that interfaces the station with a VTM 1038. In each facet, a sensor 1-18 is used to detect the passage of the wafer 1026 as it moves between the corresponding stations.

[0245] A robot 1022 transfers wafers 1026 between stations. In one embodiment, the robot 1022 has one arm, while in another embodiment, the robot 1022 has two arms, each of which has an end effector 1024 for picking up a wafer (e.g., wafer 1026) for transport. In an atmospheric transfer module (ATM) 1040, a front-end robot 1032 is used to transfer wafers 1026 from a cassette or front-opening wafer transfer pod (FOUP) 1034 in a load port module (LPM) 1042 to an airlock 1030. A module center 1028 within the processing modules 1020a-1020d is where the wafers 1026 are placed. An aligner 1044 in the ATM 1040 is used to align the wafers.

[0246] In an exemplary processing method, a wafer is placed in one of the FOUPs 1034 in the LPM 1042. The front-end robot 1032 transfers the wafer from the FOUP 1034 to the aligner 1044, which allows the wafer 1026 to be properly centered before being etched or processed. After alignment, the front-end robot 1032 moves the wafer 1026 into the airlock 1030. Because the airlock 1030 has the ability to match the environments between the ATM 1040 and the VTM 1038, the wafer 1026 can be moved between the two pressure environments without damage. The robot 1022 moves the wafer 1026 from the airlock 1030, via the VTM 1038, to one of the processing modules 1020a-1020d. To accomplish this wafer movement, the robot 1022 uses an end effector 1024 on each of its arms. Once the wafer 1026 has been processed, the robot 1022 moves it from the process modules 1020a-1020d to the airlock 1030. From there, the front end robot 1032 may move the wafer 1026 to one of the FOUPs 1034 or to the aligner 1044.

[0247] It should be noted that the computer controlling the wafer movement may be internal to the cluster architecture, or may be external to the cluster architecture located in the manufacturing site, or located in a remote location and connected to the cluster architecture via a network. Figure 4 The controller can be Figure 6 A machine-readable medium containing instructions for controlling the processing operations according to the present invention may be coupled to the system controller.

[0248] In some embodiments, a system for processing a semiconductor substrate includes: one or more etch chambers; and a system controller having program instructions for performing any of the processes or sub-processes described herein.

[0249] In some embodiments, an apparatus is provided, wherein the apparatus includes: a process chamber having a substrate holder configured to hold a semiconductor substrate during etching, and an inlet for introducing one or more reactants into the process chamber; an optional plasma generator configured to generate plasma in a process gas; and a controller. The controller includes program instructions for implementing any of the methods described herein.

[0250] In another aspect, a non-transitory computer machine readable medium comprising program code for causing the execution of any of the methods described herein is presented. Other implementation solutions

[0251] The apparatus and processes described herein can be used in conjunction with photolithographic patterning tools or processes, e.g., for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, these apparatus and processes will be used or operated together in a common manufacturing facility. Photolithographic patterning of films typically includes some or all of the following steps, each of which utilizes multiple available tools: (1) applying photoresist to a workpiece, i.e., a substrate, using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or UV curing tool; (3) exposing the photoresist to visible light or UV light or X-rays using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist and thereby pattern it using a tool such as a wet cleaning station; (5) transferring the resist pattern to an underlying film or workpiece using a dry or plasma assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper. In some embodiments, these steps are performed sequentially to form a patterned mask layer prior to etching the target layer.

Claims

1. A method for etching a material on a semiconductor substrate, the method comprising: (a) providing a semiconductor substrate having an exposed layer of a mask material, a recessed feature, and a layer of a target material below the layer of the mask material, wherein the target material is exposed at a bottom of the recessed feature; (b) etching the target material using a plasma and thereby increasing the depth of the recessed feature, wherein the etching of the target material causes narrowing or blocking of the recessed feature at least in one location due to deposition of blocking material; and (c) etching the blocking material by contacting the semiconductor substrate with a halogen source but not contacting the substrate with an organic solvent and not contacting the substrate with water.

2. The method of claim 1, wherein the halogen source and a carrier gas are provided to a processing chamber housing the substrate. 3 . The method of claim 1 , wherein the halogen source is provided to a processing chamber housing the substrate without a carrier gas. 4 . The method according to claim 1 , wherein the etching (b) of the target material and the etching (c) of the blocking material are performed in one process chamber.

5. The method of claim 1, wherein (c) comprises activating the halogen source in a plasma. The method of claim 5 , wherein (c) is performed without applying an external bias to the substrate.

7. The method of claim 5, wherein the plasma in (c) is a transformer coupled plasma.

8. The method according to claim 7, wherein the plasma power in (c) is not more than 500 W.

9. The method of claim 5, wherein a chamber pressure of a chamber accommodating the substrate during (c) is 100 mTorr to 1 Torr.

10. The method of claim 9, wherein a chamber pressure of a chamber containing the substrate during (a) is less than 100 mTorr.

11. The method of claim 1, wherein (c) is performed without applying an external bias to the semiconductor substrate.

12. The method of claim 5, wherein the plasma in (c) is pulsed.

13. The method of claim 4, wherein transitioning from (b) to (c) comprises: The chamber pressure of the process chamber is increased. The method of claim 1 , wherein the blocking material comprises silicon oxide.

15. The method of claim 1, wherein the target material is selected from the group consisting of carbon and silicon.

16. The method of claim 1, wherein the mask material is selected from the group consisting of silicon oxynitride, silicon nitride, silicon oxide, silicon oxycarbide, silicon boride, boron-doped carbon, tungsten, tungsten-doped carbon, and boron-doped carbon.

17. The method of claim 1, wherein the etching of the blocking material has an etch selectivity greater than 1 to both the mask material and the target material.

18. The method of claim 1, wherein (c) is performed in the absence of a plasma.

19. The method of claim 18, wherein a chamber pressure of a chamber containing the substrate during (c) is between 100 mTorr and 100 Torr.

20. The method of claim 1, wherein the substrate temperature is maintained during the processing.

21. A method of etching a material on a semiconductor substrate, the method comprising: (a) providing a semiconductor substrate having an exposed layer of a mask material, a recessed feature, and a layer of a target material below the layer of the mask material, wherein the target material is exposed at a bottom of the recessed feature; (b) etching the target material using a plasma and thereby increasing the depth of the recessed feature, wherein the etching of the target material causes narrowing or blocking of the recessed feature at least in one location due to deposition of blocking material; and (c) etching the blocking material by contacting the semiconductor substrate with a plasma generated by a gas phase halogen source.

22. The method of claim 21, wherein the etching (b) of the target material and the etching (c) of the blocking material are performed in one process chamber.

23. The method of claim 21, wherein the blocking material comprises silicon oxide.

24. The method of claim 21, wherein the target material is selected from the group consisting of carbon and silicon.

25. The method of claim 21, wherein the mask material is selected from the group consisting of silicon oxynitride, silicon nitride, silicon oxide, silicon oxycarbide, silicon boride, boron-doped carbon, tungsten, tungsten-doped carbon, and boron-doped carbon.

26. The method of claim 21, wherein the etching of the blocking material has an etch selectivity greater than 1 to both the mask material and the target material.

27. The method of claim 21, wherein (c) is performed without applying an external bias to the semiconductor substrate.

28. The method of claim 1, further comprising: Repeat steps (b)-(c).

29. The method of claim 21, wherein the etching of the blocking material comprises: The semiconductor substrate is contacted with a plasma generated by the halogen source and by a vapor of a liquid selected from the group consisting of an organic solvent and water.

30. The method of claim 21, wherein the etching of the blocking material comprises: The semiconductor substrate is sequentially contacted with the halogen source and a vapor of a liquid selected from the group consisting of an organic solvent and water.

31. The method of claim 21, wherein (c) further comprises: The semiconductor substrate is contacted with an additive selected from the group consisting of an amine, a heterocyclic compound, and a bifluoride source.

32. The method of claim 21, wherein the etching of the blocking material is performed at a pressure between about 0.01 Torr - 1 Torr and a temperature between about -60°C - 250°C.

33. The method of claim 21, wherein the recessed features of the semiconductor substrate provided in (a) have a width of approximately 5 nm - 300 nm.

34. The method of claim 21, wherein the semiconductor substrate comprises a device selected from the group consisting of a partially fabricated 3D NAND device, a DRAM device, and a logic device.

35. The method of claim 21, wherein after the etching is completed, the aspect ratio of the recessed features is at least about 5:

1.

36. The method of claim 21, wherein the halogen source is selected from the group consisting of nitrogen tribromide (NBr3), nitrogen trichloride (NCl3), chlorine trifluoride (ClF3), hydrogen fluoride (HF), hydrogen chloride (HCl) and hydrogen bromide (HBr).

37. The method of claim 21, wherein the plasma etching in (b) comprises: The substrate is contacted with an oxygen-containing reactant.

38. The method of claim 22, wherein transitioning from (b) to (c) comprises: The chamber pressure of the process chamber is increased.

39. The method of claim 21, wherein the plasma in (c) is pulsed.

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