Passivation of benzyl compounds for selective deposition and selective etching protection.

Abstract

The method includes forming a first layer and a second layer on a substrate; exposing the first layer and the second layer to a benzyl compound to form a passivation layer on a surface of the first layer without forming a passivation layer on the second layer; and, after forming the passivation layer on the first layer, at least one of depositing a third layer on the second layer or etching the second layer.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to the fabrication of electronic devices. In particular, embodiments of the present disclosure relate to passivation of benzyl compounds for selective deposition and selective etch protection. [Background technology]

[0002] An electronic device manufacturing apparatus may include multiple chambers, such as process chambers and load lock chambers. Such an electronic device manufacturing apparatus may employ a robotic device in a transfer chamber configured to transport substrates between the multiple chambers. In some cases, multiple substrates are transferred together. Process chambers may be used in an electronic device manufacturing apparatus to perform one or more processes on a substrate, such as a deposition process and an etching process. Multiple process gases are flowed into the process chamber. Electronic devices, such as semiconductor devices, are manufactured by performing a series of steps, which may include deposition, oxidation, photolithography, ion implantation, and etching, to form multiple patterned layers. Summary of the Invention

[0003] According to one embodiment, a method is provided that includes forming a first layer and a second layer on a substrate, exposing the first layer and the second layer to a benzyl compound to form a passivation layer on a surface of the first layer without forming a passivation layer on the second layer, and, after forming the passivation layer on the first layer, at least one of depositing a third layer on the second layer or etching the second layer.

[0004] According to one embodiment, a system is provided that includes at least one chamber. The at least one chamber is configured to form a passivation layer on a surface of the first layer without forming a passivation layer on the surface of the second layer by exposing the first layer and the second layer to a benzyl compound. The first layer and the second layer are formed on a substrate. The at least one chamber is further configured to at least one of depositing a third layer on the second layer using a deposition process or etching the second layer after forming the passivation layer. [Brief explanation of the drawings]

[0005] The present disclosure is illustrated by way of example, and not by way of limitation, in the accompanying drawings, in which like elements are designated with like reference numerals. It should be noted that various references to "an" or "one" embodiment in this disclosure are not necessarily to the same embodiment, and that such references mean at least one.

[0006] [Figure 1] FIG. 1 is a flow diagram of an exemplary method for performing benzylic compound passivation for selective deposition and selective etch protection, according to some embodiments. [Figure 2] FIG. 1 is a block diagram of an exemplary electronic device processing system that can be used to perform benzylic compound passivation for selective deposition and selective etch protection, according to some embodiments. [Figure 3A-B] 1A-1D are cross-sectional views of example device fabrications implementing benzylic compound passivation for selective deposition and selective etch protection according to some embodiments. [Figure 3C-D] 1A-1D are cross-sectional views of example device fabrications implementing benzylic compound passivation for selective deposition and selective etch protection according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0007] Embodiments described herein relate to passivation of benzyl compounds for selective deposition and selective etching protection. Electronic devices can include multiple different types of layers. For example, electronic devices can include a dielectric layer formed from a dielectric material, a conductive layer formed from a conductive material, and a semiconducting layer formed from a semiconducting material. Electronic device processing techniques can include performing patterning (e.g., photolithography) to create structures (e.g., trenches for conductive lines and / or holes for vias). For example, patterning can include multiple repeated processes of deposition and etching, such as wet etching or dry etching (e.g., plasma etching), using a photomask ("mask") and a resist film.

[0008] Some electronic devices may include a first layer and a second layer, each disposed on a substrate and, optionally, an additional layer. For example, the first layer may be disposed adjacent to the second layer. In embodiments, the first layer and the second layer may each be an exposed layer. The first layer may include a first material, and the second layer may include a second material different from the first material. During electronic device fabrication, there may be situations where a third layer must be selectively deposited on the second layer in preference to the first layer (i.e., without being deposited on the first layer), i.e., situations where it is undesirable to form a material on the first layer. Alternatively, during electronic device fabrication, there may be situations where a second layer must be selectively etched in preference to the first layer, i.e., situations where it is undesirable to etch the first layer. However, as electronic devices decrease in size (e.g., to the nanometer scale), it becomes more difficult to selectively deposit material onto the second layer and / or to selectively etch the second layer relative to the first layer.

[0009] To address these and other drawbacks, embodiments described herein can enable passivation of benzyl compounds for selective deposition and selective etch protection. Specifically, a first layer and a second layer can be deposited on a substrate (e.g., the first layer can be adjacent to the second layer). The first layer can include a material that can form a passivation layer on the surface of the first layer when exposed to an appropriate passivant. The second layer can be formed from a material that does not form a passivation layer when exposed to the same passivant.

[0010] For example, the passivant can include a benzyl compound. In some embodiments, the benzyl compound includes benzyl alcohol. Benzyl alcohol is an aromatic alcohol molecule that can include a benzyl group (CHCH-) attached to a hydroxyl functional group (-OH). Specifically, a benzyl group can be formed by attaching a benzene ring (CH) to a CH group. Thus, benzyl alcohol can be represented by the formula CHCHOH, CHO, or BOH (where "B" refers to the benzyl group). In some embodiments, the benzyl compound includes a benzyl alcohol derivative. Specifically, the benzyl alcohol derivative can take the form RCCHCHOH. For example, where R=C to C 10 is.

[0011] In some embodiments, the benzyl compound comprises a benzyl halide. A benzyl halide is a halocarbon compound (e.g., an organofluorine compound, an organochlorine compound, an organobromine compound, or an organoiodine compound) that can contain a benzyl group (CHCH-) bonded to a halogen. For example, the benzyl compound can be benzyl chloride, which is an organochlorine compound that can contain a benzyl group bonded to a chlorine (-Cl). In some embodiments, the benzyl compound comprises a benzyl halide derivative (e.g., a benzyl chloride derivative). Specifically, the benzyl halide derivative can take the form RC6H4CH2. For example, where R=C1 to C 10 is.

[0012] The first layer and the second layer each comprise a respective material such that, during exposure to the benzyl compound, the surface of the first layer undergoes catalytic polymerization of the benzyl compound, but the surface of the second layer does not, i.e., polymerization of the benzyl compound is highly selective to the surface of the first layer.

[0013] For example, the first layer can include a dielectric material. In some embodiments, the first layer includes a native oxide formed on a conductive material. For example, the first layer can be a metal oxide (e.g., a transition metal oxide) formed from a metal (e.g., a transition metal). Examples of suitable dielectric materials from which the first layer can be formed include tungsten oxide (e.g., WO2, WO3, W2O3, or W2O5), molybdenum oxide (e.g., MoO2 or MoO3), manganese oxide (e.g., MnO, MnO2, MnO3, Mn2O3, Mn3O4, Mn2O7, Mn5O8, Mn7O 12 , or MnO 13 ), nickel oxides (e.g., NiO or Ni2O3), nickelates, and the like.

[0014] In some embodiments, the second layer includes a dielectric material. For example, the second layer can include an oxide. By way of example, the oxide can be silicon oxide or a metal oxide (e.g., a transition metal oxide). For example, the metal oxide can be different from the metal oxide used to form the first layer. As another example, the second layer can include a nitride. By way of example, the nitride can be silicon nitride or a metal nitride (e.g., a transition metal nitride). Examples of suitable dielectric materials that can be used to form the second layer include silicon dioxide (SiO), carbon-doped silicon oxide (e.g., SiOC, SiCOH), silicon nitride (SiN), aluminum oxide (AlO), aluminum nitride (AlN), etc. In some embodiments, the second layer includes a conductive material. For example, the second layer can include a metal. By way of example, the conductive material can include cobalt (Co), copper (Cu), silver (Ag), tungsten (W), molybdenum (Mo), etc.

[0015] Catalyzed polymerization of the benzyl compound by the first layer forms a passivation layer comprising a polymer that adsorbs to the surface of the first layer. In some embodiments, the passivation layer comprises poly(phenylenemethylene) (PPM). PPM is a hydrocarbon polymer comprising multiple monomers, each monomer comprising a phenylene unit (C6H4-) and a methylene unit (-CH2). Thus, PPM has the formula (C6H4[CH2]) n Polymerization of the benzyl compound into the PPM can include converting the residue of the benzyl compound into dibenzyl ether (C6H5CH2)2O, which can then be polymerized into the PPM.

[0016] In some embodiments, passivation is performed in situ. In some embodiments, passivation is performed ex situ. The process of forming the passivation layer can include performing multiple cycles. Each cycle can include pulsing the benzyl compound, soaking, and purging. Each step of the cycle can be performed using any suitable process parameters. The process parameters can control the thickness of the passivation layer. Examples of process parameters for performing passivation include temperature, pressure, number of cycles, pulse time (i.e., the length of time for each monomer), purge time (i.e., the length of time purge gas is introduced between pulses), etc. Further details regarding the formation of the passivation layer are provided below with reference to FIG. 1.

[0017] In some embodiments, a cleaning process is performed prior to passivation of the conductive material (i.e., pre-cleaning). The pre-cleaning process can optionally be performed to improve selectivity of the passivation layer relative to the surface of the first layer and / or to reduce deposition of the passivation layer on the surface of the second layer. For example, the pre-cleaning process can remove contaminants from the surface of the first layer and / or reduce defect growth on the conductive material. For example, the pre-cleaning process can include a thermal moisture treatment, a hydrogen treatment, a water vapor treatment, an oxygen dosing treatment, etc. Further details regarding the pre-cleaning process are described below with reference to FIG. 1 .

[0018] After passivation (and any pre-cleaning before passivation), at least one processing step can be performed. In particular, the passivation layer can act as a barrier layer during at least one processing step.

[0019] In some embodiments, at least one processing step includes depositing a third layer on the surface of the second layer. Specifically, the passivation layer prevents (e.g., blocks) the adsorption of deposition precursors (i.e., prevents nucleation of the deposition precursors) during the subsequent deposition process that forms the third layer, thereby allowing the third layer to be selectively deposited on the surface of the second layer in preference to the passivation layer. This can prevent (e.g., inhibit) the formation of the third layer on the passivation layer. The third layer can be deposited to a target thickness on the surface of the second layer (e.g., by performing an appropriate number of deposition cycles).

[0020] The third layer can comprise any suitable material. In some embodiments, the third layer comprises a dielectric material. The third layer can comprise any suitable dielectric material. In some embodiments, the third layer comprises a nitride (e.g., a metal nitride). Examples of suitable nitrides that can be used to form the third layer include tantalum nitride (TaN), titanium nitride (TiN), molybdenum nitride (MoN), tungsten nitride (e.g., WN, WN, WN), manganese nitride (MnN, MnN), etc. In some embodiments, the third layer comprises an oxide. Examples of suitable oxides that can be used to form the third layer include Al2O3, SiO2, hafnium dioxide (HfO2), titanium dioxide (TiO2), zirconium dioxide (ZrO2), vanadium oxides (e.g., VO, VO2, VO3, VO5), niobium oxides (e.g., NbO, NbO2, Nb2O5), tantalum pentoxide (Ta2O5), tungsten oxides (e.g., WO2, WO3, W2O3, W2O5), molybdenum oxides (e.g., MoO2, MoO3), and the like. In some embodiments, the third layer comprises a conductive material. The third layer can include any suitable conductive material. Examples of suitable conductive materials include cobalt (Co), copper (Cu), silver (Ag), tungsten (W), molybdenum (Mo), and the like.

[0021] The deposition process can be any suitable deposition process. In some embodiments, the deposition process is an ALD process. In some embodiments, the deposition process is a chemical vapor deposition (CVD) process. The deposition process can utilize any suitable deposition precursor and any suitable process parameters. For example, if the third layer includes a metal oxide, the deposition process can utilize a metal oxide precursor (e.g., a metal alkoxide precursor). As another example, if the third layer includes a conductive material (e.g., a metal), the deposition process can utilize a conductive material precursor (e.g., a metal precursor). The process parameters of the deposition process (e.g., a CVD process or a thermal ALD process) can depend on the one or more deposition precursors used to form the second layer and the target thickness of the resulting second layer.

[0022] In some embodiments, at least one processing step includes etching the second layer. The passivation layer can provide selective etch protection for the surface of the first layer during etching of the second layer. Specifically, the passivation layer can be resistant to the particular etch chemistry used to etch the second layer. For example, if the etch process is a dry etch process, the etch chemistry can include nitrogen trifluoride (NF3) gas to generate an NF3 plasma. Further details regarding passivation of benzyl compounds for selective deposition and selective etch protection are described below with reference to FIG. 1.

[0023] 1 illustrates an exemplary method 100 for performing passivation of a benzylic compound for selective deposition and selective etch protection, according to some embodiments. Method 100 can be performed within an electronic device processing system. Specifically, method 100 can be performed within one or more processing chambers of the electronic device processing system. Further details regarding electronic device processing systems are described below with reference to FIG. 2.

[0024] In step 110, a base structure for the device is formed, including a first layer and a second layer. The first layer can include a first material, and the second layer can include a second material different from the first material. In some embodiments, the first layer is formed adjacent to the second layer. For example, the first layer and the second layer can be formed on a substrate. For example, the substrate can be an initial layer of the device. The substrate can include any suitable material according to embodiments described herein. In some embodiments, the substrate is a silicon (Si) substrate.

[0025] The first layer and second layer can each be formed from a respective material such that, upon subsequent exposure to a benzyl compound, the first layer undergoes catalytic polymerization of the benzyl compound and the second layer does not undergo catalytic polymerization of the benzyl compound, i.e., polymerization of the benzyl compound is highly selective to the first layer.

[0026] The first layer can include a dielectric material. In some embodiments, the first layer includes a native oxide formed on a conductive material. For example, the first layer can be a metal oxide (e.g., a transition metal oxide) formed from a metal (e.g., a transition metal). Examples of suitable dielectric materials that can be used to form the first layer include tungsten oxide (e.g., WO2, WO3, W2O3, or W2O5), molybdenum oxide (e.g., MoO2 or MoO3), ruthenium oxide (e.g., RuO2 or RuO4), manganese oxide (e.g., MnO, MnO2, MnO3, Mn2O3, Mn3O4, Mn2O7, Mn5O8, Mn7O 12 , or MnO 13 ), nickel oxides (e.g., NiO or Ni2O3), nickelates, and the like.

[0027] In some embodiments, the second layer includes a dielectric material. For example, the second layer can include an oxide. By way of example, the oxide can be silicon oxide or a metal oxide (e.g., a transition metal oxide). As another example, the second layer can include a nitride. By way of example, the nitride can be silicon nitride or a metal nitride (e.g., a transition metal nitride). Examples of suitable dielectric materials that can be used to form the second layer include SiO, carbon-doped silicon oxide (e.g., SiOC, SiCOH), SiN, AlO, AlN, etc. In some embodiments, the second layer includes a conductive material. For example, the second layer can include a metal. By way of example, the conductive material can include Co, Cu, Ag, W, Mo, etc.

[0028] In step 120, an optional pre-cleaning process is performed. Specifically, the base structure including the first layer and the second layer may be cleaned. The pre-cleaning process may be optionally performed to improve selectivity of the passivation layer relative to the surface of the first layer and / or to reduce deposition of the passivation layer on the surface of the second layer. For example, the pre-cleaning process may remove contaminants from the surface of the first layer and / or reduce defect growth on the conductive material. The pre-cleaning process may include a thermal moisture treatment, a hydrogen treatment, a water vapor treatment, an oxygen dosing treatment, etc.

[0029] The pre-cleaning process can be carried out using any suitable process parameters. Example process parameters for carrying out the pre-cleaning include the amount of time, temperature, pressure, etc. For example, the thermal moisture treatment can be carried out at a temperature ranging from about 200°C to about 300°C (e.g., about 250°C) for a time ranging from about 0.2 seconds (s) to about 10 seconds. In some embodiments, the pressure ranges from about 100 mTorr to about 10 Torr. In some embodiments, the pressure ranges from about 500 mTorr to about 10 Torr. In some embodiments, the pressure ranges from about 1 Torr to about 10 Torr.

[0030] In step 130, a passivation layer is formed on the surface of the first layer. Specifically, forming the passivation layer can include exposing the first layer to a benzyl compound. The benzyl compound can react strongly with the first layer to form a passivation layer that adsorbs to the surface of the first layer. In some embodiments, during a single passivation process, the first conductive material is exposed to benzyl alcohol. In some embodiments, the benzyl compound includes benzyl alcohol. In some embodiments, the benzyl compound includes a benzyl alcohol derivative. In some embodiments, the benzyl compound includes a benzyl halide. For example, the benzyl halide can include benzyl chloride. In some embodiments, the benzyl compound includes a benzyl halide derivative.

[0031] Specifically, the first layer allows catalytic polymerization of a benzyl compound to form a passivation layer, and the passivation layer comprises a polymer adsorbed to the surface of the first layer. In some embodiments, the passivation layer comprises a PPM. For example, polymerizing the benzyl compound into a PPM can include converting a residue of the benzyl compound into a dibenzyl ether, which can then be polymerized into a PPM.

[0032] In some embodiments, the passivation layer is formed in situ. In some embodiments, the passivation layer is formed ex situ. Formation of the passivation layer can be carried out using any suitable process parameters. The process parameters can control the thickness of the passivation layer. Example process parameters for carrying out passivation include temperature, pressure, cycles, pulse time (i.e., the length of time for each monomer), purge time (i.e., the length of time that purge gas is introduced between pulses), etc.

[0033] For example, forming a passivation layer can include pulsing a benzyl compound at a suitable pressure for a suitable pulse time. In some embodiments, the benzyl compound is pulsed for a pulse time ranging from about 0.1 seconds to about 10 seconds and at a pressure ranging from about 500 millitorr to about 50 torr. In some embodiments, the benzyl compound is pulsed for a pulse time ranging from about 2 seconds to about 5 seconds and at a pressure ranging from about 1 to about 5 torr. In some embodiments, the benzyl compound is pulsed for a pulse time of about 3 seconds and at a pressure of about 1.8 torr.

[0034] Forming the passivation layer can further include pulsing the benzyl compound followed by immersion at a suitable pressure for a suitable immersion time. In some embodiments, the immersion is performed for a immersion time ranging from about 1 s to about 40 s and at a pressure ranging from about 500 mTorr to about 50 Torr. In some embodiments, the immersion is performed for a immersion time ranging from about 10 s to about 30 s and at a pressure ranging from about 1 Torr to about 5 Torr. In some embodiments, the immersion is performed for a immersion time ranging from about 20 s and at a pressure of about 1.8 Torr.

[0035] Forming the passivation layer can further include performing a purge after the immersion for a suitable immersion time at a suitable pressure. The purge can be performed using any suitable purge gas (e.g., Ar or N2). In some embodiments, the purge is performed for a purge time ranging from about 1 s to about 20 s and at a pressure ranging from about 500 mTorr to about 10 Torr. In some embodiments, the purge is performed for a purge time ranging from about 5 s to about 15 s and at a pressure ranging from about 1 Torr to about 5 Torr. In some embodiments, the purge is performed for a purge time ranging from about 10 s to about 0.8 Torr.

[0036] The above steps constitute a single cycle. Each step of the cycle can be carried out at a suitable temperature. In some embodiments, the temperature ranges from about 100°C to about 400°C. In some embodiments, the temperature ranges from about 300°C to about 375°C. In some embodiments, the temperature is about 350°C.

[0037] Any suitable number of cycles can be performed to achieve a suitable passivation layer thickness. In some embodiments, the passivation layer thickness can range from about 0.5 nanometers (nm) to about 100 nm. In some embodiments, the number of cycles ranges from about 1 cycle to about 50 cycles. In some embodiments, the number of cycles ranges from about 15 cycles to about 35 cycles. In some embodiments, the number of cycles is about 20 cycles.

[0038] At least one processing step is performed in step 140. Specifically, the at least one processing step may be performed after forming a passivation layer (and any pre-cleaning before forming the passivation layer). The passivation layer may function as a barrier layer during the at least one processing step.

[0039] In some embodiments, at least one processing step includes depositing a third layer on the surface of the second layer. Specifically, the passivation layer prevents (e.g., blocks) the adsorption of deposition precursors (i.e., prevents nucleation of the deposition precursors) during the subsequent deposition process that forms the third layer, thereby enabling selective deposition of the third layer on the surface of the second layer in preference to the passivation layer. This can prevent (e.g., inhibit) the formation of the third layer on the passivation layer. The third layer can be deposited to a target thickness on the surface of the second layer (e.g., by performing an appropriate number of deposition cycles).

[0040] The third layer can comprise any suitable material. In some embodiments, the third layer comprises a dielectric material. The third layer can comprise any suitable dielectric material. In some embodiments, the third layer comprises a nitride (e.g., a metal nitride). Examples of suitable nitrides that can be used to form the third layer include TaN, TiN, MoN, tungsten nitride (e.g., WN, WN, WN), manganese nitride (MnN, MnN), etc. In some embodiments, the third layer comprises an oxide. Examples of suitable oxides that can be used to form the third layer include Al2O3, SiO2, HfO2, TiO2, ZrO2, vanadium oxides (e.g., VO, VO2, VO3, VO5), niobium oxides (e.g., NbO, NbO2, Nb2O5), Ta2O5, tungsten oxides (e.g., WO2, WO3, W2O3, W2O5), molybdenum oxides (e.g., MoO2, MoO3), and the like. In some embodiments, the third layer is a conductive layer. The third layer can include any suitable conductive material. Examples of suitable conductive materials include Co, Cu, Ag, W, Mo, and the like.

[0041] The deposition process can be any suitable deposition process. In some embodiments, the deposition process is an ALD process. In some embodiments, the deposition process is a CVD process. The deposition process can utilize any suitable deposition precursor and any suitable process parameters. For example, if the third layer includes a metal oxide, the deposition process can utilize a metal oxide precursor (e.g., a metal alkoxide precursor). As another example, if the third layer includes a conductive material (e.g., a metal), the deposition process can utilize a conductive material precursor (e.g., a metal precursor). The process parameters of the deposition process (e.g., an ALD process or a CVD process) can depend on the one or more deposition precursors used to form the third layer and the target thickness of the resulting third layer.

[0042] In some embodiments, at least one processing step includes etching the second layer. The passivation layer can be resistant to a particular etching chemistry used to etch the second layer, thereby allowing selective etch protection of the first layer during etching of the second layer.

[0043] In step 150, an optional post-cleaning process may be performed. Specifically, the post-cleaning process may be performed after forming the third layer. Performing the post-cleaning process may include removing a passivation layer from the surface of the first layer. As another example, performing the post-cleaning process may further include removing defects.

[0044] 2 is a block diagram of an exemplary electronic device processing system ("system") 200 that can be used to perform benzylic compound passivation for selective deposition and selective etch protection, according to some embodiments. For example, system 200 can be used to perform method 100 described above with reference to FIG.

[0045] As shown, system 200 includes a passivation chamber 210, a transfer chamber 220, and at least one process chamber 230. Interface 240-1 can be disposed between passivation chamber 210 and transfer chamber 220, and interface 240-2 can be disposed between the transfer chamber and process chamber 230. In some embodiments, interfaces 240-1 and 240-2 are respective gate valves. Transfer chamber 220 can include a transfer robot (not shown). In some embodiments, process chamber 230 is a deposition chamber. In some embodiments, process chamber 230 is an etch chamber.

[0046] The transfer chamber 220, passivation chamber 210, and process chamber 230 may each be maintained under vacuum (e.g., zero or near-zero humidity) at controlled conditions. Although not shown, the system 200 may further include at least one load lock chamber and at least one factory interface to allow substrates to be moved from the atmosphere to the transfer chamber 220. Thus, substrates may be transferred between chambers without breaking vacuum and therefore exposing the substrates to air and / or moisture.

[0047] The passivation chamber 210 can receive a substrate including a first layer and a second layer and form a passivation layer on the first layer by exposing the first layer to a benzyl compound (e.g., benzyl alcohol or benzyl chloride). The passivation chamber 210 can be operably coupled to at least one passivation gas reservoir 212. For example, the at least one passivation gas reservoir 212 can include a benzyl compound reservoir. The at least one passivation gas reservoir 212 can further include a purge gas reservoir. The purge gas reservoir can include any suitable inert gas (e.g., Ar or N) for purging the passivation chamber 212 during the passivation process. The passivation process can be carried out using any suitable passivation process parameters. Further details regarding the formation of the passivation layer are described above with reference to FIG. 1.

[0048] After forming the passivation layer on the surface of the first layer, the transfer robot can transfer the substrate to the process chamber 230. After receiving the substrate, the process chamber 230 can perform at least one process. For example, the at least one process can include a deposition process that selectively forms a third dielectric layer on the surface of the second layer. In some embodiments, the deposition process is a CVD process. In some embodiments, the deposition process is an ALD process. As another example, the at least one process can include an etching process that etches the second layer. In some embodiments, the etching process is a dry etching process.

[0049] The process chamber 230 can be operably coupled to at least one process gas reservoir 232. For example, the at least one process gas reservoir 232 can include a deposition precursor reservoir for performing a deposition process. The deposition precursor reservoir can include one or more suitable deposition precursors for forming the third layer. As another example, the at least one process gas reservoir 232 can include an etch precursor reservoir for performing an etch process. The etch precursor reservoir can include one or more suitable etch precursors for etching the second layer. As yet another example, the at least one process gas reservoir 232 can include a purge gas reservoir. The purge gas reservoir can include any suitable inert gas for purging the process chamber 230 (e.g., Ar or N). The deposition and / or etch processes can be performed using any suitable process parameters. Further details regarding performing the deposition and / or etch processes are described above with reference to FIG. 1 .

[0050] In some embodiments, the deposition process and / or the etching process is performed in the passivation chamber 210 (i.e., the passivation chamber 210 is a process chamber configured to perform the passivation process and the deposition process and / or the etching process). In such embodiments, at least one process gas reservoir 232 can be operably coupled to the passivation chamber 210. In some embodiments, the passivation process is performed in the process chamber 230 (i.e., the process chamber 230 is a process chamber configured to perform the passivation process and the deposition process and / or the etching process). In such embodiments, at least one passivation gas reservoir 212 can be operably coupled to the process chamber 230.

[0051] In some embodiments, system 200 may optionally include a cleaning chamber 250 to perform any cleaning process before passivation (i.e., a pre-cleaning process) and / or any cleaning process after formation of the second layer (i.e., a post-cleaning process). Interface 240-3 may be disposed between cleaning chamber 250 and transfer chamber 220. In some embodiments, cleaning chamber 250 is an in-situ cleaning chamber and interface 240-3 is a gate valve. In some embodiments, cleaning chamber 250 is an ex-situ cleaning chamber and interface 240-3 is a load lock chamber. The pre-cleaning process and / or post-cleaning process may be performed using any suitable pre-cleaning process parameters.

[0052] For example, performing the post-cleaning process may include heating the device to a temperature of 350° C. or greater. As another example, performing the post-cleaning process may further include removing defects (e.g., portions of dielectric material that may have formed on the conductive material during the deposition process). As another example, the post-cleaning process may be a plasma cleaning process. As yet another example, the post-cleaning process may be a remote plasma cleaning process. The post-cleaning process may be performed using any suitable post-cleaning process parameters.

[0053] The cleaning chamber 250 can be operably coupled to at least one cleaning gas reservoir 252. The at least one cleaning gas reservoir 252 can contain a suitable cleaning chemistry. The at least one cleaning gas reservoir 252 can further include a purge gas reservoir. The purge gas reservoir can contain any suitable inert gas (e.g., Ar or N) for purging the cleaning chamber 252 during the passivation process.

[0054] In some embodiments, the pre-cleaning process can be performed in the same chamber as the passivation (e.g., the passivation chamber 210 or at least one process chamber 230). In such embodiments, at least one cleaning gas reservoir 252 can be operably coupled to the passivation chamber 210 and / or at least one process chamber 230. In some embodiments, the post-cleaning process can be performed in the passivation chamber 210 and / or at least one process chamber 230. In such embodiments, at least one cleaning gas reservoir 252 can be operably coupled to the passivation chamber 210 and / or at least one process chamber 230. Further details regarding performing the cleaning processes (e.g., the pre-cleaning process and / or the post-cleaning process) are described above with reference to FIG. 1 .

[0055] 3A-3D are cross-sectional views of an example fabrication of a device 300 that performs passivation of a benzyl compound for selective deposition and selective etch protection, according to some embodiments. As shown in FIG. 3A, the device 300 can include a base structure 302 including a substrate 305, a layer 310 disposed on the substrate 305, and a layer 320 disposed on the substrate 305 adjacent to a conductive layer. The substrate 305 can include at least one layer including a substrate layer (e.g., a Si substrate layer). The at least one layer of the substrate 305 can further include one or more additional layers disposed between the substrate layer 305 and layers 310 and 320.

[0056] Layer 310 may include any suitable conductive material. For example, layer 310 may include a metal (e.g., a transition metal). Examples of suitable transition metals include W, Mo, Ru, Mn, Ni, etc. In some embodiments, layer 320 includes a dielectric material. Layer 320 may include any suitable dielectric material. For example, layer 320 may include an oxide. By way of example, the oxide may be silicon oxide or a metal oxide (e.g., a transition metal oxide). As another example, the second layer may include a nitride. By way of example, the nitride may be silicon nitride or a metal nitride (e.g., a transition metal nitride). Examples of suitable dielectric materials that may be used to form dielectric layer 320 include SiO, carbon-doped silicon oxide (e.g., SiOC, SiCOH), SiN, AlO, AlN, etc. In some embodiments, layer 320 includes a conductive material. For example, the second layer may include a metal. By way of example, the conductive material may include Co, Cu, Ag, W, Mo, etc.

[0057] As further shown, a native oxide layer 312 can be formed on layer 310. For example, the first layer can be a metal oxide (e.g., a transition metal oxide). By way of example, if layer 310 includes W, native oxide layer 312 can include tungsten oxide (e.g., WO2, WO3, W2O3, or W2O5). If layer 310 includes Mo, native oxide layer 312 can include molybdenum oxide (e.g., MoO2 or MoO3). If layer 310 includes Mn, native oxide layer 312 can include manganese oxide (e.g., MnO, MnO2, MnO3, Mn2O3, Mn3O4, Mn2O7, Mn5O8, Mn7O). 12 , or MnO 13 ). When layer 310 includes Mo, native oxide layer 312 can include a nickel oxide (e.g., NiO or Ni2O3) or nickelate. Further details regarding the formation of base structure 302 are described above with reference to FIGS. 1-2.

[0058] 3B, passivation layer 330 is formed on native oxide layer 312. Specifically, forming passivation layer 330 can include exposing native oxide layer 312 to a benzyl compound. The benzyl compound can react strongly with native oxide layer 312 to form passivation layer 330 that adsorbs to the surface of native oxide layer 312. In some embodiments, the benzyl compound includes benzyl alcohol. In some embodiments, the benzyl compound includes a benzyl alcohol derivative. In some embodiments, the benzyl compound includes a benzyl halide. For example, the benzyl halide can include benzyl chloride. In some embodiments, the benzyl compound includes a benzyl halide derivative.

[0059] Specifically, the native oxide 312 allows for the catalytic polymerization of the benzyl compound to form a passivation layer 330 comprising the polymer. In some embodiments, the passivation layer 330 comprises PPM. The native oxide 312 can be exposed to the benzyl compound in any suitable number of passivation processes to achieve a desired passivation layer thickness. In some embodiments, the native oxide 312 is exposed to the benzyl compound during a single passivation process. Further details regarding the formation of the passivation layer 330 are described above with reference to FIGS. 1-2.

[0060] After passivation layer 330 is formed, at least one processing step can be performed using passivation layer 330 as a barrier layer. In some embodiments, as shown in FIG. 3C , at least one processing step includes depositing layer 340 on the surface of layer 320. Specifically, the passivation layer enables selective deposition of layer 340 on the surface of layer 320 in preference to passivation layer 330. Specifically, the passivation layer can prevent (e.g., block) adsorption of deposition precursors (i.e., prevent nucleation of the deposition precursors) during the deposition process that forms layer 340. This can prevent (e.g., inhibit) the formation of a third layer on the passivation layer. The third layer can be deposited to a target thickness on the surface of the second layer (e.g., by performing an appropriate number of deposition cycles).

[0061] Layer 340 can include any suitable material. In some embodiments, layer 340 includes a dielectric material. Layer 340 can include any suitable dielectric material. In some embodiments, the third layer can include a nitride (e.g., a metal nitride). Examples of suitable nitrides that can be used to form layer 340 include TaN, TiN, MoN, tungsten nitrides (e.g., WN, WN, WN), manganese nitrides (e.g., MnN, MnN), etc. In some embodiments, layer 340 includes an oxide. Examples of suitable oxides that can be used to form layer 340 include Al2O3, SiO2, HfO2, TiO2, ZrO2, vanadium oxides (e.g., VO, VO2, VO3, VO2O5), niobium oxides (e.g., NbO, NbO2, Nb2O5), Ta2O5, tungsten oxides (e.g., WO2, WO3, W2O3, W2O5), molybdenum oxides (e.g., MoO2, MoO3), and the like. In some embodiments, layer 340 comprises a conductive material. Examples of suitable conductive materials that can be used to form layer 340 include Co, Cu, Ag, W, Mo, and the like.

[0062] The deposition process can be any suitable deposition process. In some embodiments, the deposition process is an ALD process. In some embodiments, the deposition process is a CVD process. The deposition process can utilize any suitable deposition precursor and any suitable process parameters. For example, if layer 340 includes a metal oxide, the deposition process can utilize a metal oxide precursor (e.g., a metal alkoxide precursor). As another example, if layer 340 includes a conductive material (e.g., a metal), the deposition process can utilize a conductive material precursor (e.g., a metal precursor). The process parameters of the deposition process (e.g., an ALD process or a CVD process) can depend on the one or more deposition precursors used to form layer 340 and the target thickness of the resulting layer 340.

[0063] In some embodiments, as shown in Figure 3D, the at least one processing step includes etching layer 320. Passivation layer 330 can be resistant to the particular etching chemistry used to etch layer 320, which can provide adequate etch protection during etching of layer 320. Further details regarding the performance of the at least one processing step are described above with reference to Figures 1-2.

[0064] In some embodiments, at least one cleaning process may be performed. For example, the at least one cleaning process may include a pre-cleaning process performed prior to forming the passivation layer 330 and / or a post-cleaning process performed after at least one processing step. Further details regarding performing the at least one cleaning process are described above with reference to FIGS. 1-2.

[0065] The foregoing description sets forth numerous specific details, such as examples of specific systems, components, and methods, to provide a thorough understanding of some embodiments of the present disclosure. However, it will be apparent to those skilled in the art that at least some embodiments of the present disclosure may be practiced without these specific details. In other instances, well-known components or methods have not been described in detail or have been presented in simple block diagram form to avoid unnecessarily obscuring the present disclosure. Thus, the specific details described are merely exemplary. Particular implementations may vary from these example details and still be considered within the scope of the present disclosure.

[0066] Throughout this specification, a reference to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the appearances of "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. In addition, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." When the term "about" or "approximately" is used herein, it is intended to mean that the stated nominal value is accurate to within ±10%.

[0067] Although the steps of the methods herein are illustrated and described in a particular order, the order of each method step may be changed, some steps may be performed in reverse order, or some steps may be performed at least partially concurrently with other steps. In alternative embodiments, the order of separate steps or substeps may be intermittent and / or alternating.

[0068] It should be understood that the above description is intended to be illustrative, and not limiting. Many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. Accordingly, the scope of the present disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. forming a first layer and a second layer on a substrate; exposing the first layer and the second layer to a benzyl compound to form a passivation layer on the surface of the first layer without forming a passivation layer on the surface of the second layer; after forming the passivation layer on the first layer, depositing a third layer on the second layer or etching the second layer; A method comprising:

2. The method of claim 1 , further comprising performing a pre-cleaning process to clean the surface of the first layer prior to forming the passivation layer.

3. 10. The method of claim 1, wherein depositing the third layer on the second layer comprises using at least one of an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process.

4. 2. The method of claim 1, wherein forming the passivation layer comprises using the first layer to cause catalytic polymerization of the benzyl compound, and the passivation layer comprises poly(phenylenemethylene) (PPM).

5. The method of claim 1 , wherein the first layer comprises a transition metal oxide.

6. The method of claim 5 , wherein the first layer comprises at least one of tungsten oxide, molybdenum oxide, or nickel oxide.

7. The method of claim 1 , wherein the second layer comprises a dielectric layer.

8. The method of claim 7 , wherein the second layer comprises at least one of silicon dioxide, carbon-doped silicon oxide, silicon nitride, a transition metal oxide, or a transition metal nitride.

9. The method of claim 1 , wherein the second layer comprises a conductive material.

10. The method of claim 1 , wherein the third layer comprises a metal oxide or a metal nitride.

11. 1. A system comprising at least one chamber, the at least one chamber comprising: exposing a first layer and a second layer formed on a substrate to a benzyl compound to form a passivation layer on a surface of the first layer without forming a passivation layer on a surface of the second layer; After forming the passivation layer, depositing a third layer on the second layer using a deposition process or etching the second layer. The system is configured as follows:

12. 12. The system of claim 11, wherein the at least one chamber is further configured to perform a pre-cleaning process to clean a surface of the first layer prior to forming the passivation layer.

13. 12. The system of claim 11, wherein depositing the third layer on the second layer includes using at least one of an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process.

14. 12. The system of claim 11, wherein forming the passivation layer comprises using the first layer to cause catalytic polymerization of the benzyl compound, and the passivation layer comprises poly(phenylenemethylene) (PPM).

15. The system of claim 11 , further comprising a deposition precursor reservoir operably coupled to the at least one chamber.

16. The system of claim 11 , wherein the first layer comprises at least one of tungsten oxide, molybdenum oxide, or nickel oxide.

17. The system of claim 11 , wherein the second layer comprises a dielectric layer.

18. 20. The system of claim 17, wherein the second layer comprises at least one of silicon dioxide, carbon-doped silicon oxide, silicon nitride, a transition metal oxide, or a transition metal nitride.

19. The system of claim 11 , wherein the second layer comprises a conductive material.

20. The system of claim 11 , wherein the third layer comprises a metal oxide or a metal nitride.

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