Vapor deposition of carbon-based films

Abstract

To provide a method for direct growth of graphene hard mask films on arbitrary substrates without the use of metal catalysts at relatively low temperatures.SOLUTION: A method of forming a film comprises: exposing 112 a substrate to an aromatic precursor in a processing chamber; purging 114 the processing chamber of the aromatic precursor; heating 116 the substrate to a temperature less than 600°C to polymerize the aromatic precursor and deposit a graphene hard mask film on the substrate; and purging 118 the processing chamber.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001]

[0001] Embodiments of the present disclosure generally relate to methods for depositing or forming graphene. Some embodiments of the present disclosure relate to methods for forming graphene hardmask films on dielectric substrates. Some embodiments relate to methods for improving substrate surface quality or deposition parameters while depositing graphene. [Background technology]

[0002] Graphene has attracted much attention in semiconductor manufacturing as a result of its excellent optical and electrical properties. Due to its unique 2D honeycomb-shaped lattice and one atomic layer structure, graphene, a single layer of carbon atoms arranged in a hexagonal lattice, holds tremendous potential for the future of the electronics industry. Graphene is the thinnest material with a thickness of one carbon atom of about 3.35 angstroms. Hence, graphene has the highest specific surface area (SSA) recorded among carbon materials. This high SSA brings the promising attribute that graphene can store more energy than other carbonaceous materials. In addition, the delocalized electrons in a graphene sheet have a density of about 2-2.5×10 5 cm 2 Graphene can move at high speeds with an intrinsic mobility of 100 nm / vs, which helps it carry electric current efficiently. Due to its thin thickness and high electron mobility, graphene can be used as a replacement for traditional metal barrier layers in next-generation semiconductor devices, as metal lines become increasingly resistive as thickness and dimensions continue to shrink. Graphene also exhibits high optical transparency that can be used in flexible electronics, for example in smartwatch applications.

[0003]

[0003] Conventional graphene CVD growth requires high temperatures (>1000°C) and metal foils as catalysts. These high temperatures can damage most materials used in electronic applications. In addition, the metal foils need to be removed after graphene growth. The transfer process is expensive, can damage the graphene hardmask film, and can also cause metal contamination. For this reason, low-temperature growth without metal catalysts is highly desirable.

[0004]

[0004] Currently, chemical vapor deposition (CVD) with metal catalysts is used to grow graphene films. High-quality graphene films can be deposited by CVD growth, but it requires high growth temperatures, usually above 800-1000°C. This is not compatible with the current integration flow in the semiconductor industry, because the metal lines and low-k films on the device wafer cannot withstand such high temperatures. In addition, graphene deposited by high-temperature CVD also needs to be transferred from metal foils. The transfer process is expensive and can lead to film damage, defects in the film, and metal contamination. Therefore, high-temperature CVD by known methods is neither convenient nor feasible for industrial applications. Therefore, it is highly desirable to grow it directly on any substrate without the use of metal catalysts at relatively low temperatures.

[0005]

[0005] Therefore, there is a need for improved methods for depositing graphene hardmask films. Summary of the Invention

[0006]

[0006] One or more embodiments of the present disclosure are directed to a method of forming a graphene hardmask film, the method including exposing a substrate to an aromatic precursor in a process chamber, purging the aromatic precursor from the process chamber, heating the substrate to a temperature less than 600° C. to polymerize the aromatic precursor and deposit a graphene hardmask film on the substrate, and purging the process chamber. Includes.

[0007]

[0007] Additional embodiments of the present disclosure are directed to a method of forming a film. In one or more embodiments, the method includes forming a flowable graphene hardmask film on a substrate by exposing the substrate to an aromatic precursor and exposing the substrate to a plasma.

[0008]

[0008] A further embodiment of the present disclosure is directed to a non-transitory computer-readable medium containing instructions that, when executed by a controller of a processing chamber, cause the processing chamber to perform the steps of exposing a substrate to an aromatic precursor in the processing chamber, purging the aromatic precursor from the processing chamber, heating the substrate to a temperature less than 600°C to polymerize the aromatic precursor and deposit a graphene hardmask film on the substrate, and purging the processing chamber.

[0009]

[0009] So that the above-mentioned features of the present disclosure can be understood in detail, a more particular description of the present disclosure as outlined above can be obtained by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the present disclosure is open to other equally effective embodiments, and therefore the accompanying drawings merely illustrate typical embodiments of the present disclosure, and should not be considered as limiting the scope of the present disclosure. [Brief description of the drawings]

[0010] [Figure 1] 1 shows a process flow diagram of a method according to one or more embodiments of the present disclosure. [Diagram 2]

[0011] FIG. 1 shows a process flow diagram of a method according to one or more embodiments of the present disclosure. [Diagram 3]

[0012] 1 illustrates a cluster tool in accordance with one or more embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011]

[0013] Before describing certain example embodiments of the present disclosure, it is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description as the present disclosure is capable of other embodiments and of being practiced or carried out in various ways.

[0012]

[0014] As used herein and in the appended claims, the term "substrate" refers to a surface or a portion of a surface on which a process acts. Those skilled in the art will also understand that a reference to a substrate may refer to only a portion of the substrate unless the context clearly indicates otherwise. Additionally, a reference to depositing on a substrate may refer to both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0013]

[0015] As used herein, "substrate" refers to any substrate or material surface formed on a substrate on which a film treatment is performed during a manufacturing process. For example, substrate surfaces on which treatment can be performed include materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, but are not limited to, semiconductor wafers. Substrates may be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure, and / or bake the substrate surface. In addition to film treatment directly on the surface of the substrate itself, in the present disclosure, any of the disclosed film treatment steps may be performed on an underlayer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such underlayers as the context indicates. Thus, for example, when a layer or sub-layer is being deposited on a substrate surface, the exposed surface of the newly deposited layer may be described as the substrate surface.

[0014]

[0016] The method of one or more embodiments is a back-end-of-line (BEOL) integration scheme. In one or more embodiments, the substrate includes one or more of titanium nitride (TiN), tantalum nitride (TaN), silicon (Si), cobalt (Co), titanium (Ti), silicon dioxide (SiO2), copper (Cu), and a low-k dielectric material, such as Black Diamond. As used herein, the term "Black Diamond" refers to a low-k dielectric film manufactured by Applied Materials, Inc. As used herein, the term "low-k dielectric" refers to a material that has a low relative dielectric constant (k) compared to silicon dioxide (SiO2). In one or more embodiments, the low-k dielectric can be any acceptable material known to one of ordinary skill in the art. In one or more embodiments, the low-k dielectric is Black Diamond.

[0015]

[0017] Embodiments of the present disclosure relate to methods for forming graphene hardmask films. Further embodiments of the present disclosure relate to methods for improving graphene deposition processes. Some embodiments of the present disclosure advantageously provide methods for forming graphene hardmask films at lower temperatures. Some embodiments of the present disclosure advantageously provide methods for forming graphene hardmask films of a given thickness at lower temperatures. Some embodiments of the present disclosure advantageously provide methods for forming graphene hardmask films having lower resistance.

[0016]

[0018] According to one or more embodiments, the method uses a chemical vapor deposition (CVD) process. As used herein, "chemical vapor deposition" refers to a process in which a substrate surface is exposed to precursors and / or co-reagents simultaneously or substantially simultaneously. As used herein, "substantially simultaneously" refers to either co-flow or where there is an overlap for the majority of the exposure of the precursors.

[0017]

[0019] According to one or more embodiments, the method uses chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes. In such embodiments, the substrate surface is exposed to the precursors (or reactive gases) sequentially or substantially sequentially. As used throughout this specification, "substantially sequential" means that the majority of the duration of the precursor exposure does not overlap with the exposure to the co-reagent, although there may be some overlap. In this specification and the accompanying claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gas species that can react with the substrate surface.

[0018]

[0020] As used herein, "atomic layer deposition" or "cyclic deposition" refers to the sequential exposure of two or more reactive compounds to deposit layers of material on a substrate surface. The substrate or a portion of the substrate is separately exposed to two or more reactive compounds that are introduced into a reaction zone of a processing chamber. In a time-domain ALD process, the exposure to each reactive compound is separated by a time delay so that each compound can deposit and / or react on the substrate surface and then be purged from the processing chamber. These reactive compounds are said to be sequentially exposed to the substrate. In a spatial ALD process, different portions of the substrate surface, or materials on the substrate surface, are simultaneously exposed to two or more reactive compounds such that any given point on the substrate is not substantially exposed to multiple reactive compounds at the same time. As used herein and in the appended claims, the term "substantially" as used in this respect means that, as will be understood by those skilled in the art, a small portion of the substrate may be exposed to multiple reactive gases at the same time due to diffusion, and simultaneous exposure is not intended.

[0019]

[0021] In one embodiment of a time-domain ALD process, a first reactive gas (i.e., a first precursor or compound A, e.g., an aromatic precursor) is pulsed into the reaction zone followed by a first time delay. Then, a second precursor or compound B (e.g., an oxidizer) is pulsed into the reaction zone followed by a second delay. During each time delay, a purge gas, such as argon, is introduced into the process chamber to purge or otherwise remove any residual reactive compounds or reaction by-products from the reaction zone. Alternatively, the purge gas may flow continuously throughout the deposition process such that only the purge gas flows during the time delay between pulses of reactive compounds. The reactive compounds are pulsed alternately until a desired film or film thickness is formed on the substrate surface. In either case, the ALD process of pulsing compound A, purge gas, compound B, and purge gas is a cycle. The cycle may start with either compound A or compound B and continue in each order of the cycle until a film having a predetermined thickness is achieved.

[0020]

[0022] In an embodiment of a spatial ALD process, a first reactive gas and a second reactive gas (e.g., nitrogen gas) are simultaneously supplied to a reaction zone but separated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas supply such that any given point on the substrate is exposed to the first reactive gas and the second reactive gas.

[0021]

[0023] As used herein, "pulse" or "dose" is intended to refer to an amount of source gas that is intermittently or non-continuously introduced into a processing chamber. The amount of a particular compound in each pulse may vary over time, depending on the duration of the pulse. A particular process gas may include a single compound or a mixture / combination of two or more compounds, such as the process gases described below.

[0022]

[0024] The duration of each pulse / dose can be varied and can be adjusted, for example, to accommodate the spatial volume of the processing chamber and the capacity of the vacuum system connected to the processing chamber. In addition, the dose time of the process gas can vary depending on the flow rate of the process gas, the temperature of the process gas, the type of control valve, the type of processing chamber used, and the ability of the components of the process gas to adsorb on the substrate surface. The dose time can also vary based on the type of layer being formed and the geometry of the device being formed. The dose time should be long enough to provide a sufficient amount of compound to adsorb / chemisorb on substantially the entire surface of the substrate and form a layer of the process gas component thereon.

[0023]

[0025] According to one or more embodiments, graphene can be grown by chemical vapor deposition and / or atomic layer deposition for many applications. One or more embodiments of the present disclosure advantageously provide a process of chemical vapor deposition for forming a graphene hardmask film. As used herein and in the appended claims, the term "graphene hardmask film" refers to a film comprising graphene. Graphene is an allotrope of carbon in the form of a single layer of atoms in a two-dimensional hexagonal lattice with one atom forming each vertex. It can be considered as the ultimate case of an infinitely large family of aromatic molecules, i.e., flat polycyclic aromatic hydrocarbons.

[0024]

[0026] Figure 1 illustrates a process flow diagram of a method according to one or more embodiments. The method illustrated in Figure 1 represents a chemical vapor deposition (CVD) process, where reactive gases are mixed in a processing chamber to allow for gas phase reaction of the reactive gases and deposition of a thin film. In some embodiments, the method illustrated in Figure 1 represents an atomic layer deposition (ALD) process, where a substrate or substrate surface is sequentially exposed to reactive gases in a manner that prevents or minimizes gas phase reaction of the reactive gases.

[0025]

[0027] FIG. 1 illustrates a flow diagram of a method 100 for depositing a film according to one or more embodiments of the present disclosure. With reference to FIG. 1, the method 100 includes a deposition cycle 110. The method 100 begins by preparing a substrate to be processed in step 102. In some embodiments, the method includes a chemical vapor deposition (CVD) process in which reactive gases are mixed in a processing chamber to enable gas-phase reaction of the reactive gases and deposition of a hardmask film on the substrate. In a CVD reaction, the substrate (or substrate surface) can be exposed to a gas mixture of precursors and reactants to deposit a graphene hardmask film having a predetermined thickness. In a CVD reaction, the graphene hardmask film can be deposited in a single exposure to the reactive gas mixture, or in multiple exposures to the reactive gas mixture with purges in between. In some embodiments, the method 100 represents an atomic layer deposition (ALD) process in which the substrate or substrate surface is exposed to reactive gases sequentially to prevent or minimize gas-phase reaction of the reactive gases.

[0026]

[0028] In some embodiments, preparing the substrate 102 includes a pretreatment step. The pretreatment can be any suitable pretreatment known to one of skill in the art. Suitable pretreatments include, but are not limited to, preheating, cleaning, soaking, native oxide removal, or deposition of an adhesion layer (e.g., titanium nitride (TiN), tantalum nitride (TaN), etc.).

[0027]

[0029] In one or more embodiments, the substrate is cleaned. Cleaning may be performed by any suitable technique known to those skilled in the art, including, but not limited to, an isopropyl alcohol (IPA) clean, standard cleans known to those skilled in the art including standard clean 1 (SC1) and standard clean 2 (SC2), gas phase cleans such as automated process control (APC) cleans, e-APC cleans, etc. After the substrate is cleaned, it is loaded into a processing chamber.

[0028]

[0030] In deposition 110, a process is performed to deposit a graphene hardmask film on a substrate (or substrate surface). The deposition process may include one or more steps to form a hardmask on the substrate. In step 112, the substrate (or substrate surface) is exposed to an aromatic precursor to deposit a graphene hardmask film on the substrate (or substrate surface).

[0029]

[0031] In deposition 110, a process cycle may be performed to deposit a graphene hardmask film on a substrate (or substrate surface). The deposition process may include one or more steps to form a hardmask film on the substrate. In step 112, the substrate (or substrate surface) is exposed to an aromatic precursor to deposit a graphene hardmask film on the substrate (or substrate surface). The aromatic precursor may be any suitable aromatic compound that can react with the substrate surface (i.e., adsorb or chemisorb onto the substrate surface) to leave an aromatic species on the substrate surface.

[0030]

[0032] The substrate is then loaded into a process chamber along with one or more precursors and the substrate is exposed to the precursors in step 112. In some embodiments, the precursors include aromatic precursors. Aromatic precursors include at least one aromatic ring.

[0031]

[0033] As used herein, in one or more embodiments, the term "aromatic precursor" refers to a precursor that is aromatic. As recognized by those skilled in the art, aromaticity is a property of a cyclic (ring-shaped), planar (flat) structure with rings of resonance bonds that provide increased stability compared to other geometries or bond arrangements with the same set of atoms. Aromatic molecules are very stable and do not easily break down to react with other substances. Aromaticity refers to a conjugated system that is often made of alternating single and double bonds in the ring. This configuration allows the electrons in the pi system of the molecule to be delocalized around the ring, increasing the stability of the molecule.

[0032]

[0034] In one or more embodiments, the aromatic precursor can include any aromatic precursor known to those skilled in the art. In some embodiments, the aromatic precursor includes one or more of benzene, substituted benzene, naphthalene, substituted naphthalene, anthracene, and substituted anthracene. In one or more embodiments, the aromatic precursor can be substituted with one or more alkyl groups, one or more alkoxy groups, one or more vinyl groups, one or more silane groups, one or more amine groups, or one or more halides.

[0033]

[0035] Unless otherwise stated, the terms "lower alkyl," "alkyl," or "alk" as used herein alone or as part of another group include both straight and branched chain hydrocarbons containing from 1 to 20 carbons in the normal chain, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, and the various branched chain isomers thereof. Such groups may optionally contain from 1 to 4 substituents.

[0034]

[0036] As used herein, the term "alkoxy" includes any of the above alkyl groups attached to an oxygen atom.

[0035]

[0037] As used herein, the term "vinyl" or "vinyl-containing" refers to a group that contains the vinyl group (-CH=CH2).

[0036]

[0038] As used herein, the term "amine" refers to any organic compound containing at least one basic nitrogen atom, such as, for example, NR', where R' is independently selected from hydrogen (H) or alkyl.

[0037]

[0039] As used herein, the term "silane" refers to the compound SiR'3, where R' is independently selected from hydrogen (H) or alkyl.

[0038]

[0040] As used herein, the term "halide" refers to a biphasic compound, one part of which is a halogen atom and the other part of which is an element or radical that is less electronegative than the halogen, creating a fluoride, chloride, bromide, iodide, or astatide compound. A halide ion is a negatively charged halogen atom. As known to those skilled in the art, halide anions include fluoride (F-), chloride (Cl-), bromide (Br-), iodide (I-), and astatide (At-).

[0039]

[0041] In one or more embodiments, the aromatic precursor comprises a small aromatic molecule having a temperature-sensitive functional group. In one or more specific embodiments, the aromatic precursor is selected from one or more of naphthalene, 2,6-dibromonaphthalene, trimethyl 1,3,5-benzenetricarboxylate, 9,10-dibromoanthracene, benzoic acid, 2,6-ditert-butylnaphthalene, 1,3,5-trimethoxybenzene, and hexabromobenzene.

[0040]

[0042] The substrate can be any substrate known to those skilled in the art. In one or more embodiments, the substrate comprises one or more of titanium nitride (TiN), tantalum nitride (TaN), silicon (Si), cobalt (Co), titanium (Ti), silicon dioxide (SiO2), copper (Cu), and low-k dielectric materials, such as Black Diamond.

[0041]

[0043] In step 114, the process chamber is purged. Purging (i.e., creating a vacuum) can be accomplished using any suitable gas that is non-reactive with the substrate, the film on the substrate, and / or the process chamber walls. Suitable purge gases include, but are not limited to, N2, He, and Ar. A purge gas can be used to purge the aromatic precursor and / or oxidant from the process chamber. In some embodiments, the same purge gas is used for each purge step. In other embodiments, different purge gases are used for the various purge steps. In one or more embodiments, the purge pressure is in the range of 0.1 mTorr to about 100 Torr, including in the range of about 0.5 mTorr to about 50 Torr and in the range of about 1 mTorr to about 100 Torr.

[0042]

[0044] In step 114, the process chamber is purged to remove unreacted aromatic precursors, reaction products and by-products. When used in this manner, the term "processing chamber" also includes the portion of the process chamber adjacent to the substrate surface, without encompassing the complete interior space of the process chamber. For example, the tellurium precursor is purged from the portion of the process chamber adjacent to the substrate surface by any suitable technique, including, but not limited to, moving the substrate through a gas curtain to a portion or sector of the process chamber that is free or substantially free of aromatic precursors in a spatially separated sector of the process chamber. In some embodiments, purging the process chamber includes flowing a purge gas over the substrate. In some embodiments, the portion of the process chamber refers to a micro- or small-volume processing station within the process chamber. The term "adjacent" referring to the substrate surface refers to a physical space close to the surface of the substrate that can provide sufficient space for surface reactions (e.g., precursor adsorption) to occur.

[0043] In step 116, the substrate (or substrate surface) is heated to a temperature of about 150° C. to about 700° C. In one or more embodiments, the chamber temperature is less than about 500° C. In other embodiments, the deposition process is carried out at a temperature in the range of about 0° C. to about 500° C., including about 25° C., about 50° C., about 75° C., about 100° C., about 125° C., about 150° C., about 175° C., about 200° C., about 225° C., about 250° C., about 275° C., about 300° C., about 325° C., about 350° C., about 375° C., about 400° C., about 425° C., about 450° C., about 475° C., and about 500° C.

[0044]

[0045] In one or more embodiments, the functional groups of the aromatic precursor decompose and activate the molecules toward 2D polymerization to form a graphene hardmask film on the substrate. In other embodiments, reactants may be introduced to the process chamber in step 116. The reactants may react with aromatic-containing species on the substrate surface to form a graphene hardmask film. In some embodiments, the reactants include a reducing agent. In one or more embodiments, the reducing agent may include any reducing agent known to one of skill in the art. In other embodiments, the reactants include an oxidizing agent. In one or more embodiments, the oxidizing agent may include any oxidizing agent known to one of skill in the art. In further embodiments, the reactants include one or more of an oxidizing agent and a reducing agent.

[0045]

[0046] In step 116, the temperature of the substrate in the process chamber is brought to a temperature in the range of about 150° C. to about 700° C., including temperatures of about 150° C., about 200° C., about 250° C., about 300° C., about 350° C., about 400° C., about 450° C., about 500° C., about 550° C., about 600° C., about 650° C., and about 700° C. In one or more embodiments, a hardmask film is deposited on the substrate. During deposition, functional groups on the aromatic precursor decompose, activating the molecules toward 2D polymerization and forming a graphene hardmask film on the substrate.

[0046]

[0047] In step 118, the process chamber is cooled and purged, and the substrate can be removed from the process chamber. Purging (i.e., creating a vacuum) can be accomplished with any suitable gas that is non-reactive with the substrate, the film on the substrate, and / or the process chamber walls. Suitable purge gases include, but are not limited to, N2, He, and Ar. A purge gas can be used to purge aromatic precursors and / or oxidizers from the process chamber. In some embodiments, the same purge gas is used for each purge step. In other embodiments, different purge gases are used for the various purge steps.

[0047]

[0048] The processing chamber is purged in step 118. Purging the processing chamber in step 118 may be the same process as the purging in step 114 or may be a different process. Purging the processing chamber, a portion of the processing chamber, an area adjacent to the substrate surface, etc., removes unreacted reactants, reaction products, and by-products from the area adjacent to the substrate surface.

[0048]

[0049] The deposition cycles 110 may be performed until a predetermined thickness of graphene is formed. In step 120, the thickness of the formed graphene hardmask film is evaluated to determine if the predetermined thickness has been reached. If not, the method 100 returns to step 112 for further formation. If so, the method 100 moves to an optional post-processing step in step 130 or the method 100 ends.

[0049]

[0050] In decision 120, the thickness of the deposited graphene hardmask film or the number of aromatic precursor cycles is considered. If the deposited hardmask film reaches a predetermined thickness or if a predetermined number of process cycles have been performed, the method 100 moves to an optional post-treatment step 130. If the deposited hardmask film thickness or the number of process cycles has not reached a predetermined threshold, the method 100 returns to step 110 and continues by again exposing the substrate surface to the aromatic precursor in step 112.

[0050]

[0051] The optional post-treatment step 130 can be, for example, a process to modify the film properties (e.g., annealing) or a further film deposition process to grow an additional film (e.g., additional ALD or CVD process). In some embodiments, the optional post-treatment step 130 can be a process to modify the properties of the deposited hardmask film. In some embodiments, the optional post-treatment step 130 includes annealing the deposited film. In some embodiments, the annealing is performed at a temperature in the range of about 300° C., 400° C., 500° C., 600° C., 700° C., 800° C., 900° C., or 1000° C. The annealing environment in some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N2), argon (Ar)), or a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)), or an oxidizing agent (e.g., but not limited to, oxygen (O2), ozone (O3), or a peroxide). The annealing can be performed for any suitable length of time. In some embodiments, the film is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the deposited hardmask film increases the density, decreases the resistance, and / or increases the purity of the film.

[0051]

[0052] Method 100 can be performed at any suitable temperature, depending on, for example, the aromatic precursor, reactants, or heat balance of the device. In some embodiments, the exposure to the aromatic precursor (step 112) and the exposure to the reactants (step 116) are performed at the same temperature. In some embodiments, the substrate is maintained at a temperature in the range of about 150° C. to about 700° C., or in the range of about 150° C. to about 650° C., or in the range of about 150° C. to about 500° C. The temperature of the substrate surface can be controlled during the formation of the graphene hardmask film. In some embodiments, the substrate surface is maintained at a temperature of about 700° C. or less, about 650° C. or less, about 600° C. or less, about 500° C. or less, about 400° C. or less, about 300° C. or less, about 200° C. or less, about 100° C. or less, about 50° C. or less, or about 25° C. or less.

[0052]

[0053] Typically, CVD processes for forming graphene hardmask films are carried out at temperatures above 1000° C. One or more embodiments provide methods for depositing graphene hardmask films at lower temperatures, i.e., less than about 700° C., or less than about 600° C., or less than about 500° C., or less than about 400° C. Without intending to be bound by theory, it is believed that these lower temperatures are more compatible with the thermal budget of electronic devices during fabrication.

[0053]

[0054] In some embodiments, the graphene hardmask films formed by the disclosed methods comprise about 1 or less, about 2 or less, about 5 or less, about 10 or less, about 20 or less, about 25 or less, or about 30 or less monolayers of graphene. In some embodiments, the graphene hardmask films formed by the disclosed methods comprise in the range of about 0.5 to about 25 monolayers of graphene, or in the range of about 0.5 to about 10 monolayers, or in the range of about 1 to about 5 monolayers, or in the range of about 5 to about 10 monolayers. In some embodiments, the graphene hardmask films formed by the disclosed methods have a thickness of about 3 Å or less, about 5 Å or less, about 10 Å or less, about 15 Å or less, about 20 Å or less, about 25 Å or less, about 30 Å or less, about 40 Å or less, or about 50 Å or less.

[0054]

[0055] In some embodiments, the method 100 can be performed in a relatively short time. In some embodiments, the graphene hardmask film is formed in a period of about 15 minutes or less, about 10 minutes or less, about 5 minutes or less, about 2 minutes or less, or about 1 minute or less. In other embodiments, the graphene hardmask film is formed in a period of time ranging from about 1 hour to about 48 hours.

[0055]

[0056] In some embodiments, the improved substrate surface quality results in increased smoothness, in some embodiments, the improved substrate surface quality results in reduced hydrogen concentration, in some embodiments, the improved substrate surface quality results in reduced contamination.

[0056]

[0057] In some implementations, improved deposition parameters increase film thickness. In some implementations, improved deposition parameters decrease film resistance. In some implementations, improved deposition parameters increase uniformity. These improvements are relative to graphene hardmask films deposited with similar process parameters (e.g., reactants, temperature, plasma power, deposition time).

[0057]

[0058] With reference to Figure 2, one or more embodiments of the present disclosure are directed to a method 200 of depositing a graphene hardmask film. The method shown in Figure 2 represents a plasma-enhanced process in which reactive gases are mixed within a processing chamber to enable gas-phase reaction of the reactive gases and deposition of a thin film.

[0058]

[0059] In some embodiments, the method 200 includes a pretreatment step 205. The pretreatment can be any suitable pretreatment known to one of skill in the art. Suitable pretreatments include, but are not limited to, preheating, cleaning, soaking, native oxide removal, or deposition of a layer (e.g., titanium nitride (TiN)).

[0059]

[0060] In a deposition step 210, a process is performed to deposit a graphene hardmask film on a substrate (or substrate surface). The deposition process may include one or more steps to form a graphene hardmask film on the substrate. In step 212, the substrate (or substrate surface) is exposed to an aromatic precursor to deposit a film on the substrate (or substrate surface).

[0060]

[0061] In one or more embodiments, the aromatic precursor can include any aromatic precursor known to those skilled in the art. In some embodiments, the aromatic precursor includes one or more of benzene, substituted benzene, naphthalene, substituted naphthalene, anthracene, and substituted anthracene. In one or more embodiments, the aromatic precursor can be substituted with one or more alkyl groups, one or more alkoxy groups, one or more vinyl groups, one or more silane groups, one or more amine groups, or one or more halides.

[0061]

[0062] In one or more embodiments, the aromatic precursor comprises a small aromatic molecule having a temperature-sensitive functional group. In one or more specific embodiments, the aromatic precursor is selected from one or more of naphthalene, 2,6-dibromonaphthalene, trimethyl 1,3,5-benzenetricarboxylate, 9,10-dibromoanthracene, benzoic acid, 2,6-ditert-butylnaphthalene, 1,3,5-trimethoxybenzene, and hexabromobenzene.

[0062]

[0063] The substrate can be any substrate known to those skilled in the art. In one or more embodiments, the substrate comprises one or more of titanium nitride (TiN), silicon (Si), cobalt (Co), titanium (Ti), silicon dioxide (SiO2), copper (Cu), and low-k dielectric materials, such as Black Diamond.

[0063]

[0064] In step 214, the process chamber is purged to remove unreacted precursors, reaction products, and by-products.

[0064]

[0065] In one or more embodiments, the deposition process includes a remote plasma enhanced chemical vapor deposition (PECVD) process. After forming the graphene hardmask film on the substrate, the substrate is exposed to a plasma in step 216. In one or more embodiments, exposing the graphene hardmask film to a plasma in the processing chamber improves film properties. For example, in one or more embodiments, the wet etch rate is improved, indicating that the graphene hardmask film is densified by the plasma treatment. In one or more embodiments, the plasma includes one or more of nitrogen (N2), argon (Ar), helium (He), hydrogen (H2), carbon monoxide (CO), or carbon dioxide (CO2). In some embodiments, the plasma is a remote plasma. In other embodiments, the plasma is a direct current plasma.

[0065]

[0066] In one or more embodiments, the plasma can be generated remotely or in the process chamber. In one or more embodiments, the plasma is an inductively coupled plasma (ICP) or a conductively coupled plasma (CCP). Any suitable power can be used, depending on, for example, the reactants, or other process conditions. In some embodiments, the plasma is generated with a plasma power in the range of about 10 W to about 3000 W. In some embodiments, the plasma is generated with a plasma power of about 3000 W or less, about 2000 W or less, about 1000 W or less, about 500 W or less, or about 250 W or less.

[0066]

[0067] In step 218, the processing chamber is optionally purged after exposure to the plasma. Purging the processing chamber in step 218 may be the same process as purging in step 214 or may be a different process. Purging the processing chamber, a portion of the processing chamber, an area adjacent to the substrate surface, etc., removes plasma, reaction products, and by-products from the area adjacent to the substrate surface.

[0067]

[0068] In decision step 220, in one or more embodiments, the thickness of the deposited film or the number of precursor and reactant cycles is considered. In one or more embodiments, if the deposited film reaches a predetermined thickness or if a predetermined number of process cycles have been performed, the method 200 moves to a post-treatment step 230. In one or more embodiments, if the thickness of the deposited film or the number of process cycles has not reached a predetermined threshold, the method 200 returns to the deposition step 210 and continues by again exposing the substrate surface to an aromatic precursor in step 212.

[0068]

[0069] In one or more embodiments, the optional post-treatment step 230 includes, for example, a process to modify the film properties (e.g., annealing) or a further film deposition process to grow additional films (e.g., additional ALD or CVD processes). In some embodiments, the post-treatment step 230 is a process that modifies the properties of the deposited film. In some embodiments, the post-treatment step 230 includes annealing the deposited film. In some embodiments, the annealing is performed at a temperature in the range of about 300° C., 400° C., 500° C., 600° C., 700° C., 800° C., 900° C., or 1000° C. The annealing environment in some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N2), argon (Ar)), or a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)), or an oxidizing agent (e.g., but not limited to, oxygen (O2), ozone (O3), or a peroxide). In one or more embodiments, the annealing is performed for any suitable length of time. In some embodiments, the graphene hardmask film is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the deposited film increases the density, decreases the resistance, and / or increases the purity of the film.

[0069]

[0070] In one or more embodiments, the method 200 can be performed at any suitable temperature depending, for example, on the precursors, reactants, or heat budget of the device, hi some embodiments, the substrate is maintained at a temperature ranging from about 0° C. to about 500° C.

[0070]

[0071] In one or more embodiments, the substrate (or substrate surface) is exposed to precursors in a PE-CVD reaction, in which the substrate (or substrate surface) is exposed to a gas mixture of precursors and, optionally, reactants to deposit a graphene hardmask film having a predetermined thickness. In a PE-CVD reaction, the graphene hardmask film can be deposited in a single exposure to the reactive gas mixture, or in multiple exposures to the reactive gas mixture with intervening purges.

[0071]

[0072] In one or more embodiments, the deposition process is carried out in the processing space at a pressure ranging from about 0.1 mTorr to 100 Torr, including pressures of about 0.1 mTorr, about 10 mTorr, about 100 mTorr, about 1000 mTorr, about 5000 mTorr, about 1 Torr, about 20 Torr, about 30 Torr, about 40 Torr, about 50 Torr, about 60 Torr, about 70 Torr, about 80 Torr, about 90 Torr, and about 100 Torr.

[0072]

[0073] The precursor-containing gas mixture may further include one or more diluent gases selected from helium (He), argon (Ar), xenon (Xe), nitrogen (N2), or hydrogen (H2). The diluent gas in some embodiments includes a compound that is an inert gas with respect to the reactants and substrate materials.

[0073]

[0074] The plasma (e.g., capacitively coupled plasma) can be formed from either top and bottom electrodes or side electrodes. The electrodes can be formed from a single powered electrode, dual powered electrodes, or more electrodes with multiple frequencies (e.g., but not limited to, 350 KHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, and 100 MHz) and used alternately or simultaneously in a CVD system with any or all of the reactant gases listed herein to deposit thin films of dielectric materials. In some embodiments, the plasma is a capacitively coupled plasma (CCP). In some embodiments, the plasma is an inductively coupled plasma (ICP). In some embodiments, the plasma is a microwave plasma.

[0074]

[0075] In one or more embodiments, the deposition step 210 can be repeated to form a graphene hardmask film having a predetermined thickness. In some embodiments, the deposition step 210 is repeated to provide a graphene hardmask film having a thickness greater than about 0.1 nm, or in a range of about 0.1 nm to about 1000 nm, including about 10 nm to about 500 nm, about 10 nm to about 100 nm, about 5 nm to about 50 nm, about 10 nm to about 50 nm, or about 20 nm to about 30 nm.

[0075]

[0076] In some embodiments, the graphene hardmask film is deposited in a chamber with the substrate pedestal maintained at less than about 700° C., or less than about 600° C., or less than about 500° C., or less than about 400° C., or less than about 300° C., and the pressure maintained at about 5 Torr, using a plasma (i.e., a direct current plasma) generated at the wafer level by applying a bias of about 200 Watts to the electrostatic chuck. In some embodiments, an additional RF power of about 1000 Watts at 2 MHz is also supplied to the electrostatic chuck to generate a dual bias plasma at the wafer level.

[0076]

[0077] Generally, according to one or more embodiments, the following exemplary deposition process parameters may be used to form a deposited film: In one or more embodiments, the wafer temperature may range from about 150° C. to about 700° C., or from about 150° C. to about 500° C. The chamber pressure may range from about 0.1 mTorr to about 100 Torr. The flow rate of the precursor-containing gas mixture may range from about 10 sccm to about 1,000 sccm. The flow rates of the dilution gases may individually range from about 50 sccm to about 50,000 sccm.

[0077]

[0078] In one or more embodiments, the graphene hardmask film may be deposited to a thickness in the range of about 5 A to about 60,000 A (including in the range of about 300 A to about 10,000 A, about 2000 A to about 3000 A, or about 5 A to about 200 A).

[0078]

[0079] According to one or more embodiments, before and / or after the formation of the layer, the substrate is subjected to processing. This processing can be performed in the same chamber or in one or more separate processing chambers. In one or more embodiments, the substrate is then transferred to another processing chamber for further processing. The substrate can be transferred directly from the physical vapor deposition chamber to a separate processing chamber, or the substrate can be transferred from the physical vapor deposition chamber to one or more transfer chambers and then to a separate processing chamber. Thus, the processing apparatus can include multiple chambers in communication with a transfer station. This type of apparatus can be referred to as a "cluster tool" or a "clustered system", etc.

[0079]

[0080] Generally, a cluster tool is a modular system with multiple chambers that perform various functions including center detection and orientation, degassing, annealing, deposition and / or etching of the substrate. According to one or more embodiments, the cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber can house a robot that can transfer the substrate back and forth between the processing chambers and the load lock chamber. The transfer chamber is typically maintained under vacuum and provides an intermediate stage for transferring the substrate from one chamber to another and / or to the load lock chamber positioned at the front end of the cluster tool. Two well-known cluster tools that may be adapted for the present invention are the Centura® and Endura®, both available from Applied Materials, Inc., Santa Clara, Calif. However, the exact arrangement and combination of chambers may be altered for the purposes of performing the specific steps of the processes described herein. Other processing chambers that may be used include, but are not limited to, cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitridation, degassing, alignment, hydroxylation, and other substrate treatments. By performing the process in a chamber on a cluster tool, surface contamination of the substrate from atmospheric impurities can be avoided without oxidation prior to depositing the next film.

[0080]

[0081] According to one or more embodiments, the substrate is continuously under vacuum or "load-lock" conditions and is not exposed to ambient air when it is transferred from one chamber to the next. The transfer chamber is thus under vacuum and is "pumped down" to vacuum pressure. An inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants. According to one or more embodiments, a purge gas is injected at the outlet of the deposition chamber to prevent the reactants from transferring from the deposition chamber to the transfer chamber and / or to the additional processing chamber. In this way, a flow of inert gas forms a curtain at the outlet of the chamber.

[0081]

[0082] Substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed in a continuous manner, similar to a conveyor system, where multiple substrates are loaded individually into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The geometry of the chamber and associated conveyor system can form a linear or curved path. Additionally, the processing chamber can be a carousel, where multiple substrates move about a central axis and are exposed to deposition, etching, annealing, cleaning, etc. throughout the path of the carousel.

[0082]

[0083] During processing, the substrate may be heated or cooled. Such heating or cooling may be accomplished by any suitable means, including, but not limited to, changing the temperature of the substrate support and flowing a heated or cooled gas over the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas used (reactive or inert) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned in the chamber adjacent to the substrate surface to change the substrate temperature by convection.

[0083]

[0084] The substrate may also be stationary or rotated during processing. A rotating substrate may be rotated continuously or in non-continuous steps. For example, the substrate may be rotated throughout the entire process or may be rotated in small increments between exposures to various reactive or purge gases. Rotating the substrate (continuously or in steps) during processing may help provide a more uniform deposition or etching, for example by minimizing the effects of local variability in gas flow geometry.

[0084]

[0085] An additional embodiment of the present disclosure is directed to a processing tool 900 for forming devices and performing the described methods, as shown in Figure 3. The cluster tool 900 includes at least one central transfer station 921, 931 having multiple sides. Robots 925, 935 are disposed within the central transfer station 921, 931 and configured to move a robot blade and a wafer to each of the multiple sides.

[0085]

[0086] The cluster tool 900 includes multiple processing chambers, also referred to as process stations, 902, 904, 906, 908, 910, 912, 914, 916, and 918 connected to a central transfer station. The various processing chambers provide separate processing regions that are separate from adjacent processing stations. The processing chambers may be any suitable chambers, including, but not limited to, physical vapor deposition chambers, UV curing chambers, ICP chambers, etch chambers, etc. The particular arrangement of processing chambers and components may vary depending on the cluster tool and should not be construed as limiting the scope of the present disclosure.

[0086]

[0087] In some embodiments, the cluster tool 900 includes at least one physical vapor deposition chamber. In some embodiments, the cluster tool 900 includes a physical vapor deposition chamber having a remote plasma source connected to a central transfer station.

[0087]

[0088] 3, a factory interface 950 is connected to the front of the cluster tool 900. The factory interface 950 includes a loading chamber 954 and an unloading chamber 956 on the front side 951 of the factory interface 950. Although the loading chamber 954 is shown on the left and the unloading chamber 956 is shown on the right, one of ordinary skill in the art will appreciate that this is merely representative of one possible configuration.

[0088]

[0089] The size and shape of the loading chamber 954 and the unloading chamber 956 can vary depending on, for example, the substrate being processed in the cluster tool 900. In the illustrated embodiment, the loading chamber 954 and the unloading chamber 956 are sized to hold a wafer cassette with multiple wafers disposed within the cassette.

[0089]

[0090] The robot 952 is in the factory interface 950 and can move between a loading chamber 954 and an unloading chamber 956. The robot 952 can transfer wafers from a cassette in the loading chamber 954 to a load lock chamber 960 through the factory interface 950. The robot 952 can also transfer wafers from the load lock chamber 962 to a cassette in the unloading chamber 956 through the factory interface 950. As will be appreciated by those skilled in the art, the factory interface 950 can include multiple robots 952. For example, the factory interface 950 can include a first robot that transfers wafers between the loading chamber 954 and the load lock chamber 960 and a second robot that transfers wafers between the load lock chamber 962 and the unloading chamber 956.

[0090]

[0091] The illustrated cluster tool 900 has a first section 920 and a second section 930. The first section 920 is connected to a factory interface 950 through load lock chambers 960, 962. The first section 920 includes a first transfer chamber 921 with at least one robot 925 disposed therein. The robot 925 is also referred to as a robotic wafer transport mechanism. The first transfer chamber 921 is centrally located relative to the load lock chambers 960, 962, the processing chambers 902, 904, 916, 918, and the buffer chambers 922, 924. The robot 925 in some embodiments is a multi-arm robot capable of independently moving multiple wafers at a time. In some embodiments, the first transfer chamber 921 includes multiple robotic wafer transfer mechanisms. The robot 925 in the first transfer chamber 921 is configured to move wafers between chambers around the first transfer chamber 921. Individual wafers are supported on a wafer transport blade located at the distal end of the first robotic mechanism.

[0091]

[0092] After processing the wafer in the first section 920, the wafer may pass through a pass-through chamber to the second section 930. For example, the chambers 922, 924 may be unidirectional or bidirectional pass-through chambers. The pass-through chambers 922, 924 may be used, for example, to cryo-cool the wafer before processing in the second section 930 or to allow for wafer cooling or post-processing before returning to the first section 920.

[0092]

[0093] The system controller 990 is in communication with the first robot 925, the second robot 935, the first plurality of processing chambers 902, 904, 916, 918, and the second plurality of processing chambers 906, 908, 910, 912, 914. The system controller 990 may be any suitable component capable of controlling the processing chambers and robots. For example, the system controller 990 may be a computer including a central processing unit (CPU) 992, memory 994, input / output (I / O) 996, and support circuits 998. The controller 990 may control the processing tool 900 directly or through computers (or controllers) associated with particular processing chambers and / or support system components.

[0093]

[0094] In one or more embodiments, the controller 990 can be one of any form of general-purpose computer processor that can be used in an industrial environment to control various chambers and sub-processors. The memory 994 or computer readable medium of the controller 990 can be one or more of readily available memory, such as non-transitory memory (e.g., random access memory (RAM)), read-only memory (ROM), a floppy disk, a hard disk, an optical storage medium (e.g., a compact disk or digital video disk), a flash drive, or any other form of digital storage, local or remote. The memory 994 can hold a set of instructions operable by the processor (CPU 992) to control parameters and components of the processing tool 900.

[0094]

[0095] The support circuits 998 are connected to the CPU 992 for supporting the processor in a conventional manner. These circuits include cache, power supplies, clock circuits, input / output circuits and subsystems, etc. One or more processes may be stored in the memory 994 as software routines that, when executed or invoked by the processor, cause the processor to control the operation of the processing tool 900 or individual processing units in the manner described herein. The software routines may also be stored and / or executed by a second CPU (not shown) located remote from the hardware controlled by the CPU 992.

[0095]

[0096] Some or all of the processes and methods of the present disclosure may also be implemented in hardware. Thus, the processes may be implemented in software and executed using a computer system, in hardware, for example as an application specific integrated circuit or other type of hardware implementation, or as a combination of software and hardware. The software routines, when executed by a processor, transform a general purpose computer into a special purpose computer (controller) that controls chamber operation so that processes are performed.

[0096]

[0097] In some embodiments, the controller 990 has one or more configurations for performing individual processes or sub-processes to perform a method. The controller 990 may be coupled to and configured to operate intermediate components to perform the functions of a method. For example, the controller 990 may be connected to and configured to control a physical vapor deposition chamber.

[0097]

[0098] The processes may generally be stored in the memory 994 of the system controller 990 as software routines that, when executed by a processor, cause the processing chamber to perform the processes of the present disclosure. The software routines may also be stored and / or executed by a second processor (not shown) located remotely from the hardware controlled by the processor. Some or all of the methods of the present disclosure may also be performed in hardware. Thus, the processes may be implemented in software and executed using a computer system, in hardware, for example as an application specific integrated circuit or other type of hardware implementation, or as a combination of software and hardware. The software routines, when executed by a processor, transform a general-purpose computer into a special-purpose computer (controller) that controls the chamber operation so that the processes are performed.

[0098]

[0099] In some embodiments, the system controller 990 is configured to control the physical vapor deposition chamber to deposit a film on the wafer at a temperature in the range of about 20° C. to about 400° C. and to control a remote plasma source to form a polysilazane film on the wafer.

[0099]

[0100] In one or more embodiments, the processing tool includes a central transfer station including a robot configured to move the wafer; a plurality of process stations, each process station connected to the central transfer station and providing a processing area isolated from the processing areas of adjacent process stations, including a physical vapor deposition chamber and a remote plasma source; a UV cure chamber; an ICP chamber; and a controller connected to the central transfer station and the plurality of process stations, the controller configured to activate the robot to move the wafer between the process stations and to control the process at each of the process stations.

[0100]

[0101] The use of "a" and "an," "the," and similar referents in the context of describing the materials and methods discussed herein (particularly in the context of the claims that follow) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of numerical ranges herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to better describe the materials and methods and does not limit the scope unless specifically claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0101]

[0102] Throughout this specification, references to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of phrases such as "in one or more embodiments," "a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0102]

[0103] Although the disclosure of this specification has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. 1. A method of forming a membrane, comprising: exposing the substrate to an aromatic precursor in a processing chamber; purging the aromatic precursor from the processing chamber; heating the substrate to a temperature less than 600° C. to polymerize the aromatic precursor and deposit a graphene hardmask film on the substrate; purging the processing chamber; Including, The method, wherein the aromatic precursor is selected from one or more of naphthalene, 2,6-dibromonaphthalene, trimethyl 1,3,5-benzenetricarboxylate, 9,10-dibromoanthracene, benzoic acid, 2,6-ditert-butylnaphthalene, 1,3,5-trimethoxybenzene, and hexabromobenzene.

2. 10. The method of claim 1, wherein the aromatic precursor comprises one or more of benzene, substituted benzene, naphthalene, substituted naphthalene, anthracene, and substituted anthracene.

3. The substrate may be made of titanium nitride (TiN), tantalum nitride (TaN), silicon (Si), cobalt (Co), titanium (Ti), silicon dioxide (SiO ２ 2. The method of claim 1, wherein the insulating layer comprises one or more of: copper (Cu); and a low-k dielectric material.

4. The method of claim 1, further comprising repeating the method to provide a graphene hardmask film having a thickness of 0.3 nm to 100 nm.

5. The method of claim 1 , further comprising exposing the substrate to a reactant.

6. The method of claim 5 , wherein the substrate is exposed to the aromatic precursor and the reactant simultaneously.

7. The method of claim 5 , wherein the substrate is exposed to the aromatic precursor and the reactant sequentially.

8. 16. A non-transitory computer readable medium comprising instructions, which when executed by a controller of a process chamber, cause the process chamber to: exposing a substrate to an aromatic precursor in the processing chamber; purging the aromatic precursor from the processing chamber; heating the substrate to a temperature less than 600° C. to polymerize the aromatic precursor and deposit a graphene hardmask film on the substrate; purging the processing chamber; Run the command, The non-transitory computer readable medium, wherein the aromatic precursor is selected from one or more of naphthalene, 2,6-dibromonaphthalene, trimethyl 1,3,5-benzenetricarboxylate, 9,10-dibromoanthracene, benzoic acid, 2,6-ditert-butylnaphthalene, 1,3,5-trimethoxybenzene, and hexabromobenzene.

9. A non-transitory computer-readable medium comprising instructions that, when executed by a controller of a process chamber, cause the process chamber to: exposing a substrate to an aromatic precursor in the processing chamber; purging the aromatic precursor from the processing chamber; heating the substrate to a temperature less than 600° C. to polymerize the aromatic precursor and deposit a graphene hardmask film on the substrate; purging the processing chamber; Run the command, The non-transitory computer readable medium, wherein the aromatic precursor comprises one or more of substituted benzene, naphthalene, substituted naphthalene, anthracene, and substituted anthracene.

10. The substrate may be made of titanium nitride (TiN), tantalum nitride (TaN), silicon (Si), cobalt (Co), titanium (Ti), silicon dioxide (SiO ２ 10. The non-transitory computer readable medium of claim 8 or 9, comprising one or more of: copper (Cu), copper (Cu), and a low-k dielectric material.

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