Hard masks and processes for hard mask formation by plasma chemical vapor deposition

Abstract

Embodiments of the present disclosure generally relate to hardmasks and processes for forming them by plasma-enhanced chemical vapor deposition (PECVD). In one embodiment, a process for forming a hardmask on a substrate is provided. The process includes introducing a substrate into a processing space of a PECVD chamber, the substrate being positioned on a substrate support, the substrate support including an electrostatic chuck, and flowing a process gas into the processing space in the PECVD chamber, the process gas including a carbon-containing gas. The process further includes generating an excited process gas from the process gas in the processing space under plasma conditions, electrostatically chucking the substrate to the substrate support, and, while the substrate is electrostatically chucked, depositing a first carbon-containing layer on the substrate and a second carbon-containing layer on the substrate to form a hardmask layer.

Description

Technical Field

[0001]

[0001] Embodiments of the present disclosure relate generally to a hard mask and a process for forming a hard mask by plasma chemical vapor deposition.

Background Art

[0002]

[0002] Carbon-based hard masks are typically employed as an etching-resistant mask in patterning and linewidth trimming applications, for example, due to the mechanical properties of the carbon-based hard mask. Carbon-based hard masks are typically manufactured by plasma enhanced chemical vapor deposition (PECVD). Conventionally, plasma conditions for forming such hard masks employ argon and / or helium alone. However, under plasma conditions, high-energy bombardment of nuclides such as argon and / or helium can damage the underlying dielectric material on which the hard mask is formed, particularly during substrate chucking. Damage to the underlying dielectric material can, as a result, lead to degradation of device performance.

[0003]

[0003] For example, there is a need for a new and improved process that reduces damage to the underlying layer during hard mask formation.

Summary of the Invention

[0004]

[0004] Embodiments of the present disclosure relate generally to a hard mask and a process for forming a hard mask by PECVD. The embodiments described herein reduce or eliminate damage to the underlying layer during hard mask formation and improve the adhesion between the hard mask and the substrate.

[0005]

[0005] In one embodiment, a process for forming a hard mask on a substrate is provided. The process includes introducing a substrate into the processing space of a PECVD chamber, wherein the substrate is placed on a substrate support, the substrate support includes an electrostatic chuck, and flowing a process gas into the processing space within the PECVD chamber, wherein the process gas includes a carbon-containing gas. The process further includes forming a hard mask layer by generating an excited process gas from the process gas in the processing space under plasma conditions, electrostatically chucking the substrate to the substrate support, depositing a first carbon-containing layer on the substrate while the substrate is electrostatically chucked, and depositing a second carbon-containing layer on the substrate.

[0006]

[0006] In another embodiment, a process for forming a hard mask on a substrate is provided. The process includes introducing the substrate into the processing space of a PECVD chamber, wherein the substrate is placed on a substrate support, the substrate support includes an electrostatic chuck, and flowing a process gas into the processing space within the PECVD chamber. The process gas includes a carbon-containing gas. In this case, the carbon-containing gas includes a carbon-containing compound, or the carbon-containing gas is produced from a carbon-containing compound. The carbon-containing compound is substituted or unsubstituted C1-C 40 Hydrocarbons, substituted or unsubstituted C6-C 20 Aromatic hydrocarbons, C1-C 40 The carbon-containing material is a halogenated hydrocarbon, or a combination thereof. The process further comprises forming a hard mask layer by generating an excited process gas from a process gas in a processing space under plasma conditions, electrostatically chucking a substrate to a substrate support, depositing a first carbon-containing layer on the substrate while the substrate is electrostatically chucked, and depositing a second carbon-containing layer on the substrate. While the first carbon-containing layer, the second carbon-containing layer, or both thereof are being deposited, the substrate is maintained at a temperature of about -40°C to about 40°C, and the pressure in the processing space is about 1 mTorr to about 20 mTorr, or a combination thereof.

[0007]

[0007] In another embodiment, a process for forming a hard mask on a substrate is provided. The process includes introducing the substrate into the processing space of a PECVD chamber, wherein the substrate is placed on a substrate support, the substrate support includes an electrostatic chuck, and flowing a process gas into the processing space within the PECVD chamber. The process gas includes a carbon-containing gas. In this case, the carbon-containing gas includes a carbon-containing compound, or the carbon-containing gas is produced from a carbon-containing compound. The carbon-containing compound is substituted or unsubstituted C1-C 20 The process includes generating an excited process gas from a process gas in a processing space under plasma conditions, wherein the plasma conditions include applying an RF bias power of about 200 W to about 5000 W to a substrate support; electrostatically chucking a substrate to the substrate support; depositing a first carbon-containing layer on the substrate while the substrate is electrostatically chucked; and forming a hard mask layer by depositing a second carbon-containing layer on the substrate. While the first carbon-containing layer, the second carbon-containing layer, or both thereof are being deposited, the substrate is maintained at a temperature of about -40°C to about 40°C, and the pressure in the processing space is about 1 mTorr to about 20 mTorr, or a combination thereof.

[0008]

[0008] To enable a detailed understanding of the features of the present disclosure described above, a more specific description of the present disclosure, which has been briefly summarized above, can be obtained by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings only show exemplary embodiments and should not be considered to limit the scope of the present disclosure, and other equally valid embodiments may also be permitted. [Brief explanation of the drawing]

[0009] [Figure 1]

[0009] This is a schematic side cross-sectional view of an exemplary processing chamber according to at least one embodiment of the present disclosure. [Figure 2A]

[0010] This is a schematic cross-sectional view of an exemplary substrate support according to at least one embodiment of the present disclosure. [Figure 2B]

[0011] This is an enlarged cross-sectional view of a portion of an exemplary substrate support shown in Figure 2A, according to at least one embodiment described in this disclosure. [Figure 3]

[0012] This flowchart shows selected operations of an exemplary method for processing a substrate according to one exemplary embodiment of the present disclosure. [Modes for carrying out the invention]

[0010]

[0013] For ease of understanding, the same reference numerals were used to indicate identical elements common to the drawings where possible. It is assumed that elements and features of one embodiment can be usefully incorporated into several other embodiments without additional description.

[0011]

[0014] Embodiments of this disclosure broadly relate to hard masks and processes for hard mask formation by PECVD. The inventors have found novel and improved processes and resulting hard mask structures that overcome one or more drawbacks of conventional methods for forming hard masks. For example, several embodiments described herein reduce substrate damage during hard mask formation and improve adhesion between the hard mask and the surface on which the hard mask is placed. Briefly, in some embodiments, a substrate is electrostatically chucked to a substrate support in the presence of a carbon-containing gas. A first carbon-containing layer is formed while the substrate is electrostatically chucked. Then, a second carbon-containing layer (e.g., a diamond-like carbon (DLC) film or sp) is formed. 3 A hard mask layer is formed by depositing a film with a fraction of more than 60% onto a substrate. The resulting carbon-containing layer prevents or at least reduces damage to the underlying layer caused by high-energy ion bombardment, thereby reducing wafer impingement.

[0012]

[0015] Conventional methods for plasma strike (e.g., ignition) typically utilize a non-reactive gas (e.g., argon or helium) alone, with the primary deposition operation utilizing a precursor / carrier (e.g., acetylene / helium) mixture. As a result, high-energy bombardments of ions collide with the dielectric beneath the carbon hard mask before a carbon hard mask is formed on the dielectric layer. In contrast, several embodiments described herein utilize a carbon-containing gas (with or without a non-reactive gas) to strike the plasma and form an initiation layer while the substrate is electrostatically chucked. During the deposition operation, a carbon-containing gas (with or without a non-reactive gas) can be used to form a carbon hard mask. After the carbon-based hard mask is removed, a wavy morphology of the resulting dielectric material may be observed. In contrast, several embodiments described herein eliminate or at least mitigate damage to the underlying dielectric material; therefore, several embodiments described herein enable, for example, improved device performance.

[0013]

[0016] Figure 1 is a schematic side cross-sectional view of an exemplary processing chamber 100 suitable for carrying out a deposition process according to at least one embodiment. A suitable chamber can be obtained from Applied Materials, Inc. in Calif, Santa Clara, California. The system described below is an exemplary chamber, and it should be understood that other chambers, including chambers from other manufacturers, may be used or modified to carry out multiple embodiments of this disclosure (e.g., process 300 described below). In some embodiments, the processing chamber 100 may be configured to deposit an advanced patterning film, such as a hard mask film (e.g., an amorphous carbon hard mask film), onto a substrate.

[0014]

[0017] The processing chamber 100 includes a lid assembly 105, a spacer 110 positioned on the chamber body 192, a substrate support 115, and a variable pressure system 120. The lid assembly 105 includes a lid plate 125 and a heat exchanger 130. In one illustrated embodiment, the lid assembly 105 also includes a shower head 135. However, in several other embodiments, the lid assembly 105 includes a concave or dome-shaped gas introduction plate.

[0015]

[0018] The lid assembly 105 is coupled to a first processing gas source 140. The first processing gas source 140 contains a precursor gas for forming a film on a substrate 145 supported on a substrate support 115. In one embodiment, the first processing gas source 140 contains a precursor gas such as, among other things, a carbon-containing gas, a hydrogen-containing gas, or a non-reactive gas (e.g., helium). In a particular embodiment, the carbon-containing gas includes acetylene (C2H2). The first processing gas source 140 supplies the precursor gas to a plenum 190 located within the lid assembly 105. The lid assembly includes one or more channels for guiding the precursor gas from the first processing gas source 140 into the plenum 190. The precursor gas flows from the plenum through a showerhead 135 into the processing space 160. In some embodiments, a second processing gas source 142 is fluidly coupled to the processing space 160 via an inlet 144 located through a spacer 110. In one embodiment, the second processing gas source 142 includes, among other things, a precursor gas such as a carbon-containing gas, a hydrogen-containing gas, or an inert gas (e.g., helium), such as C2H2. In some embodiments, the total flow rate of the precursor gas into the processing space 160 is from about 100 sccm to about 2 slm. The flow of the precursor gas in the processing space 160 via the second processing gas source 142 regulates the flow of the precursor gas through the showerhead 135. This ensures that the precursor gas is uniformly dispersed within the processing space 160. In one embodiment, a plurality of inlets 144 may be distributed radially around the spacer 110. In such an embodiment, the gas flow to each of the inlets 144 may be controlled separately to further promote the uniformity of the gas within the processing space 160.

[0016]

[0019] The lid assembly 105 is also coupled to an optional remote plasma source 150. The optional remote plasma source 150 is coupled to a cleaning gas source 155 for supplying cleaning gas to a processing space 160 formed inside the spacer 110 between the lid assembly 105 and the substrate 145. In one embodiment, the cleaning gas is supplied through a central conduit 191 formed axially through the lid assembly 105. In another embodiment, the cleaning gas is supplied through the same channel that supplies the precursor gas. Exemplary cleaning gases include oxygen-containing gases such as oxygen and / or ozone, as well as fluorine-containing gases such as NF3, or combinations thereof.

[0017]

[0020] In addition to or as an alternative to the optional remote plasma source 150, the lid assembly 105 is also coupled to a first or upper radio frequency (RF) power supply 165. The first RF power supply 165 facilitates the maintenance or generation of plasma, such as plasma generated from a cleaning gas. In one embodiment, the optional remote plasma source 150 is omitted, and the cleaning gas is ionized in situ into the plasma via the first RF power supply 165. The substrate support 115 is coupled to a second or lower RF power supply 170. The first RF power supply 165 may be a high-frequency RF power supply (e.g., from about 13.56 MHz to about 120 MHz), and the second RF power supply 170 may be a low-frequency RF power supply (e.g., from about 2 MHz to about 13.56 MHz). Note that other frequencies are also considered. In some embodiments, the second RF power supply 170 is a mixed-frequency RF power supply, providing both high-frequency and low-frequency power. In particular, the use of a dual-frequency RF power supply for the second RF power supply 170 improves film deposition. In some embodiments, dual-frequency power is obtained by utilizing the second RF power supply 170. In some embodiments, a first frequency, for example, from about 2 MHz to about 13.56 MHz, improves the injection of nuclides into the deposited film, while a second frequency, for example, from about 13.56 MHz to about 120 MHz, increases the ionization and film deposition rates.

[0018]

[0021] One or both of the first RF power supply 165 and the second RF power supply 170 can be used to generate or maintain plasma within the processing space 160. For example, the second RF power supply 170 may be used during the deposition process, and the first RF power supply 165 may be used (alone or in combination with an optional remote plasma source 150) during the cleaning process. In some deposition processes, the first RF power supply 165 is used in combination with the second RF power supply 170. During the deposition or etching process, one or both of the first RF power supply 165 and the second RF power supply 170 can provide power ranging from about 100 watts (W) to about 20,000 W within the processing space 160 to promote the ionization of the precursor gas. In some embodiments, at least one of the first RF power supply 165 and the second RF power supply 170 is pulsed. In at least one embodiment, RF power is applied to the lid plate 125.

[0019]

[0022] The substrate support 115 is coupled to an actuator 175 (i.e., a lift actuator). The actuator 175 provides movement of the substrate support 115 in the Z direction. The substrate support 115 is also coupled to an equipment cable 178. The equipment cable 178 is flexible and allows vertical movement of the substrate support 115 while maintaining communication with the second RF power supply 170 and other power sources, and fluid connections. A spacer 110 is positioned on the chamber body 192. The height of the spacer 110 allows vertical movement of the substrate support 115 within the processing space 160. The height of the spacer 110 ranges from approximately 0.5 inches to approximately 20 inches. In one embodiment, the substrate support 115 is movable from a first distance 180A to a second distance 180B relative to the lid assembly 105 (e.g., relative to the underside of the shower head 135). In some embodiments, the second distance 180B is approximately 2 / 3 of the first distance 180A. For example, the difference between the first distance 180A and the second distance is approximately 5 to 6 inches. Therefore, from the position shown in Figure 1, the substrate support 115 is movable only about 5 to 6 inches relative to the underside of the showerhead 135. In another embodiment, the substrate support 115 is fixed at either the first distance 180A or the second distance 180B. In contrast to conventional plasma chemical vapor deposition (PECVD) processes, the spacer 110 significantly increases the distance between the substrate support 115 and the lid assembly 105 (and therefore the space between them). The increased distance between the substrate support 115 and the lid assembly 105 reduces collisions of ionized species in the processing space 160, resulting in the deposition of a film with a lower neutral stress, such as less than 2.5 gigapascals (GPa). A deposited film with a lower neutral stress facilitates improved flatness of the substrate on which the film is formed (e.g., less warping). Reducing substrate warping results in improved accuracy in downstream patterning operations.

[0020]

[0023] The variable pressure system 120 includes a first pump 182 and a second pump 184. The first pump 182 is a roughing pump that may be used during the cleaning process and / or the substrate transfer process. Roughing pumps are generally configured to move higher volumetric flow rates and / or operate at relatively higher pressures (though still below atmospheric pressure). In one non-limiting embodiment, during the cleaning process, the first pump 182 maintains the pressure in the processing chamber at less than about 500 mTorr, such as less than about 50 mTorr. In another embodiment, the first pump 182 maintains the pressure in the processing chamber 100 at, for example, less than about 500 mTorr, for example less than about 50 mTorr, for example from about 0.5 mTorr to about 10 mTorr, or from about 5 mTorr to about 15 mTorr. By using a roughing pump during the cleaning operation, the pressure and / or volumetric flow rate of the cleaning gas are relatively higher (compared to the deposition operation). Relatively high pressure and / or volumetric flow rate during the cleaning operation improves cleaning of the chamber surface.

[0021]

[0024] The second pump 184 may be either a turbopump or a cryogenic pump. The second pump 184 may be used during the deposition process. The second pump 184 is generally configured to operate at relatively low volumetric flow rates and / or pressures. In one non-limiting embodiment, the second pump 184 is configured to maintain the processing space 160 of the process chamber at a pressure of less than about 500 mTorr, such as less than about 50 mTorr. In another embodiment, the second pump 184 maintains the pressure in the processing chamber 100 at, for example, less than about 500 mTorr, for example less than about 50 mTorr, for example from about 0.5 mTorr to about 10 mTorr, or from about 5 mTorr to about 15 mTorr. The reduced pressure in the processing space 160 maintained during deposition results in reduced neutral stress and / or increased sp when depositing a carbon-based hard mask. 2 -sp 3 This facilitates the deposition of films with transformation properties. Therefore, the processing chamber 100 is configured to utilize both relatively low pressure to improve deposition and relatively high pressure to improve washing.

[0022]

[0025] In some embodiments, both the first pump 182 and the second pump 184 are utilized during the deposition process to maintain the processing chamber 160 at a pressure of less than approximately 500 mTorr, such as less than approximately 50 mTorr. In several other embodiments, the first pump 182 and the second pump 184 maintain the processing chamber 160 at a pressure of, for example, approximately 0.5 mTorr to approximately 10 mTorr or approximately 5 mTorr to approximately 15 mTorr. A valve 186 is used to control the conduction path to one or both of the first pump 182 and the second pump 184. The valve 186 also provides symmetrical pumping from the processing chamber 160.

[0023]

[0026] The processing chamber 100 also includes a substrate transfer port 185. The substrate transfer port 185 is selectively sealed by an internal door 186A and an external door 186B. Each of the doors 186A and 186B is coupled to an actuator 188 (i.e., a door actuator). The doors 186A and 186B facilitate depressurized sealing of the processing space 160. The doors 186A and 186B also provide symmetrical RF application and / or plasma symmetry within the processing space 160. In one embodiment, at least the door 186A is formed of a material that promotes the conductivity of RF power, such as stainless steel, aluminum, or an alloy thereof. A seal 116, such as an O-ring, positioned at the interface between the spacer 110 and the chamber body 192 may further seal the processing space 160. A controller 194 coupled to the processing chamber 100 is configured to control various aspects of the processing chamber 100 during processing.

[0024]

[0027] Figure 2A is a schematic cross-sectional view of one embodiment of the substrate support 115. Figure 2B is an enlarged cross-sectional view of a portion of the substrate support 115 shown in Figure 2A. As described above, the substrate support 115 may include an electrostatic chuck 230. The electrostatic chuck 230 includes a pack 260. The pack 260 includes one or more electrodes 205 embedded inside (a first electrode 205A and a second electrode 205B shown in Figure 2B). The first electrode 205A is used as a chuck electrode, and the second electrode 205B is used as an RF bias electrode. The substrate support 115 may be biased by providing RF power to the second electrode 205B at a frequency of about 300 kHz to about 120 MHz, for example, from about 300 kHz to about 60 MHz. The frequency provided to the second electrode 205B may be pulsed. The pack 260 is typically formed from a dielectric material such as a ceramic material, for example, aluminum nitride (AlN).

[0025]

[0028] Pack 260 is supported by a dielectric plate 210 and a base plate 215. The dielectric plate 210 may be made of an electrically insulating material such as quartz, or a thermoplastic material such as a high-performance plastic sold under the trade name REXOLITE®. The base plate 215 may be made of a metallic material such as aluminum. During operation, while Pack 260 is RF energized, the base plate 215 is either coupled to ground or electrically floating. At least Pack 260 and the dielectric plate 210 are surrounded by an insulating ring 220. The insulating ring 220 may be made of a dielectric material such as quartz, silicon, or ceramic material. The base plate 215 and a portion of the insulating ring 220 are surrounded by a grounding ring 225 made of aluminum. The insulating ring 220 prevents or minimizes arc discharge between Pack 260 and the base plate 215 during operation. The end of the equipment cable 178 is shown within an opening formed in the pack 260, dielectric plate 210, and base plate 215. Power for the electrodes of the pack 260, as well as fluid from the gas supply (not shown) to the substrate support 115, are supplied by the equipment cable 178.

[0026]

[0029] An edge ring (not shown) is positioned adjacent to the inner circumference of the insulator ring 220. The edge ring may, in particular, contain dielectric materials such as quartz, silicon, crosslinked polystyrene and divinylbenzene (e.g., REXOLITE®), PEEK, Al2O3, and AIN. By utilizing an edge ring containing such dielectric materials, the plasma coupling can be adjusted without changing the plasma output, thereby controlling the voltage (V) to the substrate support. dc Plasma properties such as ) can be adjusted, and therefore the properties of the hard mask film deposited on the substrate can be improved. By adjusting the RF coupling with the wafer or substrate via the edge ring material, the elastic modulus of the film can be separated from the film's stress.

[0027]

[0030] Each of the pack 260, dielectric plate 210, and base plate 215 includes an axially aligned opening formed inside or through the pack 260 for accommodating the equipment cable 178. The pack 260 includes an opening 295 molded to engage with the equipment cable 178. For example, the opening 295 may be configured as a female socket for receiving the equipment cable 178. The dielectric plate 210 includes an opening 296 axially aligned with the opening 295. The opening 296 includes an upper portion 296a having a diameter approximately equal to the diameter of the opening 295, an intermediate portion 296b having a larger diameter than the upper portion, and a lower portion 296c having a larger diameter than the intermediate portion 296b. The base plate 215 includes an opening 297, which includes an upper portion 297a having a first diameter and a lower portion 297b having a second diameter smaller than the first diameter. The multiple diameters of the openings 296 and 297 can facilitate the securing of the equipment cable 178 inside.

[0028]

[0031] Pack 260 includes a plurality of fluid channels 231 formed inside. Each of the fluid channels 231 is in fluid communication with an inlet channel 232. The inlet channel 232 is fluidly coupled to an inlet conduit 234. The inlet conduit 234 is coupled to a coolant source 221. Each of the fluid channels 231 and the inlet channel 232 is sealed by a cap plate 236. The cap plate 236 may be made of the same material as pack 260 or of aluminum and may be welded or otherwise joined to pack 260 to seal the fluid channels 231 and the inlet conduit 234. Although not shown, an outlet conduit is provided within the substrate support 115, similar to the inlet conduit 234, so that the cooling fluid can be recirculated internally.

[0029]

[0032] A portion of the inlet conduit 234 is formed by a tubular member 238. The tubular member 238 is made of a dielectric material such as a ceramic material. A seal 240 is provided at the end of the annular member 238, adjacent to the cap plate 236 and the base plate 215. The tubular member 238 prevents arc discharge that may be caused by the cooling fluid flowing through it. The tubular member 238 may also thermally insulate the dielectric plate 210 from the relatively cold cooling fluid flowing inside in order to prevent cracking of the dielectric plate 210.

[0030]

[0033] The substrate support 115 also includes a plurality of lift pins 242 (only one is shown in Figure 2A). Each of the lift pins 242 is movably positioned within a dielectric bushing 244. Each of the lift pins 242 may be formed from a ceramic material such as AlN, sapphire, or quartz. The dielectric bushing 244 is provided within or through each of the pack 260, dielectric plate 210, and base plate 215. The dielectric bushing 244 is made from a polymer material such as polytetrafluoroethylene (PTFE). The dielectric bushing 244 includes an opening 246 along its longitudinal direction. The lift pins 242 are guided within the opening 246. The opening 246 is sized to be slightly larger than the dimensions (diameter) of the lift pins 242. Thereafter, a conduction path is formed within the dielectric bushing 244. For example, the opening 246 is coupled to a variable pressure system 120. This provides reduced pressure conduction between the processing space 160 and the dielectric bushing 244, and through the dielectric bushing 244 to the variable pressure system 120. The conduction path provided by the opening 246 prevents arc discharge of the lift pin. The dielectric bushing 244 includes a number of steps 248, which are sections with varying diameters. The steps 248 reduce arc discharge between the pack 260 and the base plate 215 by increasing the length of the path to which electricity may travel, and by introducing angled turns along the path.

[0031]

[0034] The substrate support 115 also includes a plurality of fastening devices 250 (only one is shown). The fastening devices 250 are used to attach the pack 260 to the dielectric plate 210. Each fastening device 250 includes a fastener 252, a washer 254, and a fastener cap 256 (the washer 254 and fastener cap 256 are shown in Figure 2B). When the fastener 252 is tightened, the washer 254 is pressed against the surface 258 of an opening 268 formed in the dielectric plate 210. The washer 254 and fastener 252 are made of a metallic material such as stainless steel. The washer 254 includes a rounded upper corner 262. The rounded upper corner 262 prevents cracking of the material of the dielectric plate 210 when the fastener 252 is tightened.

[0032]

[0035] The fastener cap 256 is used to fill the remainder of the opening 268 in the dielectric plate 210. The fastener cap 256 includes a pocket 264 sized to receive the head of the fastener 252. The fastener cap 256 is formed from a dielectric material such as a polymer (e.g., polyetheretherketone (PEEK)). The outer surface of the fastener cap 256 includes a step 266. The step 266 reduces arc discharge between the pack 260 and the base plate 215 by increasing the length of the path through which electricity may travel.

[0033]

[0036] The substrate support 115 also includes a plurality of gaps between its layers. A first gap 270 is provided between the pack 260 and the dielectric plate 210. A second gap 272 is provided between the dielectric plate 210 and the base plate 215. The first gap 270 and the second gap 272 are in fluid communication with a gas supply (not shown). Fluids from the gas supply can be flowed into the first gap 270 and the second gap 272 to prevent compression between adjacent layers. The fluids within the first gap 270 and the second gap 272 are sealed at the edges of the substrate support 115 by an edge ring. The edge ring may be sized to provide a controlled leakage of fluids from the first gap 270 and the second gap 272.

[0034] method

[0037] Multiple embodiments of the present disclosure generally relate to methods of processing a substrate, such as a process for forming a hard mask layer on a substrate. Conventional methods typically use a mixed gas of argon and / or helium during plasma strike, resulting in damage to the underlying layer. In contrast, multiple embodiments described herein utilize a carbon-containing gas (with or without a non-reactive gas) to strike a plasma and form an intermediate / initiation layer on the substrate while the substrate is electrostatically chucked. This intermediate layer formation operation using low RF bias power prevents Ar ion bombardment into the underlying layer during pre-chucking and serves as a blocking (intermediate / initiation) layer to prevent high-energy bombardment of CH2+ ions during deposition, as identified by transmission electron microscope images. For example, due to the lower RF bias power used during the intermediate layer formation operation compared to the main deposition operation, CH2+ ions also do not adversely affect the underlying layer. During the main deposition operation as well, a carbon hard mask can be formed using a carbon-containing gas (with or without a non-reactive gas). Further, the resulting hard mask film properties are not affected by this thin carbon-containing initiation layer (formed during plasma strike). Typically, the carbon-containing initiation layer has a lower sp than the layer formed from the main deposition operation. 3It has a carbon content and its thickness is less than approximately 100 Å. In addition, plasma strikes using carbon-containing gases, with or without non-reactive gases, can help mitigate damage to the underlying layers. As described below, the chucking / starting layer is formed with a lower RF bias power than the main deposition operation.

[0035]

[0038] Figure 3 is a flowchart showing selected operations of an exemplary process 300 for forming a hard mask film on a substrate according to at least one embodiment of the present disclosure. The process eliminates (or at least mitigates) damage to the underlying layer during the formation of the carbon hard mask and improves the adhesion between the hard mask and the underlying layer on which the hard mask is formed.

[0036]

[0039] Process 300 includes operation 310, which involves introducing the substrate into the processing area of ​​the substrate processing chamber (e.g., by transferring or transporting it). In one embodiment, the substrate (e.g., substrate 145) is transferred into the processing chamber 100 and onto the substrate support 115 by any suitable means (e.g., by a substrate transfer port 185). The substrate support 115 can be adjusted to the processing position by an actuator 175, as shown in Figure 1. The substrate support 115 includes an electrostatic chuck, such as an electrostatic chuck 230. The substrate may contain one or more materials such as nitrides, oxides, silicon, and / or metals (e.g., tungsten, molybdenum, titanium, etc.).

[0037]

[0040] Process 300 further includes, in operation 320, flowing one or more process gases into the processing space within the PECVD chamber. In one embodiment, one or more process gases from one or more sources are supplied to the processing space 160, for example, by passing through a showerhead 135. Thereafter, the one or more process gases are uniformly distributed within the processing space 160. In one embodiment, a plurality of inlets 144 may be distributed radially around the spacer 110, and the gas flow to each of the plurality of inlets 144 may be controlled separately to further promote the uniformity of the gas within the processing space 160.

[0038]

[0041] The process gas contains one or more carbon-containing compounds. Furthermore, or alternatively, the process gas is generated from one or more carbon-containing compounds. For example, compounds that are not in a gaseous state at standard temperature and pressure can be converted into carbon-containing compounds. Therefore, in some embodiments, the carbon-containing gas contains carbon-containing compounds, or the carbon-containing gas is generated from carbon-containing compounds, or a combination thereof.

[0039]

[0042] Non-limiting examples of carbon-containing compounds include, in particular, hydrocarbons, aromatic hydrocarbons, and halogenated compounds. In some embodiments, the carbon-containing compound is, for example, C1-C 100 For example, C1~C 40 For example, C1~C 20 For example, C1~C 10 It has the number of carbon atoms. Carbon-containing compounds may be linear or branched, cyclic or acyclic, and / or substituted or unsubstituted. A carbon-containing compound is defined as one in which at least one hydrogen atom of the carbon-containing compound is substituted with at least one heteroatom (halogen, e.g., fluorine (F), chlorine (Cl), bromine (Br), and / or iodine (I)) or a heteroatom-containing group (functional group, e.g., -NR*2, -OR*, -SiR*3, -GeR*3, etc., where each R* is independently hydrogen or a linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbon).

[0040]

[0043] A non-limiting example of hydrocarbons is the empirical formula C n H 2n+2 Alkanes having empirical formula C n H 2n Alkenes having the empirical formula C n H 2n-2Examples of alkynes include, but are not limited to, those having the properties of alkanes, alkenes, and alkynes. Each of these can be linear or branched, cyclic or acyclic, aromatic or non-aromatic, substituted or unsubstituted. Non-limiting examples of alkanes include, for example, methane, ethane, and isomers of propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and eikosane. Non-limiting examples of alkenes include, for example, ethene, and isomers of propene, butane, pentane, hexene, heptane, octane, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecane, heptadecane, octadecene, nonadecane, and eikosane. Non-limiting examples of alkynes include, for example, acetylene, as well as isomers of propyne, butine, pentine, hexine, heptone, octone, noin, desine, undecine, dodecine, tridecine, tetradecine, pentadecine, hexadesine, heptadesine, octadecine, nonadesine, and aicosine.

[0041]

[0044] Non-limiting examples of aromatic hydrocarbons include C4-C 30 Aromatic hydrocarbons, for example, C6-C 20 Aromatic hydrocarbons include, but are not limited to, benzene, toluene, xylene, and naphthalene. Aromatic hydrocarbons are either unsubstituted or substituted. If substituted, at least one hydrogen atom of the aromatic hydrocarbon is substituted with at least one heteroatom (halogen, e.g., fluorine (F), chlorine (Cl), bromine (Br), and / or iodine (I)) or a heteroatom-containing group (functional group, e.g., -NR*2, -OR*, -SiR*3, -GeR*3, etc., where each R* is independently hydrogen or a linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbon).

[0042]

[0045] Non-limiting examples of halogenated compounds include those with empirical formula C n HxX' (2n+2-x) Examples of compounds having the following characteristics include, but are not limited to, X' = F, Cl, Br, and / or I, and n = 1 to 100 (e.g., 1 to 40, 1 to 30, 1 to 20, 1 to 10, etc., 1 to 6). Examples of halogenated compounds include, but are not limited to, CF4, CH2F2, C4F6, or combinations thereof.

[0043]

[0046] In some embodiments, the process gas further comprises one or more nonreactive gases. Examples of nonreactive gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), or combinations thereof.

[0044]

[0047] Process 300 further includes, in operation 330, generating an excited process gas from a process gas. The excited process gas is generated by a plasma under plasma conditions. Here, for example, RF power supplies 165 and / or RF power supplies 170 can supply RF power at any suitable frequency or power level for plasma generation. The RF power generates an electromagnetic field that excites the process gas within the processing space 160. Non-limiting examples of process conditions for generating plasma are provided below.

[0045]

[0048] Process 300 further includes, in operation 340, electrostatically chucking the substrate to a substrate support, and in operation 350, depositing a first carbon-containing layer onto the substrate while the substrate is electrostatically chucked. A hard mask is then formed by depositing a second carbon-containing layer onto the substrate in operation 360. The first carbon-containing layer may act as a blocking (intermediate / starting) layer to prevent high-energy bombardment of C2H+ ions during the main deposition step of operation 360.

[0046]

[0049] Various operations of the exemplary processes described herein (e.g., process 300) include one or more process parameters, as described below.

[0047]

[0050] The substrate temperature may be less than or equal to about 100°C, for example, from about -40°C to about 100°C, for example, from about -30°C to about 50°C, or from about -40°C to about 10°C. In at least one embodiment, the substrate temperature is in the range T1 to T2 (in °C), where T1 and T2 are independently about -40, about -35, about -30, about -25, about -20, about -15, about -10, about -5, about 0, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, or about 100, and T1 <T2である。

[0048]

[0051] The pressure in the processing space may be approximately 500 millitorr (mTorr) or less, for example, approximately 400 mTorr or less, for example, approximately 300 mTorr or less, for example, approximately 200 mTorr or less, for example, approximately 100 mTorr or less, for example, approximately 50 mTorr or less, for example, approximately 20 mTorr or less, for example, from approximately 1 mTorr to approximately 10 mTorr, from approximately 4 mTorr to approximately 10 mTorr, or from approximately 5 mTorr to approximately 15 mTorr. In at least one embodiment, the pressure in the processing space is in the range of P1 to P2 (in mTorr units). Here, each of P1 and P2 is independently approximately 0.5 mTorr, approximately 1, approximately 2, approximately 3, approximately 4, approximately 5, approximately 6, approximately 7, approximately 8, approximately 9, approximately 10, approximately 11, approximately 12, approximately 13, approximately 14, approximately 15, approximately 16, approximately 17, approximately 18, approximately 19, approximately 20, approximately 25, approximately 50, approximately 100, approximately 200, approximately 300, approximately 400, or approximately 500, and P1 <P2である。

[0049]

[0052] The flow rate of one or more carbon-containing gases into the processing space is approximately 5000 standard cubic centimeters / minute (sccm) or less, and for example, for a 300 mm size substrate, it may range from approximately 20 sccm to approximately 5000 sccm, for example from approximately 50 sccm to approximately 200 sccm, or for example from approximately 80 sccm to approximately 160 sccm. In at least one embodiment, for a 300 mm size substrate, the flow rate of one or more carbon-containing gases is in the range of flow rate 1 to flow rate 2 (in sccm). Here, flow rates 1 and 2 are independently approximately 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000, and flow rate 1 < flow rate 2.

[0050]

[0053] In some embodiments in which one or more nonreactive gases are used, the flow rate of one or more nonreactive gases into the processing space may be approximately 3000 sccm or less, for example 500 sccm or less, for example 250 sccm or less, for example approximately 0 sccm to approximately 100 sccm, for example approximately 1 sccm to approximately 50 sccm for a 300 mm substrate. In at least one embodiment, the flow rate of one or more nonreactive gases for a 300 mm substrate is in the range of flow rate 3 to flow rate 4 (in sccm). Here, flow rates 3 and 4 are independently approximately 0, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 500, 1000, 1500, 2000, 2500, or 3000, and flow rate 3 < flow rate 4.

[0051]

[0054] In several embodiments in which one or more nonreactive gases are used, for a 300 mm substrate, the ratio of the flow rates of (one or more) carbon-containing gases to (one or more) nonreactive gases may be about 0.05 or more, for example, about 0.1 to about 100, for example, about 0.5 to about 50, for example, about 1 to about 10. In at least one embodiment, for a 300 mm substrate, the ratio of the flow rates of (one or more) carbon-containing gases to (one or more) nonreactive gases is in the range of ratio 1 to ratio 2. Here, each of ratio 1 and ratio 2 is independently approximately 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, and ratio 1 < ratio 2.

[0052]

[0055] The RF power applied to the lid plate (e.g., lid plate 125) may range from about 100 watts (W) to about 10,000 W, for example, from about 500 W to about 5,000 W, for example, from about 1,000 W to about 2,000 W, or from about 2,500 W to 4,000 W. In at least one embodiment, the RF power is in the range of power 1 to power 2 (in units of W), where each of power 1 and power 2 is independently about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, about 1,000, about 1,500, about 2,000, about 2,500, about 2,600, about 2,700, about 2,800, about 2,900, about 3,000, about 3,100, about 3,200, and about 3 300, approximately 3400, approximately 3500, approximately 3600, approximately 3700, approximately 3800, approximately 3900, approximately 4000, approximately 4500, approximately 5000, approximately 5500, approximately 6000, approximately 6500, approximately 7000, approximately 7500, approximately 8000, approximately 8500, approximately 9000, approximately 9500, or approximately 10000W, and power 1 < power 2.

[0053]

[0056] The RF bias power applied to the substrate support during deposition may range from approximately 100 watts (W) to approximately 10,000 W, for example, approximately 500 W to approximately 5,000 W, for example, approximately 1,000 W to approximately 2,000 W, or approximately 2,500 W to approximately 4,000 W. In at least one embodiment, the RF power during deposition is in the range of power 3 to power 4 (in units of W). Here, each of power 3 and power 4 is independently approximately 100, approximately 200, approximately 300, approximately 400, approximately 500, approximately 600, approximately 700, approximately 800, approximately 900, approximately 1,000, approximately 1,500, approximately 2,000, approximately 2,500, approximately 2,600, approximately 2,700, approximately 2,800, approximately 2,900, approximately 3,000, approximately 3,100, approximately 3,200, and approximately 3 300, approximately 3400, approximately 3500, approximately 3600, approximately 3700, approximately 3800, approximately 3900, approximately 4000, approximately 4500, approximately 5000, approximately 5500, approximately 6000, approximately 6500, approximately 7000, approximately 7500, approximately 8000, approximately 8500, approximately 9000, approximately 9500, or approximately 10000, and power 3 < power 4.

[0054]

[0057] The RF bias power during a plasma strike can range from approximately 100 watts (W) to approximately 1000 watts (W), for example, from approximately 100 watts to approximately 800 watts, or for example, from approximately 200 watts to approximately 500 watts. In at least one embodiment, the RF bias power during a plasma strike is in the range of power 5 to power 6 (in units of watts), where power 5 and power 6 are independently approximately 10, approximately 50, approximately 100, approximately 150, approximately 200, approximately 250, approximately 300, approximately 350, approximately 400, approximately 450, approximately 500, approximately 550, approximately 600, approximately 650, approximately 700, approximately 750, approximately 800, approximately 850, approximately 900, approximately 950, or approximately 1000, and power 5 < power 6.

[0055]

[0058] The substrate support may be biased by providing RF power at frequencies such as at least about 300 kHz, for example, from about 400 kHz to about 120 MHz, or from about 300 kHz to about 60 MHz, for example, from about 1 MHz to about 10 MHz. The frequency may be pulsed.

[0056]

[0059] The plasma used will be approximately 10 ions / cm². 3The above order of magnitude, for example, about 100 ions / cm³. 3 From approximately 1 x 10 15 Ions / cm 3 For example, approximately 1 × 10 7 Ions / cm 3 From approximately 1 x 10 15 Ions / cm 3 For example, 1 × 10 8 Ions / cm 3 From approximately 1 x 10 14 Ions / cm 3 For example, 1 × 10 9 Ions / cm 3 From approximately 1 x 10 13 Ions / cm 3 For example, 1 × 10 10 Ions / cm 3 From approximately 1 x 10 12 Ions / cm 3 It may have a plasma density of PD1 to PD2 (ions / cm³). In at least one embodiment, the plasma density (PD) is PD1 to PD2 (ions / cm³). 3 It is within the range of (units). Here, PD1 and PD2 are independently approximately 1 ion / cm³. 3 Approximately 10 ions / cm³ 3 Approximately 100 ions / cm³ 3 , about 1×10 3 Ions / cm 3 , about 1×10 4 Ions / cm 3 , about 1×10 5 Ions / cm 3 , about 1×10 6 Ions / cm 3 , about 1×10 7 Ions / cm 3 , about 1×10 8 Ions / cm 3 , about 1×10 9 Ions / cm 3 , about 1×10 10 Ions / cm 3 , about 1×10 11 Ions / cm 3 , about 1×10 12 Ions / cm 3 , about 1×10 13 Ions / cm 3 , about 1×10 14 Ions / cm3 or about 1×10 15 ions / cm 3 and PD1 < PD2. The plasma density can be measured within the processing space of the substrate processing chamber.

[0057]

[0060] The deposition time of the carbon-containing layer can be about 1 second (s) or more, for example, from about 1 s to about 2000 s, for example, from about 1 s to about 1000 s, or from about 1000 s to about 1500 s. In at least one embodiment, the deposition time is in the range of time 1 to time 2 (in units of s). Here, time 1 and time 2 are independently about 1, about 10, about 30, about 60, about 90, about 120, about 150, about 200, about 240, about 300, about 360, about 420, about 480, about 540, about 600, about 660, about 720, about 780, about 840, about 900, about 960, about 1000, about 1020, about 1080, about 1140, about 1200, about 1260, about 1320, about 1380, about 1440, about 1500, about 1560, about 1620, about 1680, about 1740, about 1800, about 1860, about 1920, about 1980, or about 2000, and time 1 < time 2.

[0058]

[0061] The thickness of the carbon-containing layer formed may be at least about 25 angstroms (Å), for example, from about 50 Å to about 50,000 Å, or from about 100 Å to about 25,000 Å. In at least one embodiment, the thickness of the carbon-containing layer is in the range of 1 to 2 (in Å). Here, thickness 1 and thickness 2 are independently approximately 50, 100, 200, 300, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, and 240. 00, approximately 25000, approximately 26000, approximately 27000, approximately 28000, approximately 29000, approximately 30000, approximately 31000, approximately 32000, approximately 33000, approximately 34000, approximately 35000, approximately 36000, approximately 37000, approximately 38000, approximately 39000, approximately 40000, approximately 41000, approximately 42000, approximately 43000, approximately 44000, approximately 45000, approximately 46000, approximately 47000, approximately 48000, approximately 49000, or 50000, and thickness 1 < thickness 2.

[0059]

[0062] The deposition rate of the carbon-containing layer may be greater than or equal to about 1 angstrom / min (Å / min), for example, from about 1 Å / min to about 5000 Å / min, for example, from about 10 Å / min to about 3000 Å / min, or for example, from about 100 Å / min to about 2000 Å / min. In at least one embodiment, the deposition rate of the carbon-containing layer is in the range of DR1 to DR2 (in Å / min). Here, DR1 and DR2 are independently approximately 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, and 240. 0, approximately 2500, approximately 2600, approximately 2700, approximately 2800, approximately 2900, approximately 3000, approximately 3100, approximately 3200, approximately 3300, approximately 3400, approximately 3500, approximately 3600, approximately 3700, approximately 3800, approximately 3900, approximately 4000, approximately 4100, approximately 4200, approximately 4300, approximately 4400, approximately 4500, approximately 4600, approximately 4700, approximately 4800, approximately 4900, or approximately 5000, and DR1 <DR2である。

[0060]

[0063] In some embodiments, when the deposited carbon-containing layer is identified by Raman spectroscopy, it contains at least 10% sp 3 It has hybridized atoms. That is, the carbon-containing layer is sp 3 The mixed content may be at least 10%. 3 The mixed content may range from about 1% to about 100%, for example, about 5% to about 90%, for example, about 10% to about 75%, for example, about 25% to about 50%, or at least about 60%. In at least one embodiment, the carbon-containing layer is sp 3 The mixed content is in the range of content 1 to content 2 (in percent). Here, each of content 1 and content layer 2 is independently approximately 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, and content layer 1 < content layer 2.

[0061]

[0064] Novel and improved processes and structures that overcome one or more drawbacks of conventional methods for forming hard masks are described herein. Multiple embodiments described herein, for example, reduce damage to the underlying layer during hard mask formation and improve adhesion between the hard mask and the substrate. Therefore, multiple embodiments described herein enable, for example, improved device performance.

[0062]

[0065] As is evident from the above general descriptions and specific embodiments, several forms of the disclosure have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the disclosure. Therefore, it is not intended that the disclosure is limited thereto. Similarly, the term “comprising” is to be considered synonymous with the term “including.” Similarly, where the transition phrase “comprising” precedes a composition, element, or group of elements, it is understood that the same composition or group of elements is also being considered, with the transition phrase “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the composition, element, or group of elements, and vice versa.

[0063]

[0066] For the purposes of this disclosure, unless otherwise specified, all numerical values ​​in the detailed description and claims herein take into consideration that the indicated values ​​may be modified "approximately" or "nearly," and that they include experimental errors and variations that can be expected by those skilled in the art.

[0064]

[0067] Certain embodiments and features have been described using a set of numerical upper bounds and a set of numerical lower bounds. Unless otherwise specified, it should be understood that any pair of values, e.g., any lower and upper value combination, any two lower values ​​combination, and / or any two upper values ​​combination, are considered. Specific lower values, upper values, and ranges appear in one or more of the following claims.

[0065]

[0068] While the above description applies to embodiments of the present disclosure, other embodiments and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure, and the scope of the present disclosure is defined by the following claims.

Claims

1. A method for forming a hard mask on a substrate, The process of introducing the substrate into the processing space of a plasma chemical vapor deposition (PECVD) chamber, wherein the substrate is placed on a substrate support, and the substrate support includes an electrostatic chuck. The method involves depositing a first carbon-containing layer having a thickness of approximately 100 Å or less onto the substrate while the substrate is electrostatically chucked to the substrate support, Flowing a process gas into the processing space within the PECVD chamber, wherein the process gas contains a carbon-containing gas, and The method involves applying a first RF bias power to the electrostatic chuck to strike the process gas with plasma and deposit the first carbon-containing layer, wherein the first RF bias power is approximately 200 W to approximately 500 W, and the method involves striking the plasma with plasma to deposit the first carbon-containing layer. A first carbon-containing layer, including the above, is deposited on the substrate, The hard mask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while the substrate is electrostatically chucked to the substrate support, wherein the second carbon-containing layer has a thickness of approximately 200 Å to approximately 50,000 Å, and the deposition of the second carbon-containing layer is performed as follows: Flowing the process gas into the processing space within the PECVD chamber, and The method involves applying a second RF bias power to the electrostatic chuck to deposit the second carbon-containing layer, wherein the second RF bias power is approximately 1,000 W to approximately 10,000 W. Forming the hard mask including Methods that include...

2. The carbon-containing gas contains or is produced from a carbon-containing compound, and the carbon-containing compound is substituted or unsubstituted. １ ~C ４０ Hydrocarbons, substituted or unsubstituted C ６ ~C ２０ Aromatic hydrocarbons, C １ ~C ４０ The method according to claim 1, wherein a halogenated hydrocarbon or a combination thereof.

3. The method according to claim 2, wherein the carbon-containing compound includes an alkyne.

4. The method according to claim 3, wherein the carbon-containing compound comprises acetylene.

5. The method according to claim 2, wherein the process gas further comprises a non-reactive gas.

6. The method according to claim 5, wherein the carbon-containing compound comprises acetylene and the non-reactive gas comprises helium.

7. The method according to claim 1, wherein the first carbon-containing layer, the second carbon-containing layer, or both thereof are deposited while the substrate is maintained at a temperature of about -40°C to about 40°C.

8. The first carbon-containing layer, the second carbon-containing layer, or both thereof, when identified by Raman spectroscopy, have an sp of approximately 60% or more. ３ The method according to claim 1, comprising hybrid atoms.

9. The first carbon-containing layer is deposited while the processing space is maintained at a first pressure, The method according to claim 1, wherein the second carbon-containing layer is deposited while the processing space is maintained at a second pressure.

10. The method according to claim 9, wherein the first pressure is from about 20 mTorr to about 500 mTorr, and the second pressure is from about 1 mTorr to about 10 mTorr.

11. A method for forming a hard mask on a substrate, Placing the substrate in the processing space of a plasma chemical vapor deposition (PECVD) chamber, wherein the substrate is placed on an electrostatic chuck, and placing the substrate, The method involves depositing a first carbon-containing layer having a thickness of approximately 100 Å or less onto the substrate while the substrate is electrostatically chucked, Flowing a process gas into the processing space in the PECVD chamber, the process gas including a carbon-containing gas, the carbon-containing gas including a carbon-containing compound or the carbon-containing gas being generated from a carbon-containing compound, the carbon-containing compound being a substituted or unsubstituted C １ ~C ４０ hydrocarbon, a substituted or unsubstituted C ６ ~C ２０ aromatic hydrocarbon, C １ ~C ４０ halogenated hydrocarbon, or a combination thereof, flowing the process gas The processing space is operated at a first pressure of approximately 20 mTorr to approximately 500 mTorr, and The method involves applying a first RF bias power to the electrostatic chuck to strike the process gas with plasma and deposit the first carbon-containing layer, wherein the first RF bias power is approximately 200 W to approximately 500 W, and the method involves striking the plasma with plasma to deposit the first carbon-containing layer. A first carbon-containing layer, including the above, is deposited on the substrate, The hard mask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while the substrate is electrostatically chucked, wherein the second carbon-containing layer has a thickness of approximately 200 Å to approximately 50,000 Å, and the deposition of the second carbon-containing layer is performed as follows: Flowing process gas into the processing space within the PECVD chamber, The processing space is operated at a second pressure of approximately 0.5 mTorr to approximately 10 mTorr, and The method involves applying a second RF bias power to the electrostatic chuck to deposit the second carbon-containing layer, wherein the second RF bias power is approximately 1,000 W to approximately 10,000 W, and the second carbon-containing layer is deposited accordingly. Forming the hard mask including Methods that include...

12. The method according to claim 11, wherein the carbon-containing compound comprises an alkyne.

13. The method according to claim 11, wherein the process gas further comprises one or more nonreactive gases.

14. The method according to claim 11, wherein the first carbon-containing layer, the second carbon-containing layer, or both thereof are deposited while the substrate is maintained at a temperature of about -40°C to about 10°C.

15. The first carbon-containing layer, the second carbon-containing layer, or both thereof, when identified by Raman spectroscopy, have an sp of approximately 60% or more. ３ The method according to claim 11, comprising hybrid atoms.

16. A method for forming a hard mask on a substrate, Placing the substrate in the processing space of a plasma chemical vapor deposition (PECVD) chamber, wherein the substrate is placed on an electrostatic chuck, and placing the substrate, The method involves depositing a first carbon-containing layer having a thickness of approximately 100 Å or less onto the substrate while the substrate is electrostatically chucked, The process gas is flowed into the processing space within the PECVD chamber, wherein the process gas comprises a carbon-containing gas and a non-reactive gas, the carbon-containing gas comprises or is generated from a carbon-containing compound, and the carbon-containing compound is substituted or unsubstituted. １ ~C ２０ The process gas includes hydrocarbons, and the non-reactive gas includes helium, neon, argon, or a combination thereof. The aforementioned processing space is operated at a pressure of approximately 20 mTorr to approximately 500 mTorr, and The method involves applying a first RF bias power to the electrostatic chuck to strike the process gas with plasma and deposit the first carbon-containing layer, wherein the first RF bias power is approximately 200 W to approximately 500 W, and the method involves striking the plasma with plasma to deposit the first carbon-containing layer. A first carbon-containing layer, including the above, is deposited on the substrate, The hard mask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while the substrate is electrostatically chucked, wherein the second carbon-containing layer has a thickness of approximately 200 Å to approximately 50,000 Å or more, and the deposition of the second carbon-containing layer is performed as follows: Flowing the process gas into the processing space within the PECVD chamber, The aforementioned processing space is operated at a pressure of approximately 0.5 mTorr to 10 mTorr, and The method involves applying a second RF bias power to the electrostatic chuck to deposit the second carbon-containing layer, wherein the second RF bias power is approximately 1,000 W to approximately 10,000 W, and the second carbon-containing layer is deposited accordingly. Forming the hard mask including Includes, A method comprising depositing the first carbon-containing layer, the second carbon-containing layer, or both thereof, while the substrate is maintained at a temperature of approximately -40°C to approximately 40°C.

17. The method according to claim 16, wherein the first carbon-containing layer, the second carbon-containing layer, or both thereof are deposited while the substrate is maintained at a temperature of about -40°C to about 10°C.

18. The first carbon-containing layer, the second carbon-containing layer, or both thereof, when identified by Raman spectroscopy, have an sp of approximately 60% or more. ３ The method according to claim 16, comprising hybrid atoms.

19. The method according to claim 16, wherein the carbon-containing compound is an alkyne and the nonreactive gas is helium.

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