Method for producing high-density carbon films for hard mask and other patterning applications

Abstract

Embodiments of the present disclosure generally relate to the fabrication of integrated circuits. More specifically, embodiments described herein provide methods for producing a stress-reduced diamond-like carbon film for patterning applications. In one or more embodiments, a method includes flowing a deposition gas containing a hydrocarbon into a processing volume of a processing chamber having a substrate positioned on an electrostatic chuck, and generating a plasma above the substrate in the processing volume by applying a first RF bias to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate. The stressed diamond-like carbon film has a compressive stress of -500 MPa or greater. The method further includes heating the stressed diamond-like carbon film to produce a stress-reduced diamond-like carbon film during a thermal anneal process. The stress-reduced diamond-like carbon film has a compressive stress of less than -500 MPa.

Description

background Technical Field

[0002] The embodiments of this disclosure generally relate to the fabrication of integrated circuits. More specifically, the embodiments described and discussed herein provide techniques for depositing high-density films for patterning applications. Background Technology

[0004] Integrated circuits have evolved into complex components, which can include millions of transistors, capacitors, and resistors on a single chip. The continuous advancement of chip design demands faster circuit systems and greater circuit density. This need for faster circuits with greater circuit density places corresponding demands on the materials used to manufacture such integrated circuits. Specifically, as the size of integrated circuit components shrinks to the submicron scale, it is now necessary to use low-resistivity conductive materials and low-dielectric-constant insulating materials to obtain suitable electrical properties from these components.

[0005] The demand for higher integrated circuit density also places demands on the process sequences used in manufacturing integrated circuit components. For example, in a process sequence using conventional photolithography, an energy-sensitive resist layer is formed over a stack of material layers on a substrate. The energy-sensitive resist layer is exposed to a patterned image to form a photoresist mask. Subsequently, an etching process is used to transfer the mask pattern to one or more stacked material layers. The chemical etchant used in the etching process is selected to have greater etch selectivity to the stacked material layers compared to the energy-sensitive resist mask. That is, the chemical etchant etches one or more layers of the material stack at a much faster rate than the energy-sensitive resist. This etch selectivity to the one or more stacked material layers over the resist prevents the energy-sensitive resist from being consumed before the pattern transfer is complete.

[0006] As pattern sizes decrease, the thickness of the energy-sensitive resist correspondingly decreases to control pattern resolution. This thin resist layer may be insufficient to mask the underlying material layer during the pattern transfer step due to erosion by chemical etchants. Due to their greater resistance to chemical etchants, an intermediate layer called a hard mask (e.g., silicon oxynitride, silicon carbide, or carbon film) is often used between the energy-sensitive resist layer and the underlying material layer to facilitate pattern transfer. Hard mask materials with both high etch selectivity and high deposition rates are desirable. Current hard mask materials lack the desired etch selectivity relative to the underlying material (e.g., oxides and nitrides) and are often difficult to deposit due to the reduced critical dimension (CD).

[0007] Therefore, there is a need in the art for improved hard mask layers and methods for depositing improved hard mask layers. Summary of the Invention

[0008] The embodiments of this disclosure generally relate to the fabrication of integrated circuits. More specifically, the embodiments described and discussed herein provide techniques for depositing high-density films (such as stress-reduced diamond-like carbon films) for patterning applications. In one or more embodiments, a method of processing a substrate includes infusing a hydrocarbon-containing deposition gas into a processing volume having a processing chamber positioned on an electrostatic chuck, wherein the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating plasma above the substrate in the processing volume by applying a first RF bias to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate, wherein the stressed diamond-like carbon film has a compressive stress of -500 MPa or greater. The method further includes heating the stressed diamond-like carbon film to a temperature of about 200°C to about 600°C for about 15 seconds to about 60 minutes to produce a stress-reduced diamond-like carbon film during a thermal annealing process. The stress-reduced diamond-like carbon film has a compressive stress of less than -500 MPa and a density of greater than 1.5 g / cc. In some examples, nitrogen-doped diamond-like carbon films have densities of greater than 1.5 g / cc to about 2.1 g / cc and compressive stresses of about -20 MPa to about -400 MPa.

[0009] In some embodiments, a method of processing a substrate includes infusing a hydrocarbon-containing deposition gas into a processing volume of a plasma processing chamber having a substrate positioned on an electrostatic chuck, wherein the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating plasma above the substrate in the processing volume by applying a first RF bias voltage to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate. The stressed diamond-like carbon film contains about 50 atomic percent to about 90 atomic percent sp. 3 The carbon atoms are hybridized and possess a compressive stress of -500 MPa or greater and a density greater than 1.5 g / cc. The method also includes transferring a substrate containing a stressed diamond-like carbon film from a plasma processing chamber to a thermal annealing chamber, and heating the stressed diamond-like carbon film to a temperature of approximately 200°C to approximately 600°C for approximately 15 seconds to approximately 60 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process. The stress-reduced diamond-like carbon film contains approximately 50 atomic percent to approximately 90 atomic percent sp... 3 It consists of hybrid carbon atoms and has a compressive stress of about -20 MPa to less than -500 MPa and a density of more than 1.5 g / cc to about 2.1 g / cc.

[0010] In other embodiments, a method of processing a substrate includes flowing a hydrocarbon-containing deposition gas into a processing volume having a processing chamber positioned on an electrostatic chuck, and generating plasma above the substrate in the processing volume by applying a first RF bias voltage to the electrostatic chuck to deposit a stressed diamond-like carbon (DLC) film on the substrate. The stressed DLC film has a compressive stress of -500 MPa or greater. The method also includes heating the stressed DLC film to a temperature of about 200°C to about 600°C for about 15 seconds to about 60 minutes to produce a stress-reduced DLC film during a thermal annealing process. The stress-reduced DLC film has a compressive stress of less than -500 MPa and a density greater than 1.5 g / cc. Furthermore, the compressive stress of the stress-reduced DLC film is about 40% to about 90% less than the compressive stress of the stressed DLC film. The method further includes forming a patterned photoresist layer over a stress-reduced diamond-like carbon film, etching the stress-reduced diamond-like carbon film with a pattern corresponding to the patterned photoresist layer, and etching the pattern into the substrate.

[0011] In one or more embodiments, a stress-reducing diamond-like carbon film is provided as a lower layer in an extreme ultraviolet (EUV) lithography process, and the film contains about 50 atomic percent to about 90 atomic percent or about 60 atomic percent to about 70 atomic percent of sp. 3 Hybridized carbon atoms. The stress-reduced diamond-like carbon film has a density greater than 1.5 g / cc to about 2.1 g / cc, about 1.55 g / cc to less than 2 g / cc, or about 1.6 g / cc to about 1.8 g / cc, an elastic modulus greater than 60 GPa to about 150 GPa or about 65 GPa to about 80 GPa, and a compressive stress of about -20 MPa to less than -600 MPa, about -200 MPa to about -500 MPa, or about -250 MPa to about -400 MPa. Attached Figure Description

[0012] To gain a more detailed understanding of the features described above in this disclosure, a more specific description of the disclosure, which has been briefly summarized above, can be obtained by referring to the embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings only illustrate typical embodiments of this disclosure and are not intended to limit its scope, as this disclosure allows for other equivalent and effective embodiments.

[0013] Figure 1A A schematic cross-sectional view is depicted of a deposition system that can be used to practice one or more embodiments of the process described and discussed herein.

[0014] Figure 1BA schematic cross-sectional view of another deposition system is depicted, which can be used to practice one or more embodiments described and discussed herein.

[0015] Figure 2 One or more embodiments described and discussed herein are illustrated. Figures 1A to 1B A schematic cross-sectional view of the electrostatic chuck used in the device.

[0016] Figure 3 A flowchart is provided illustrating a method for forming a stress-reduced diamond-like carbon film on a film stack disposed on a substrate, according to one or more embodiments described and discussed herein.

[0017] Figures 4A to 4B A sequence of methods for forming stress-reduced diamond-like carbon films on film stacks formed on a substrate, according to one or more embodiments described and discussed herein.

[0018] Figure 5 A flowchart is provided illustrating a method for using a stress-reduced diamond-like carbon film according to one or more embodiments described and discussed herein.

[0019] For ease of understanding, the same reference numerals have been used to identify common elements in the figures where possible. It is contemplated that elements and features of one embodiment may be advantageously incorporated into other embodiments without further description. Detailed Implementation

[0020] The embodiments provided herein relate to stress-reducing diamond-like carbon films and methods for depositing or otherwise forming stress-reducing diamond-like carbon films on substrates. Certain details are described below and in Figures 1 to 12. Figure 5 The following description is set forth to provide a thorough understanding of the various embodiments of this disclosure. Further details describing well-known structures and systems often associated with plasma processing and diamond-like carbon film deposition are not set forth in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments.

[0021] The numerous details, dimensions, angles, and other features illustrated in the figures are merely illustrative of specific embodiments. Therefore, other embodiments may have different details, components, dimensions, angles, and features without departing from the spirit or scope of this disclosure. Furthermore, further embodiments of this disclosure may be practiced without the certain details described below.

[0022] The embodiments described herein include improved methods for fabricating stress-reduced diamond-like carbon films with high density (e.g., >1.5 g / cc), high elastic modulus (e.g., >60 GPa), and low compressive stress (e.g., <-500 MPa). The stress-reduced diamond-like carbon films fabricated according to the embodiments described herein are amorphous and exhibit greater etch selectivity along with lower stress compared to current patterned films. The stress-reduced diamond-like carbon films fabricated according to the embodiments described herein not only possess low compressive stress but also high sp... 3 Carbon content. In general, the deposition and annealing processes described in this paper are also fully compatible with current integrated solutions used in hard mask applications.

[0023] In one or more embodiments, fabricating or otherwise producing a stress-reduced diamond-like carbon film includes depositing or otherwise forming a stressed diamond-like carbon film on a substrate during a deposition process (such as a chemical vapor deposition (CVD) process), and subsequently transforming the stressed diamond-like carbon film into a stress-reduced diamond-like carbon film by annealing the substrate (such as during a thermal annealing process). For example, the method may include infusing a hydrocarbon-containing deposition gas into a processing volume having a substrate positioned on an electrostatic chuck, and generating plasma above the substrate in the processing volume by applying a first RF bias to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate. The stressed diamond-like carbon film generally has a compressive stress of -500 MPa or greater (such as from about -600 MPa to about -1000 MPa). The method also includes heating a stressed diamond-like carbon film to a temperature of about 200°C to about 600°C for about 15 seconds to about 60 minutes to produce a stress-reduced diamond-like carbon film during a thermal annealing process.

[0024] In some embodiments, the stressed diamond-like carbon film described herein can be deposited or otherwise formed by CVD (such as plasma-enhanced CVD (PE-CVD) and / or thermal CVD processes) using a deposition gas containing one or more hydrocarbons. In one or more examples, the deposition gas containing one or more hydrocarbons and optionally one or more diluent gases can flow into or otherwise introduce into a processing volume of a processing chamber. The substrate is positioned or otherwise disposed on an electrostatic chuck within the processing volume, wherein the electrostatic chuck has a clamping electrode and an RF electrode separate from the clamping electrode. The method further includes generating plasma at and / or above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the clamping electrode to deposit the stressed diamond-like carbon film on the substrate.

[0025] Exemplary hydrocarbons may be or include acetylene (C2H2), propylene (C3H6), methane (CH4), butene (C4H8), 1,3-dimethyladamantane, bicyclo[2.2.1]hept-2,5-diene (2,5-norbornadiene), adamantane (C4H8). 10 H 16 norbornene (C7H) 10 The deposition gas may include, for example, its derivatives, its isomers, or any combination thereof. The deposition gas may further include one, two, or more diluent gases, carrier gases, and / or purifying gases, such as, for example, helium, argon, xenon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof. In some examples, the deposition gas may further include etchant gases, such as chlorine (Cl2), carbon tetrafluoride (CF4), and / or nitrogen trifluoride (NF3) to improve membrane quality.

[0026] During the deposition process, the substrate and / or processing volume can be heated and maintained at an independent temperature. The substrate and / or processing volume can be heated to temperatures of about -50°C, about -40°C, about -25°C, about -10°C, about -5°C, about 0°C, about 5°C, or about 10°C to about 15°C, about 20°C, about 23°C, about 30°C, about 50°C, about 100°C, about 150°C, about 200°C, about 300°C, about 400°C, about 500°C, or about 600°C. For example, the substrate and / or processing volume can be heated to about -50°C to about 600°C, about -50°C to about 450°C, about -50°C to about 350°C, about -50°C to about 200°C, about -50°C to about 100°C, about -50°C to about 50°C, about -50°C to about 0°C, about -40°C to about 200°C, about -40°C to about 100°C, about -40°C to about 80°C, about -40°C to about 50°C, about -40°C to about 25°C, about -40°C to about 10°C. Temperatures from about -40°C to about 0°C, from about 0°C to about 600°C, from about 0°C to about 450°C, from about 0°C to about 350°C, from about 0°C to about 200°C, from about 0°C to about 120°C, from about 0°C to about 100°C, from about 0°C to about 80°C, from about 0°C to about 50°C, from about 0°C to about 25°C, from about 10°C to about 600°C, from about 10°C to about 450°C, from about 10°C to about 350°C, from about 10°C to about 200°C, from about 10°C to about 100°C, or from about 10°C to about 50°C.

[0027] During the deposition process, the processing volume of the processing chamber is maintained below atmospheric pressure. The processing volume of the processing chamber is maintained at pressures of approximately 0.1 mTorr, approximately 0.5 mTorr, approximately 1 mTorr, approximately 5 mTorr, approximately 10 mTorr, approximately 50 mTorr, or approximately 80 mTorr to approximately 100 mTorr, approximately 250 mTorr, approximately 500 mTorr, approximately 1 Torr, approximately 5 Torr, approximately 10 Torr, approximately 20 Torr, approximately 50 Torr, or approximately 100 Torr. For example, the processing volume of the processing chamber is maintained at a pressure of about 0.1 mTorr to about 10 Torr, about 0.1 mTorr to about 5 Torr, about 0.1 mTorr to about 1 Torr, about 0.1 mTorr to about 500 mTorr, about 0.1 mTorr to about 100 mTorr, about 0.1 mTorr to about 10 mTorr, about 1 mTorr to about 10 Torr, about 1 mTorr to about 5 Torr, about 1 mTorr to about 1 Torr, about 1 mTorr to about 500 mTorr, about 1 mTorr to about 100 mTorr, about 1 mTorr to about 10 mTorr, about 5 mTorr to about 10 Torr, about 5 mTorr to about 5 Torr, about 5 mTorr to about 1 Torr, about 5 mTorr to about 500 mTorr, about 5 mTorr to about 100 mTorr, or about 5 mTorr to about 10 mTorr. In one or more examples, when plasma is generated on a substrate maintained at a temperature of about 0°C to about 50°C and a stressed diamond-like carbon film is deposited, the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr, about 1 mTorr to about 500 mTorr, or about 5 mTorr to about 100 mTorr.

[0028] Plasma (e.g., capacitively coupled plasma) can be formed from top and bottom electrodes or side electrodes. Electrodes can be formed from a single powered electrode, dual powered electrodes, or multiple electrodes having multiple frequencies (such as, but not limited to, about 350 kHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, and about 100 MHz), which are used alternately or simultaneously in a CVD system having any or all of the reactant gases listed herein to deposit stress-suppressed thin films of diamond-like carbon.

[0029] In one or more embodiments, a stressed diamond-like carbon film is deposited in a processing chamber having a substrate substrate maintained at about 10°C and a pressure of about 2 mTorr, wherein plasma is generated at or above the substrate level by applying a bias of about 2500 watts (about 13.56 MHz) to an electrostatic chuck. In other embodiments, an additional 1000 watts of RF at about 2 MHz is also delivered to the electrostatic chuck, thus generating a dual-bias plasma at the substrate level.

[0030] The embodiments described and discussed herein will be referenced to plasma-enhanced chemical vapor deposition (PE-CVD) processes that can be performed using any suitable thin-film deposition system. Examples of suitable systems include those that can be used... Processing chamber System, PRECISION system, system, GT TM system, XPPrecision TM system, SE TM system, Treatment chambers and Mesa TM Processing chambers, all of which are available from Applied Materials, Inc., Santa Clara, California. Other tools capable of performing PE-CVD processes may also be adapted to benefit from the embodiments described herein. Furthermore, any system for implementing the PE-CVD process described herein can be used advantageously. The apparatus descriptions herein are illustrative and should not be construed as limiting the scope of the embodiments described herein.

[0031] In one or more embodiments, as described and discussed herein, a substrate containing a stressed diamond-like carbon (DLC) film is further exposed to one or more thermal annealing processes to transform the stressed DLC film into a stress-reduced DLC film. In some embodiments, the substrate containing the stressed DLC film may be thermally annealed in the same processing chamber (e.g., a plasma processing chamber) as where it was deposited. That is, the stressed DLC film may be deposited in the same processing chamber and subsequently annealed to produce a stress-reduced DLC film.

[0032] In other embodiments, a substrate containing a stressed diamond-like carbon (DLC) film is transferred from a first processing chamber (e.g., a plasma processing chamber) to a second processing chamber (e.g., a thermal annealing chamber) and subsequently exposed to a thermal annealing process to transform the stressed DLC film into a stress-reduced DLC film. For example, the manufacturing process may include removing the substrate containing the stressed DLC film from the first processing chamber, positioning the substrate containing the stressed DLC film in the thermal annealing chamber, heating the stressed DLC film to produce a stress-reduced DLC film during the thermal annealing process, and subsequently removing the substrate containing the stress-reduced DLC film from the thermal annealing chamber.

[0033] Stressed diamond-like carbon films, substrates, and / or processing chambers are heated at temperatures of about 200°C, about 250°C, about 300°C, about 350°C, about 375°C, about 390°C, or about 400°C to about 410°C, about 425°C, about 450°C, about 475°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, or about 800°C to produce stress-reduced diamond-like carbon films during thermal annealing processes. For example, stressed diamond-like carbon films, substrates, and / or processing chambers are subjected to temperatures ranging from about 200°C to about 800°C, from about 200°C to about 700°C, from about 200°C to about 600°C, from about 200°C to about 500°C, from about 200°C to about 450°C, from about 200°C to about 400°C, from about 200°C to about 350°C, from about 200°C to about 300°C, from about 300°C to about 600°C, from about 300°C to about 500°C, and from about 300°C to about 400°C. Heating at temperatures of 50°C, about 300°C to about 400°C, about 300°C to about 350°C, about 350°C to about 600°C, about 350°C to about 500°C, about 350°C to about 450°C, about 350°C to about 420°C, about 350°C to about 400°C, about 350°C to about 380°C, about 380°C to about 420°C, or about 390°C to about 410°C to produce a stress-reduced diamond-like carbon film during the thermal annealing process.

[0034] The stressed diamond-like carbon film, substrate, and / or processing chamber are heated for about 15 seconds, about 30 seconds, about 1 minute, about 1.5 minutes, about 2 minutes, about 3 minutes, about 4 minutes, or about 5 minutes to about 6 minutes, about 8 minutes, about 10 minutes, about 12 minutes, about 15 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 60 minutes, about 75 minutes, about 90 minutes, or longer to produce a stress-reduced diamond-like carbon film during the thermal annealing process. For example, heating a stressed diamond-like carbon film, substrate, and / or processing chamber for about 15 seconds to about 90 minutes, about 15 seconds to about 75 minutes, about 15 seconds to about 60 minutes, about 15 seconds to about 45 minutes, about 15 seconds to about 30 minutes, about 15 seconds to about 20 minutes, about 15 seconds to about 10 minutes, about 15 seconds to about 5 minutes, about 15 seconds to about 3 minutes, about 15 seconds to about 1 minute, about 15 seconds to about 30 seconds, about 1 minute to about 90 minutes, about 1 minute to about 75 minutes, about 1 minute to about 60 minutes, about 1 minute to about 45 minutes, about 1 The time intervals are approximately 1 minute to 30 minutes, 1 minute to 20 minutes, 1 minute to 10 minutes, 1 minute to 5 minutes, 1 minute to 3 minutes, 3 minutes to 90 minutes, 3 minutes to 75 minutes, 3 minutes to 60 minutes, 3 minutes to 45 minutes, 3 minutes to 30 minutes, 3 minutes to 20 minutes, 3 minutes to 10 minutes, 3 minutes to 8 minutes, 3 minutes to 5 minutes, 4 minutes to 8 minutes, or 4 minutes to 6 minutes to produce a stress-reduced diamond-like carbon film during the heat annealing process.

[0035] In one or more examples, the stressed diamond-like carbon film, substrate, and / or processing chamber are heated at a temperature of about 200°C to about 600°C for about 15 seconds to about 60 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process. In some examples, the stressed diamond-like carbon film, substrate, and / or processing chamber are heated at a temperature of about 300°C to about 500°C for about 2 minutes to about 15 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process. In other examples, the stressed diamond-like carbon film, substrate, and / or processing chamber are heated at a temperature of about 350°C to about 450°C for about 3 minutes to about 8 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process.

[0036] A substrate containing a stressed diamond-like carbon film is positioned or otherwise positioned within a processing chamber during a thermal annealing process. The processing chamber may be or includes a plasma processing chamber, a thermal annealing processing chamber, a vacuum chamber, a deposition chamber (e.g., a CVD chamber), or other types of chambers that can be used to thermally heat the substrate. During the thermal annealing process, the processing volume within the processing chamber may be in a vacuum and / or environment containing a processing gas or annealing gas. Exemplary processing gases or annealing gases may be or include nitrogen (N2), argon, helium, neon, or any combination thereof.

[0037] During the hot annealing process, the processing volume in the processing chamber can have a pressure of about 0.5 mTorr, about 1 mTorr, about 5 mTorr, about 10 mTorr, about 50 mTorr, about 100 mTorr, or about 500 mTorr to about 800 mTorr, about 1 Torr, about 2 Torr, about 5 Torr, about 8 Torr, about 10 Torr, about 20 Torr, about 50 Torr, or about 100 Torr. For example, during the hot annealing process, the processing volume in the processing chamber can have approximately 5 mTorr to approximately 100 Torr, approximately 10 mTorr to approximately 100 Torr, approximately 100 mTorr to approximately 100 Torr, approximately 500 mTorr to approximately 100 Torr, approximately 1 Torr to approximately 100 Torr, approximately 5 Torr to approximately 100 Torr, approximately 10 Torr to approximately 100 Torr, approximately 25 Torr to approximately 100 Torr, approximately 50 Torr to approximately 100 Torr, approximately 0.5 mTorr to approximately 20 Torr, Pressures of approximately 5 mTorr to approximately 20 Torr, approximately 10 mTorr to approximately 20 Torr, approximately 100 mTorr to approximately 20 Torr, approximately 500 mTorr to approximately 20 Torr, approximately 1 Torr to approximately 20 Torr, approximately 5 Torr to approximately 20 Torr, approximately 10 Torr to approximately 20 Torr, approximately 0.5 mTorr to approximately 1 Torr, approximately 5 mTorr to approximately 1 Torr, approximately 10 mTorr to approximately 1 Torr, approximately 100 mTorr to approximately 1 Torr, or approximately 500 mTorr to approximately 1 Torr.

[0038] The hot annealing process significantly reduces the compressive stress from the diamond-like carbon (DLC) film, so that once transformed into a stress-reduced DLC film, most of the compressive stress in the stressed DLC film relaxes, lessens, or is otherwise removed. Many other properties of the stressed DLC film (such as density, elastic modulus, sp) are also affected. 3 The concentrations of hybridized carbon atoms and hydrogen atoms remain the same or substantially similar to those of the stress-reduced diamond-like carbon film.

[0039] The compressive stress of the stress-reduced diamond-like carbon film is less than the compressive stress of the stressed diamond-like carbon film from which the stress-reduced film is generated. In some examples, the compressive stress of the stress-reduced diamond-like carbon film is less than that of the stressed diamond-like carbon film by about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, or about 55% to about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%. For example, the compressive stress of the stress-reduced diamond-like carbon film is less than that of the stressed diamond-like carbon film by approximately 25% to approximately 95%, approximately 25% to approximately 90%, approximately 25% to approximately 80%, approximately 25% to approximately 75%, approximately 25% to approximately 70%, approximately 25% to approximately 60%, approximately 25% to approximately 55%, approximately 25% to approximately 50%, approximately 25% to approximately 40%, approximately 40% to approximately 95%, approximately 40% to approximately 90%, and approximately 4... 0% to about 80%, about 40% to about 75%, about 40% to about 70%, about 40% to about 60%, about 40% to about 55%, about 40% to about 50%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 50% to about 75%, about 50% to about 70%, about 50% to about 60%, about 60% to about 70%, about 60% to about 80%, or about 60% to about 90%.

[0040] The stressed diamond-like carbon film can have compressive stress of -500 MPa or greater, such as about -525 MPa, about -550 MPa, about -575 MPa, about -600 MPa, about -625 MPa, or about -650 MPa to about -675 MPa, about -700 MPa, about -725 MPa, about -750 MPa, about -800 MPa, about -850 MPa, about -900 MPa, about -950 MPa, about -1000 MPa, about -1100 MPa, about -1200 MPa, or greater. For example, stressed diamond-like carbon films can have pressures ranging from -500 MPa to -1200 MPa, -500 MPa to -1000 MPa, -500 MPa to -900 MPa, -500 MPa to -850 MPa, -500 MPa to -800 MPa, -500 MPa to -750 MPa, -500 MPa to -725 MPa, -500 MPa to -700 MPa, -500 MPa to -675 MPa, -500 MPa to -650 MPa, -500 MPa to -625 MPa, -500 MPa to -600 MPa, approximately -600 MPa to -1200 MPa, approximately -600 MPa to -1000 MPa, approximately -600 MPa to -900 MPa, and approximately -600 MPa. The compressive stress is approximately -850 MPa, approximately -600 MPa to approximately -800 MPa, approximately -600 MPa to approximately -750 MPa, approximately -600 MPa to approximately -725 MPa, approximately -600 MPa to approximately -700 MPa, approximately -600 MPa to approximately -675 MPa, approximately -600 MPa to approximately -650 MPa, approximately -600 MPa to approximately -625 MPa, approximately -650 MPa to approximately -1200 MPa, approximately -650 MPa to approximately -1000 MPa, approximately -650 MPa to approximately -900 MPa, approximately -650 MPa to approximately -850 MPa, approximately -650 MPa to approximately -800 MPa, approximately -650 MPa to approximately -750 MPa, approximately -650 MPa to approximately -725 MPa, or approximately -650 MPa to approximately -700 MPa.

[0041] Stress-reduced diamond-like carbon films can have compressive stresses of less than -500 MPa, such as about -10 MPa, about -20 MPa, about -50 MPa, about -80 MPa, about -100 MPa, about -125 MPa, about -150 MPa, about -175 MPa, about -200 MPa, about -225 MPa, about -250 MPa, about -275 MPa, or about -300 MPa to about -325 MPa, about -350 MPa, about -375 MPa, about -400 MPa, about -425 MPa, about -450 MPa, about -475 MPa, about -490 MPa, about -495 MPa, about -499 MPa, or less than -500 MPa. For example, stress-reducing diamond-like carbon films can have pressures ranging from approximately -20 MPa to less than -500 MPa, approximately -50 MPa to less than -500 MPa, approximately -80 MPa to less than -500 MPa, approximately -100 MPa to less than -500 MPa, approximately -150 MPa to less than -500 MPa, approximately -200 MPa to less than -500 MPa, approximately -225 MPa to less than -500 MPa, approximately -250 MPa to less than -500 MPa, and approximately -275 MPa. a to less than -500MPa, approximately -300MPa to less than -500MPa, approximately -325MPa to less than -500MPa, approximately -350MPa to less than -500MPa, approximately -375MPa to less than -500MPa, approximately -400MPa to less than -500MPa, approximately -450MPa to less than -500MPa, approximately -20MPa to approximately -400MPa, approximately -50MPa to approximately -400MPa, approximately -80MPa to approximately -400MPa Pa, approximately -100 MPa to approximately -400 MPa, approximately -150 MPa to approximately -400 MPa, approximately -200 MPa to approximately -400 MPa, approximately -225 MPa to approximately -400 MPa, approximately -250 MPa to approximately -400 MPa, approximately -275 MPa to approximately -400 MPa, approximately -300 MPa to approximately -400 MPa, approximately -325 MPa to approximately -400 MPa, approximately -350 MPa to approximately -400 MPa, approximately -375 MPa to Compressive stress of approximately -400 MPa, approximately -20 MPa to approximately -300 MPa, approximately -50 MPa to approximately -300 MPa, approximately -80 MPa to approximately -300 MPa, approximately -100 MPa to approximately -300 MPa, approximately -150 MPa to approximately -300 MPa, approximately -200 MPa to approximately -300 MPa, approximately -225 MPa to approximately -300 MPa, approximately -250 MPa to approximately -300 MPa, or approximately -275 MPa to approximately -300 MPa.

[0042] In one or more examples, the stressed diamond-like carbon film has a compressive stress of about -600 MPa to about -1000 MPa, and upon conversion, the stress-reduced diamond-like carbon film has a compressive stress of about -20 MPa to about -400 MPa or about -150 MPa to about -400 MPa. In some examples, the stressed diamond-like carbon film has a compressive stress of about -650 MPa to about -900 MPa, and upon conversion, the stress-reduced diamond-like carbon film has a compressive stress of about -50 MPa to about -350 MPa or about -200 MPa to about -350 MPa. In other examples, the stressed diamond-like carbon film has a compressive stress of about -700 MPa to about -850 MPa, and upon conversion, the stress-reduced diamond-like carbon film has a compressive stress of about -100 MPa to about -325 MPa or about -250 MPa to about -325 MPa.

[0043] In some embodiments, hydrogen radicals are fed via RPS, which results in the reduction of sp... 2 Selective etching of hybridized carbon atoms, thus further increasing the sp2 of the film. 3 The hybridized carbon atom fraction further increases etching selectivity. The high etching selectivity of stress-reduced diamond-like carbon films is achieved through higher density and modulus compared to current-generation films. Without being bound by theory, it is believed that the higher density and modulus are due to the increased spx content in stress-reduced diamond-like carbon films. 3 The high content of hybrid carbon atoms makes this possible through a combination of low pressure and plasma power.

[0044] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have an sp(t) of at least 40 atomic percent (at%), about 45 at%, about 50 at%, about 55 at%, or about 58 at% to about 60 at%, about 65 at%, about 70 at%, about 75 at%, about 80 at%, about 85 at%, about 88 at%, about 90 at%, about 92 at%, or about 95 at% based on the total amount of carbon atoms in the respective diamond-like carbon film. 3 The concentration or percentage of hybridized carbon atoms (e.g., sp). 3(Hybridized carbon atom content). For example, each of a stressed diamond-like carbon film and a stress-reduced diamond-like carbon film may independently have a total amount of carbon atoms in the respective diamond-like carbon film of at least 40 at% to about 95 at%, about 45 at% to about 95 at%, about 50 at% to about 95 at%, about 50 at% to about 90 at%, about 50 at% to about 85 at%, about 50 at% to about 80 at%, about 50 at% to about 75 at%, about 50 at% to about 70 at%, about 50 at% to about 65 at%, about 55 at% to about 75 at%, about 55 at% to about 70 at%, about 55 at% to about 65 at%, about 55 at% to about 65 at%. 60at%, about 60at% to about 80at%, about 60at% to about 75at%, about 60at% to about 70at%, about 60at% to about 65at%, about 65at% to about 95at%, about 65at% to about 90at%, about 65at% to about 85at%, about 65at% to about 80at%, about 65at% to about 75at%, about 65at% to about 70at%, about 65at% to about 68at%, about 75at% to about 95at%, about 75at% to about 90at%, about 75at% to about 85at%, about 75at% to about 80at%, or about 75at% to about 78at% of sp 3 The concentration or percentage of hybridized carbon atoms.

[0045] In some embodiments, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have a sp content of less than 60 at%, such as less than 55 at% or less than 50 at%. 2 The concentration or percentage of hybridized carbon atoms (e.g., sp). 2 (Hybridized carbon atom content). Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have a sp(x) content of approximately 5 at%, approximately 10 at%, approximately 15 at%, approximately 20 at%, approximately 25 at%, approximately 28 at%, or approximately 30 at% to approximately 32 at%, approximately 35 at%, approximately 36 at%, approximately 38 at%, approximately 40 at%, approximately 45 at%, approximately 50 at%, approximately 55 at%, or approximately 60 at% based on the total amount of carbon atoms in the respective diamond-like carbon film. 2The concentration or percentage of hybridized carbon atoms. For example, each of a stressed diamond-like carbon film and a stress-reduced diamond-like carbon film may independently have about 5 at% to about 60 at% of the total amount of carbon atoms in the respective diamond-like carbon film, about 5 at% to about 50 at% of the total amount of carbon atoms, about 5 at% to about 45 at% of the total amount of carbon atoms in the respective diamond-like carbon film, about 5 at% to about 38 at% of the total amount of carbon atoms, about 5 at% to about 36 at% of the total amount of carbon atoms, about 5 at% to about 35 at% of the total amount of carbon atoms, about 5 at% to about 32 at% of the total amount of carbon atoms, about 5 at% to about 30 at% of the total amount of carbon atoms, about 5 at% to about 25 at% of the total amount of carbon atoms, about 5 at% to about 20 at% of the total amount of carbon atoms, about 5 at% to about 15 at% of the total amount of carbon atoms, about 5 at% to about 10 at% of the total amount of carbon atoms, about 20 at% to about 60 at% of the total amount of carbon atoms, about 20 at% to about 50 at% of the total amount of carbon atoms, about 20 at% to about 45 at% of the total amount of carbon atoms, about 20 at% to about 40 at% of the total amount of carbon atoms in the respective diamond-like carbon film, about 5 at% to about 60 at% of the total amount of carbon atoms, about 20 at% to about 60 at% of the total amount of carbon atoms, about 20 at% to about 50 at% of the total amount of carbon atoms, about 20 at% to about 4 ... About 20 at% to about 38 at%; about 20 at% to about 36 at%; about 20 at% to about 35 at%; about 20 at% to about 32 at%; about 20 at% to about 30 at%; about 20 at% to about 25 at%; about 20 at% to about 22 at%; about 30 at% to about 60 at%; about 30 at% to about 50 at%; about 30 at% to about 45 at%; about 30 at% to about 40 at%; about 30 at% to about 38 at%; about 30 at% to about 36 at%; about 30 at% to about 35 at%; about 30 at% to about 32 at%; about 32 at% to about 38 at%; about 32 at% to about 36 at%; about 32 at% to about 34 at%; about 34 at% to about 38 at%; or about 34 at% to about 36 at% of sp. 2 The concentration or percentage of hybridized carbon atoms.

[0046] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film independently has a concentration greater than 1.5 g / cc (grams per cubic centimeter). 3The density of the product is approximately 1.55 g / cc, approximately 1.6 g / cc, approximately 1.65 g / cc, or approximately 1.68 g / cc to approximately 1.7 g / cc, approximately 1.72 g / cc, approximately 1.75 g / cc, approximately 1.78 g / cc, approximately 1.8 g / cc, approximately 1.85 g / cc, approximately 1.9 g / cc, approximately 1.95 g / cc, approximately 1.98 g / cc, approximately 2 g / cc, approximately 2.05 g / cc, approximately 2.1 g / cc, or greater.For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film independently has a value greater than 1.5 g / cc to about 2.1 g / cc, greater than 1.5 g / cc to about 2.05 g / cc, greater than 1.5 g / cc to about 2 g / cc, greater than 1.5 g / cc to about 1.9 g / cc, greater than 1.5 g / cc to about 1.85 g / cc, greater than 1.5 g / cc to about 1.8 g / cc, greater than 1.5 g / cc to about 1.78 g / cc, greater than 1.5 g / cc to about 1.75 g / cc, greater than 1.5 g / cc to about 1.72 g / cc, and greater than 1.5 g / cc to about 1. 0.7g / cc, greater than 1.5g / cc to about 1.68g / cc, greater than 1.5g / cc to about 1.65g / cc, greater than 1.5g / cc to about 1.6g / cc, about 1.6g / cc to about 2.1g / cc, about 1.6g / cc to about 2.05g / cc, about 1.6g / cc to about 2g / cc, about 1.6g / cc to about 1.9g / cc, about 1.6g / cc to about 1.85g / cc, about 1.6g / cc to about 1.8g / cc, about 1.6g / cc to about 1.78g / cc, about 1.6g / cc to about 1.75g / cc, about 1.6g / cc to Approximately 1.72g / cc, approximately 1.6g / cc to approximately 1.7g / cc, approximately 1.6g / cc to approximately 1.68g / cc, approximately 1.6g / cc to approximately 1.65g / cc, approximately 1.68g / cc to approximately 2.1g / cc, approximately 1.68g / cc to approximately 2.05g / cc, approximately 1.68g / cc to approximately 2g / cc, approximately 1.68g / cc to approximately 1.9g / cc, approximately 1.68g / cc to approximately 1.85g / cc, approximately 1.68g / cc to approximately 1.8g / cc, approximately 1.68g / cc to approximately 1.78g / cc, approximately 1.68g / cc to approximately 1.75g / cc, approximately Densities ranging from 1.68 g / cc to about 1.72 g / cc, from about 1.68 g / cc to about 1.7 g / cc, from about 1.7 g / cc to about 1.75 g / cc, from about 1.7 g / cc to about 1.72 g / cc, from about 1.55 g / cc to less than 2 g / cc, from about 1.6 g / cc to less than 2 g / cc, from about 1.65 g / cc to less than 2 g / cc, from about 1.68 g / cc to less than 2 g / cc, from about 1.7 g / cc to less than 2 g / cc, from about 1.72 g / cc to less than 2 g / cc, from about 1.75 g / cc to less than 2 g / cc, or from about 1.8 g / cc to less than 2 g / cc.

[0047] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film can independently possess approximately about about about about about or about to approximately about about about about about about about about about about about about about Or even thicker. For example, each of a stressed diamond-like carbon film and a stress-reduced diamond-like carbon film can independently have approximately to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately about to approximately or about to approximately The thickness.

[0048] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have a refractive index or n value (n(at 633 nm)) greater than 2, such as about 2.1, about 2.2, about 2.3, about 2,4 or about 2.5 to about 2.6, about 2.7, about 2.8, about 2,9 or about 3. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have a refractive index or n value (n(at 633 nm)) greater than 2 to about 3, greater than 2 to about 2.8, greater than 2 to about 2.5, greater than 2 to about 2.3, about 2.1 to about 3, about 2.1 to about 2.8, about 2.1 to about 2.5, about 2.1 to about 2.3, about 2.3 to about 3, about 2.3 to about 2.8, or about 2.3 to about 2.5.

[0049] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film can independently have an extinction coefficient or k-value (K(at 633 nm)) greater than 0.1, such as about 0.15, about 0.2, about 0.25, or about 0.3. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film can independently have an extinction coefficient or k-value (K(at 633 nm)) greater than 0.1 to about 0.3, greater than 0.1 to about 0.25, greater than 0.1 to about 0.2, greater than 0.1 to about 0.15, about 0.2 to about 0.3, or about 0.2 to about 0.25.

[0050] Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film can independently have an elastic modulus greater than 50 GPa or greater than 60 GPa, such as about 65 GPa, about 70 GPa, about 75 GPa, about 90 GPa, about 100 GPa, about 125 GPa, or about 150 GPa to about 175 GPa, about 200 GPa, about 250 GPa, about 275 GPa, about 300 GPa, about 350 GPa, or about 400 GPa. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film can independently have a strength greater than 60 GPa to about 400 GPa, greater than 60 GPa to about 350 GPa, greater than 60 GPa to about 300 GPa, greater than 60 GPa to about 250 GPa, greater than 60 GPa to about 200 GPa, greater than 60 GPa to about 150 GPa, greater than 60 GPa to about 125 GPa, greater than 60 GPa to about 100 GPa, greater than 60 GPa to about 80 GPa, about 65 GPa to about 400 GPa, about 65 GPa to about 350 GPa, or about 65 GPa to about 300 GPa. The elastic modulus is approximately 0 GPa, approximately 65 GPa to approximately 250 GPa, approximately 65 GPa to approximately 200 GPa, approximately 65 GPa to approximately 150 GPa, approximately 65 GPa to approximately 125 GPa, approximately 65 GPa to approximately 100 GPa, approximately 65 GPa to approximately 80 GPa, approximately 80 GPa to approximately 400 GPa, approximately 80 GPa to approximately 350 GPa, approximately 80 GPa to approximately 300 GPa, approximately 80 GPa to approximately 250 GPa, approximately 80 GPa to approximately 200 GPa, approximately 80 GPa to approximately 150 GPa, approximately 80 GPa to approximately 125 GPa, or approximately 80 GPa to approximately 100 GPa.

[0051] In some embodiments, the stress-reduced diamond-like carbon film is a lower layer for extreme ultraviolet (“EUV”) lithography. In some examples, the stress-reduced diamond-like carbon film is a lower layer for EUV lithography and has a spline density of about 40% to about 90% based on the total amount of carbon atoms in the film. 3 Hybridized carbon atoms, a density greater than 1.5 g / cc to about 1.9 g / cc, and an elastic modulus greater than or about 60 GPa to about 150 GPa or about 200 GPa.

[0052] Figure 1AA schematic diagram of a substrate processing system 132 for performing stressed diamond-like carbon film deposition according to embodiments described herein is depicted. The substrate processing system 132 includes a processing chamber 100 and a controller 110 coupled to a gas control board 130. The processing chamber 100 generally includes a top wall 124, side walls 101, and a bottom wall 122 defining a processing volume 126. A substrate support assembly 146 is provided within the processing volume 126 of the processing chamber 100. The substrate support assembly 146 generally includes an electrostatic chuck 150 supported by a rod 160. The electrostatic chuck 150 may be made generally of aluminum, ceramic, and other suitable materials. The electrostatic chuck 150 can be moved vertically within the processing chamber 100 using a shifting mechanism (not shown).

[0053] A vacuum pump 102 is coupled to a port formed in the bottom of the processing chamber 100. The vacuum pump 102 is used to maintain a desired gas pressure in the processing chamber 100. The vacuum pump 102 also evacuates the processing chamber 100 of post-process gases and byproducts.

[0054] The substrate processing system 132 may further include additional devices for controlling chamber pressure, such as valves (e.g., throttle valves and isolation valves) positioned between the processing chamber 100 and the vacuum pump 102 to control chamber pressure.

[0055] A gas distribution assembly 120 having multiple orifices 128 is disposed on top of a processing chamber 100 above an electrostatic chuck 150. The orifices 128 of the gas distribution assembly 120 are used to introduce processing gases (e.g., deposition gases, dilution gases, carrier gases, purification gases) into the processing chamber 100. The orifices 128 may have different sizes, numbers, distributions, shapes, designs, and diameters to facilitate the flow of various processing gases for different processing needs. The gas distribution assembly 120 is connected to a gas control plate 130 that allows the supply of various gases to the processing volume 126 during processing. Plasma is formed by the processing gas mixture exiting the gas distribution assembly 120 to enhance the thermal decomposition of the processing gases, resulting in material deposition on the surface 191 of the substrate 190.

[0056] Gas distribution assembly 120 and electrostatic chuck 150 may form a pair of spaced-apart electrodes within processing volume 126. One or more RF power supplies 140 provide a bias potential to gas distribution assembly 120 via an optional matching network 138 to facilitate plasma generation between gas distribution assembly 120 and electrostatic chuck 150. Alternatively, RF power supply 140 and matching network 138 may be coupled to gas distribution assembly 120 and electrostatic chuck 150, or to both gas distribution assembly 120 and electrostatic chuck 150, or coupled to an antenna (not shown) disposed outside processing chamber 100. In one or more examples, RF power supply 140 may generate power at frequencies of approximately 350 kHz, approximately 2 MHz, approximately 13.56 MHz, approximately 27 MHz, approximately 40 MHz, approximately 60 MHz, or approximately 100 MHz. In some examples, RF power supply 140 may provide approximately 100 watts to approximately 3000 watts of power at frequencies of approximately 50 kHz to approximately 13.6 MHz. In other examples, the RF power supply 140 can provide approximately 500 watts to approximately 1800 watts of power at frequencies ranging from approximately 50 kHz to approximately 13.6 MHz.

[0057] The controller 110 includes a central processing unit (CPU) 112, a memory 116, and support circuitry 114 for controlling the process sequence and adjusting the gas flow from the gas control board 130. The CPU 112 can be any type of general-purpose computer processor that can be used in an industrial environment. Software routines can be stored in the memory 116, such as random access memory, read-only memory, floppy disk, hard disk, or other forms of digital storage. The support circuitry 114 is conventionally coupled to the CPU 112 and may include cache, clock circuitry, input / output systems, power supplies, and the like. Bidirectional communication between the controller 110 and the various components of the board processing system 132 is handled via several signal cables (collectively referred to as signal buses 118), some of which are in… Figure 1A As shown in the image.

[0058] Figure 1B A schematic cross-sectional view is depicted of another substrate processing system 180 that can be used to practice the embodiments described herein. The substrate processing system 180 is similar to... Figure 1A The substrate processing system 132 differs from the substrate processing system 180 in that the substrate processing system 180 is configured such that processing gas flows from the gas control plate 130 across the surface 191 of the substrate 190 via the sidewall 101. Furthermore, Figure 1A The gas distribution assembly 120 depicted is replaced by an electrode 182. The electrode 182 may be configured for secondary electron generation. In one or more embodiments, the electrode 182 is a silicon-containing electrode.

[0059] Figure 2The embodiments described herein are depicted in detail. Figure 1A and Figure 1B A schematic cross-sectional view of the substrate support assembly 146 used in the processing system. See also Figure 2 The electrostatic chuck 150 may include a heater element 170 suitable for controlling the temperature of a substrate 190 supported on the upper surface 192 of the electrostatic chuck 150. The heater element 170 may be embedded in the electrostatic chuck 150. The electrostatic chuck 150 can be resistively heated by applying current from a heater power supply 106 to the heater element 170. The heater power supply 106 may be coupled via an RF filter 216. The RF filter 216 may be used to protect the heater power supply 106 from RF energy. The heater element 170 may be made of a nickel-iron-chromium alloy (e.g., The electrode is made of nickel-chromium wire encapsulated in an alloy sheath. The current supplied from the heater power supply 106 is adjusted by the controller 110 to control the heat generated by the heater element 170, thus maintaining the substrate 190 and the electrostatic chuck 150 at a substantially constant temperature during film deposition. The supplied current can be adjusted to selectively control the temperature of the electrostatic chuck 150 from about -50°C to about 600°C.

[0060] Referring to Figure 1, a temperature sensor 172 (such as a thermocouple) may be embedded in the electrostatic clamp 150 to monitor the temperature of the electrostatic clamp 150 in a conventional manner. The measured temperature is used by the controller 110 to control the power supplied to the heater element 170 to maintain the substrate at the desired temperature.

[0061] The electrostatic chuck 150 includes a clamping electrode 210, which may be a mesh of conductive material. The clamping electrode 210 can be embedded in the electrostatic chuck 150. The clamping electrode 210 is coupled to a clamping power supply 212, which, when powered, electrostatically clamps the substrate 190 to the upper surface 192 of the electrostatic chuck 150.

[0062] The clamping electrode 210 may be configured as a unipolar or bipolar electrode, or have another suitable arrangement. The clamping electrode 210 may be coupled to a clamping power supply 212 via an RF filter 214, which provides direct current (DC) power to electrostatically hold the substrate 190 to the upper surface 192 of the electrostatic chuck 150. The RF filter 214 prevents the RF power used to form plasma within the processing chamber 100 from damaging electrical equipment or causing electrical hazards outside the chamber. The electrostatic chuck 150 may be made of a ceramic material, such as aluminum nitride or alumina (e.g., aluminum oxide). Alternatively, the electrostatic chuck 150 may be made of a polymer, such as polyimide, polyetheretherketone (PEEK), polyaryletherketone (PAEK), and the like.

[0063] Power application system 220 is coupled to substrate support assembly 146. Power application system 220 may include heater power supply 106, clamping power supply 212, first radio frequency (RF) power supply 230, and second RF power supply 240. Power application system 220 may additionally include controller 110 and sensor assembly 250 communicating with both controller 110 and the first RF power supply 230 and the second RF power supply 240. Controller 110 may also be used to control plasma from process gas by applying RF power from the first RF power supply 230 and the second RF power supply 240 to deposit a material layer on substrate 190.

[0064] As described above, the electrostatic chuck 150 includes a clamping electrode 210, which can be used in one configuration to clamp the substrate 190 and also serves as a first RF electrode. The electrostatic chuck 150 may also include a second RF electrode 260, and together with the clamping electrode 210, can apply RF power to tune the plasma. A first RF power supply 230 may be coupled to the second RF electrode 260, and a second RF power supply 240 may be coupled to the clamping electrode 210. A first matching network and a second matching network may be provided for the first RF power supply 230 and the second RF power supply 240, respectively. The second RF electrode 260 may be a solid metal plate of conductive material as shown in the figure. Alternatively, the second RF electrode 260 may be a grid of conductive material.

[0065] The first RF power source 230 and the second RF power source 240 may generate power at the same frequency or different frequencies. In one or more embodiments, one or both of the first RF power source 230 and the second RF power source 240 may independently generate power at frequencies from about 350 kHz to about 100 MHz (e.g., 350 kHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, or 100 MHz). In one or more embodiments, the first RF power source 230 may generate power at a frequency of 13.56 MHz, and the second RF power source 240 may generate power at a frequency of 2 MHz, or vice versa. The RF power from one or both of the first RF power source 230 and the second RF power source 240 may be varied to tune the plasma. For example, the sensor assembly 250 may be used to monitor the RF energy from one or both of the first RF power source 230 and the second RF power source 240. Data from sensor assembly 250 can be communicated to controller 110, and controller 110 can be used to change the power applied by first RF power supply 230 and second RF power supply 240.

[0066] In one or more embodiments, the electrostatic chuck 150 has clamping electrodes 210a and RF electrodes that are separated from each other, and a first RF bias voltage can be applied to the RF electrode 260, and a second RF voltage can be applied to the clamping electrode 210. In one or more examples, the first RF bias voltage is provided at a frequency of about 350 kHz to about 100 MHz at a power of about 10 watts to about 3000 watts, and the second RF bias voltage is provided at a frequency of about 350 kHz to about 100 MHz at a power of about 10 watts to about 3000 watts. In other examples, the first RF bias voltage is provided at a frequency of about 13.56 MHz at a power of about 2500 watts to about 3000 watts, and the second RF bias voltage is provided at a frequency of about 2 MHz at a power of about 800 watts to about 1200 watts.

[0067] In one or more embodiments, a deposition gas containing one or more hydrocarbons may flow into or otherwise introduce into the processing volume of a processing chamber (such as a PE-CVD chamber). Hydrocarbons and dilution gases (if used) may flow into or be introduced into the processing volume independently. In some examples, one or more substrates are positioned on an electrostatic chuck within the processing chamber. The electrostatic chuck may have clamping electrodes and RF electrodes separated from each other. Plasma may be ignited or otherwise generated at or near the substrate (e.g., at substrate level) by applying a first RF bias to the RF electrodes and a second RF bias to the clamping electrodes. A stressed diamond-like carbon film is deposited or otherwise formed on the substrate. In some embodiments, a patterned photoresist layer may be deposited or otherwise formed over the stressed diamond-like carbon film, the stressed diamond-like carbon film being etched or otherwise formed with a pattern corresponding to the patterned photoresist layer, and the pattern being etched or otherwise formed into the substrate. In other embodiments, the stressed diamond-like carbon film is transformed into a stress-reduced diamond-like carbon film, and a patterned photoresist layer may be deposited or otherwise formed over the stress-reduced diamond-like carbon film. The stress-reduced diamond-like carbon film is then etched or otherwise formed with a pattern corresponding to the patterned photoresist layer, and the pattern is etched or otherwise formed into the substrate.

[0068] Generally, the following exemplary deposition process parameters can be used to form stressed diamond-like carbon films. The substrate temperature can range from about -50°C to about 350°C (e.g., about -40°C to about 100°C, about 10°C to about 100°C, or about 10°C to about 50°C). The chamber pressure can range from about 0.5 mTorr to about 10 Torr (e.g., about 2 mTorr to about 50 mTorr; or about 2 mTorr to about 10 mTorr). The hydrocarbon flow rate can be from about 20 sccm to about 5000 sccm (e.g., about 50 sccm to about 1000 sccm, about 100 sccm to about 200 sccm, or about 150 sccm to about 200 sccm). The flow rate of the dilution gas or purifying gas (e.g., He) can be from about 1 sccm to about 3000 sccm (e.g., about 5 sccm to about 500 sccm, about 10 sccm to about 150 sccm, or about 20 sccm to about 100 sccm). Stressed diamond-like carbon films can be deposited up to approximately... With the agreement The thickness (e.g., approximately) to approximately about to approximately about With the agreement or about to approximately —Depending on the application). In one or more examples, these process parameters provide examples of process parameters for 300 mm substrates in deposition chambers available from Applied Materials, Inc., Santa Clara, California.

[0069] Figure 3 A flowchart depicts a method 300 for forming a stress-reduced diamond-like carbon film on a film stack disposed on a substrate, according to an embodiment of the present disclosure. The stress-reduced diamond-like carbon film formed on the film stack can be used, for example, as a hard mask to form a step-like structure in the film stack. Figures 4A to 4B This is a schematic cross-sectional view illustrating a sequence for forming a stress-reducing diamond-like carbon film on a film stack disposed on a substrate, according to method 300. Although method 300 is described below with reference to forming a hard mask layer on the film stack for fabricating a step-like structure in a film stack of a three-dimensional semiconductor device, method 300 can also be advantageously used in other device fabrication applications. Furthermore, it should be understood that... Figure 3 The operations described in the text can be performed simultaneously and / or with... Figure 3 The order described in the text is different from the order in which they are executed.

[0070] Method 300 involves using a substrate (such as...) Figure 4AThe substrate 402 depicted in the image is positioned within the processing chamber (such as...). Figure 1A or Figure 1B Operation 310 begins in the processing volume of the processing chamber 100 (described in the image). The substrate 402 may be... Figure 1A , Figure 1B and Figure 2 The substrate 190 is depicted in the figure. The substrate 402 may be positioned on an electrostatic chuck (e.g., the upper surface 192 of the electrostatic chuck 150). If desired, the substrate 402 may be a silicon-based material on which a film stack 404 is disposed, or any suitable insulating or conductive material that may be used to form a structure 400, such as a step-like structure, in the film stack 404.

[0071] like Figure 4A As depicted in the embodiments, substrate 402 may have a substantially flat surface, a non-uniform surface, or a substantially flat surface on which structures are formed. A film stack 404 is formed on substrate 402. In one or more embodiments, film stack 404 may be used to form gate structures, contact structures, or interconnect structures in front-end or back-end processes. Method 300 may be performed on film stack 404 to form a stepped structure used in memory structures such as NAND structures. In one or more embodiments, substrate 402 may be a material such as crystalline silicon (e.g., Si). <100> or Si <111> Substrate 402 may include silicon oxide, strained silicon, germanium silicon, doped or undoped polycrystalline silicon, doped or undoped silicon substrates, patterned or unpatterned silicon on insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, and sapphire. Substrate 402 may have various sizes, such as substrates with diameters of 200 mm, 300 mm, 450 mm, or other diameters, and rectangular or square panels. Unless otherwise stated, the embodiments and examples described herein are performed on substrates having diameters of 200 mm, 300 mm, or 450 mm. In embodiments where an SOI structure is used for substrate 402, substrate 402 may include an embedded dielectric layer disposed on a crystalline silicon substrate. In one or more embodiments depicted herein, substrate 402 may be a crystalline silicon substrate.

[0072] In one or more embodiments, the film stack 404 disposed on the substrate 402 may have a plurality of vertically stacked layers. The film stack 404 may include a first layer (illustrated as 408a1, 408a2, 408a3, ..., 408a) repeatedly formed in the film stack 404. n ) and the second layer (shown as 408b1, 408b2, 408b3, ..., 408b) nThe pair consists of repeatedly formed alternating first layers (illustrated as 408a1, 408a2, 408a3, ..., 408a...). n ) and the second layer (shown as 408b1, 408b2, 408b3, ..., 408b) n (, until the desired number of pairs in the first and second layers are reached).

[0073] The 404 film stack can be part of a semiconductor chip, such as a three-dimensional memory chip. Although in Figure 4A Up to the first layer of icons in Figure B (icons are 408a1, 408a2, 408a3, ..., 408a) n ) and the second layer (shown as 408b1, 408b2, 408b3, ..., 408b) n The three repeating layers of the first and second layers can be used as needed, noting that any desired number of repeating pairs of the first and second layers can be utilized.

[0074] In one or more embodiments, the film stack 404 can be used to form multiple gate structures of a three-dimensional memory chip. The first layers 408a1, 408a2, 408a3, ..., 408a... are formed in the film stack 404. n It can be the first dielectric layer, and the second layer can be 408b1, 408b2, 408b3, ..., 408b n It can be the second dielectric layer. Suitable dielectric layers can be used to form the first layer 408a1, 408a2, 408a3, ..., 408a n And the second layer consists of 408b1, 408b2, 408b3, ..., 408b n This includes silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon carbide, titanium nitride, compounds of oxides and nitrides, at least one or more oxide layers sandwiched with a nitride layer, and combinations thereof. In one or more embodiments, the dielectric layer may be a high dielectric constant material with a dielectric constant greater than 4. Suitable examples of high dielectric constant materials include hafnium oxide, zirconium oxide, titanium oxide, hafnium silicon oxide or hafnium silicate, hafnium aluminum oxide or hafnium aluminate, zirconium silicon oxide or zirconium silicate, tantalum oxide, aluminum oxide, aluminum-doped hafnium dioxide, bismuth strontium titanium (BST), and platinum zirconium titanium (PZT), dopants thereof, or any combination thereof.

[0075] In one or more examples, the first layer is 408a1, 408a2, 408a3, ..., 408a n It is a silicon oxide layer, and the second layer is 408b1, 408b2, 408b3, ..., 408b nIt is in the first layer 408a1, 408a2, 408a3, ..., 408a n A silicon nitride layer or a polysilicon layer is disposed on top. In one or more embodiments, the first layer is 408a1, 408a2, 408a3, ..., 408a... n The thickness can be controlled to approximately to approximately Such as And each second layer is 408b1, 408b2, 408b3, ..., 408b n The thickness can be controlled to approximately to approximately Such as The 404 film stack can have approximately to approximately The total thickness. In one or more embodiments, the total thickness of the film stack 404 is from about 3 micrometers to about 10 micrometers and can vary with technological advancements.

[0076] Note that, with or without the presence of film stack 404 on substrate 402, stress-reduced diamond-like carbon film can be formed on any surface or any portion of substrate 402.

[0077] At operation 320, a clamping voltage is applied to an electrostatic chuck, and substrate 402 is clamped or otherwise disposed on the electrostatic chuck. In one or more embodiments, substrate 402 is positioned on an upper surface 192 of electrostatic chuck 150, which provides support and clamps substrate 402 during processing. Electrostatic chuck 150 flattens substrate 402 by pressing it tightly against upper surface 192, thereby preventing backside deposition. An electrical bias voltage is provided to substrate 402 via clamping electrode 210. Clamping electrode 210 is electronically communicative to clamping power supply 212, which supplies a bias voltage to clamping electrode 210. In one or more embodiments, the clamping voltage is about 10 watts to about 3000 watts, about 100 watts to about 2000 watts, or about 200 watts to about 1000 watts.

[0078] During operation 320, several process parameters can be adjusted. In one embodiment suitable for processing a 300mm substrate, the processing pressure in the processing volume can be maintained at about 0.1 mTorr to about 10 Torr (e.g., about 2 mTorr to about 50 mTorr; or about 5 mTorr to about 20 mTorr). In some embodiments suitable for processing a 300mm substrate, the processing temperature and / or substrate temperature can be maintained at about -50°C to about 350°C (e.g., about 0°C to about 50°C; or about 10°C to about 20°C).

[0079] In one or more embodiments, a constant clamping voltage is applied to substrate 402. In some embodiments, the clamping voltage may be pulsed to electrostatic chuck 150. In other embodiments, a back-side gas may be applied to substrate 402 while the clamping voltage is applied to control the temperature of the substrate. The back-side gas may be or include helium, argon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof.

[0080] At operation 330, plasma is generated at the substrate, such as adjacent to or near the substrate level, by applying a first RF bias voltage to the electrostatic chuck. The plasma generated at the substrate can be generated in a plasma region between the substrate and the electrostatic chuck. The first RF bias voltage can be from about 10 watts to about 3000 watts at frequencies from about 350 kHz to about 100 MHz (e.g., about 350 kHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In one or more embodiments, the first RF bias voltage is provided at a power of about 2500 watts to about 3000 watts at a frequency of about 13.56 MHz. In one or more embodiments, the first RF bias voltage is provided to the electrostatic chuck 150 via a second RF electrode 260. The second RF electrode 260 may be electronically communicated with a first RF power supply 230, which supplies a bias voltage to the second RF electrode 260. In one or more embodiments, the bias power is about 10 watts to about 3000 watts, about 2000 watts to about 3000 watts, or about 2500 watts to about 3000 watts. The first RF power supply 230 can generate power at frequencies from about 350 kHz to about 100 MHz (e.g., about 350 kHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz).

[0081] In one or more embodiments, operation 330 further includes applying a second RF bias to the electrostatic chuck. The second RF bias can range from about 10 watts to about 3000 watts at frequencies from about 350 kHz to about 100 MHz (e.g., about 350 kHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In some examples, the second RF bias is provided at a power of about 800 watts to about 1200 watts at a frequency of about 2 MHz. In other examples, the second RF bias is provided to the substrate 402 via a clamping electrode 210. The clamping electrode 210 may be in electronic communication with a second RF power supply 240, which supplies a bias voltage to the clamping electrode 210. In one or more examples, the bias power is about 10 watts to about 3000 watts, about 500 watts to about 1500 watts, or about 800 watts to about 1200 watts. The second RF power supply 240 can generate power at frequencies from about 350 kHz to about 100 MHz (e.g., about 350 kHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In one or more embodiments, the clamping voltage supplied in operation 320 is maintained during operation 330.

[0082] In some embodiments, during operation 330, a first RF bias is provided to the substrate 402 via clamping electrode 210, and a second RF bias may be provided to the substrate 402 via a second RF electrode 260. In one or more examples, the first RF bias is about 2500 watts (about 13.56 MHz) and the second RF bias is about 1000 watts (about 2 MHz).

[0083] During operation 340, a deposition gas is flowed into the processing volume 126 to form a stressed diamond-like carbon film on the film stack. The deposition gas may flow into the processing volume 126 through the gas distribution assembly 120 or via the sidewall 101 from the gas control panel 130. The deposition gas contains one or more hydrocarbons. The hydrocarbons may be or include one, two, or more hydrocarbons in any physical state. The hydrocarbons may be any liquid or gas, but if any precursor is vapor at room temperature, several advantages can be achieved to simplify the hardware required for material metering, control, and delivery to the processing volume.

[0084] The deposition gas may further include an inert gas, a diluent gas, an etchant gas, or any combination thereof. In one or more embodiments, the clamping voltage supplied during operation 320 is maintained during operation 340. In some embodiments, the processing conditions established during operation 320 and the plasma formed during operation 330 are maintained during operation 340.

[0085] In one or more embodiments, the hydrocarbon is a gaseous or liquid hydrocarbon. The hydrocarbon may be or include one or more alkanes, one or more alkenes, one or more alkynes, one or more aromatic compounds, or any combination thereof. In some examples, the hydrocarbon has the general formula C1. x H y Where x has a range of 1 to about 20 and y has a range of 1 to about 20. Suitable hydrocarbons include, for example, C2H2, C3H6, CH4, C4H8, 1,3-dimethyladamantane, bicyclo[2.2.1]hept-2,5-diene (2,5-norbornene), adamantane (C 10 H 16 norbornene (C7H) 10 (or any combination thereof). In one or more examples, the use of acetylene is attributed to the formation of a more stable intermediate, which allows for greater surface fluidity.

[0086] Hydrocarbons can be or include one or more alkanes (e.g., C40, C50, C6 ... n H 2n+2 Where n ranges from 1 to 20. Suitable hydrocarbons include, for example, alkanes such as methane (CH4), ethane (C2H6), propane (C3H8), and butane (C4H4). 10 ) and its isomers isobutane and pentane (C5H 12 ), hexane (C6H) 14 ) and its isomers isopentane and neopentane, hexane (C6H 14 ) and its isomers 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, and 2,2-dimethylbutane, or any combination thereof.

[0087] Hydrocarbons may be or include one or more olefins (e.g., C40, C50, C60, C40, C6 ... n H 2n (where n is from 1 to 20). Suitable hydrocarbons include, for example, alkenes such as ethylene, propylene (C3H6), butene and its isomers, pentene and its isomers, and the like, and dienes such as butadiene, isoprene, pentadiene, hexadiene, or any combination thereof. Additional suitable hydrocarbons include, for example, halogenated alkenes such as monofluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, monochloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, or any combination thereof.

[0088] Hydrocarbons may be or include one or more alkynes (e.g., C40, C50, C60, C7 ... n H 2n-2 (where n is from 1 to 20). Suitable hydrocarbons include, for example, alkynes, such as acetylene (C2H2), propyne (C3H4), butyne (C4H8), vinylacetylene, or any combination thereof.

[0089] Hydrocarbons can be or include one or more aromatic hydrocarbons, such as benzene, styrene, toluene, xylene, ethylbenzene, acetophenone, methyl benzoate, phenyl acetate, phenol, cresol, furan and the like, α-terpinene, methyl isopropylbenzene, 1,1,3,3-tetramethylbutylbenzene, tributyl ether, tributylethylene, methyl methacrylate and tributylfuran ether, compounds having the formulas C3H2 and C5H4, halogenated aromatic compounds including monofluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene, or any combination thereof.

[0090] In one or more embodiments, the deposition gas further comprises one or more diluent gases, one or more carrier gases, and / or one or more purifying gases. Suitable diluent gases, carrier gases, and / or purifying gases, such as helium (He), argon (Ar), xenon (Xe), hydrogen (H2), nitrogen (N2), ammonia (NH3), nitric oxide (NO), or any combination thereof, may flow together with the deposition gas or be otherwise supplied to the processing volume 126. Argon, helium, and / or nitrogen may be used to control the density and deposition rate of the stressed diamond-like carbon film. In some cases, as discussed below, the addition of N2 and / or NH3 may be used to control the hydrogen ratio of the stressed diamond-like carbon film. Alternatively, diluent gases may not be used during deposition.

[0091] In some embodiments, the deposition gas further contains an etchant gas. Suitable etchant gases may be or include chlorine (Cl2), fluorine (F2), hydrogen fluoride (HF), carbon tetrafluoride (CF4), nitrogen trifluoride (NF3), or any combination thereof. Without being bound by theory, it is believed that the etchant gas selectively etches the film. 2 Hybridized carbon atoms, thus increasing sp in the membrane 3 The fraction of hybrid carbon atoms increases the etching selectivity of the stressed diamond-like carbon film 412.

[0092] In one or more embodiments, after a stressed diamond-like carbon film 412 is deposited or otherwise formed on the substrate during operation 340, the stressed diamond-like carbon film 412 is exposed to hydrogen radicals. In some embodiments, the stressed diamond-like carbon film is exposed to hydrogen radicals during the deposition process of operation 340. In other embodiments, hydrogen radicals are formed in the RPS and delivered to the processing area. Without being bound by theory, it is believed that exposing the stressed diamond-like carbon film to hydrogen radicals results in selective etching sp. 2 Hybridized carbon atoms, thus increasing the sp2 of the membrane. 3 The hybridization of carbon atoms increases etching selectivity.

[0093] At operation 350, after a stressed diamond-like carbon film 412 is formed on the substrate, the substrate is released. During operation 350, the clamping voltage is turned off. The reactive gas is shut off and, if necessary, purged from the processing chamber. In one or more embodiments, during operation 350, the RF power is reduced (e.g., about 200 watts). If necessary, controller 110 monitors impedance changes to determine whether electrostatic charge is dissipated to ground via the RF path. Once the substrate is released from the electrostatic chuck, the remaining gas is purged from the processing chamber. The processing chamber is evacuated and the substrate moves upward on the lifting pin and exits the processing chamber.

[0094] In some alternative embodiments, the substrate containing the stressed diamond-like carbon film 412 may be heated before the substrate is released at operation 350 to produce a stress-reduced diamond-like carbon film during a thermal annealing process in the same processing chamber.

[0095] In one or more embodiments, after operation 350, the substrate containing the stressed diamond-like carbon film 412 is moved upward on a lifting pin and exits the plasma processing chamber. At operation 360, the substrate is introduced into another processing chamber, such as a thermal annealing chamber, a vacuum chamber, a deposition chamber, or any other type of processing chamber that can be used to perform the thermal annealing process. The substrate containing the stressed diamond-like carbon film 412 is heated to a temperature of about 200°C to about 600°C for about 15 seconds to about 60 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process.

[0096] Figure 5A flowchart depicts a method 500 using a stress-reduced diamond-like carbon film according to one or more embodiments described and discussed herein. After forming a stress-reduced diamond-like carbon film 412 on a substrate, the stress-reduced diamond-like carbon film 412 can be used as a patterning mask in an etching process to form a three-dimensional structure, such as a step-like structure. The stress-reduced diamond-like carbon film 412 can be patterned using standard photoresist patterning techniques. At operation 510, a patterned photoresist (not shown) can be formed over the stress-reduced diamond-like carbon film 412. At operation 520, the stress-reduced diamond-like carbon film 412 can be etched with a pattern corresponding to the patterned photoresist layer, and then at operation 530, the pattern is etched into the substrate 402. At operation 540, material can be deposited into the etched portion of the substrate 402. At operation 550, the stress-reduced diamond-like carbon film 412 can be removed using a solution containing hydrogen peroxide and sulfuric acid. An exemplary solution containing hydrogen peroxide and sulfuric acid is known as a Piranha solution or a Piranha etching solution. The stress-reduced diamond-like carbon film 412 can also be removed using etching chemicals containing oxygen and halogens (e.g., fluorine or chlorine), such as Cl2 / O2, CF4 / O2, and Cl2 / O2 / CF4. The stress-reduced diamond-like carbon film 412 can also be removed using a chemical mechanical polishing (CMP) process.

[0097] Extreme ultraviolet (EUV) patterning scheme

[0098] When using metal-containing photoresists in extreme ultraviolet (“EUV”) patterning schemes, the choice of the underlying layer is critical for preventing nanofailures (e.g., bridging defects and spacing defects) in semiconductor devices. The conventional underlying layer for EUV patterning (lithography) schemes is spin-on carbon (SOC) material. However, during patterning, metals (such as tin) diffuse through the SOC material, leading to nanofailures in the semiconductor component. These nanofailures result in reduced, degraded, and impaired semiconductor performance.

[0099] On the other hand, the high-density carbon films described herein possess excellent film quality, such as improved hardness and density. Compared to conventional SOC films, this hardness and density allow high-density carbon films to serve as a stronger barrier to metal dissolution and to prevent and minimize nanoscale failures to a greater extent. In one or more embodiments, a stress-reducing diamond-like carbon film is provided for use as a lower layer in extreme ultraviolet (“EUV”) lithography processes.

[0100] In one or more embodiments, the stress-reduced diamond-like carbon film used as the underlying layer in the EUV lithography process can be any film described herein. The stress-reduced diamond-like carbon film can have an spp ratio of approximately 40% to approximately 90% based on the total carbon atoms in the stress-reduced diamond-like carbon film. 3 The hybrid carbon atom content, compressive stress of about -20 MPa to less than -600 MPa, about -150 MPa to less than -600 MPa, or about -200 MPa to less than -600 MPa (such as about -225 MPa to about -500 MPa or about -250 MPa to about -400 MPa), elastic modulus of greater than 60 GPa to about 200 GPa or greater than 60 GPa to about 150 GPa, and density of greater than 1.5 g / cc to about 2.1 g / cc (such as about 1.55 g / cc to less than 2 g / cc, for example, about 1.6 g / cc to about 1.8 g / cc, about 1.65 g / cc to about 1.75 g / cc, or about 1.68 g / cc to about 1.72 g / cc).

[0101] Therefore, methods and apparatus are provided for forming a hard mask layer (which is or contains a stress-reducing diamond-like carbon film) that can be used to form a stepped structure for three-dimensional stacking of semiconductor devices. By utilizing a stress-reducing diamond-like carbon film as a hard mask layer with desired robust film properties and etch selectivity, improved control over the size and profile of the resulting structure formed in the film stack can be obtained, and the electrical performance of the chip assembly can be enhanced in the application of three-dimensional stacking of semiconductor devices.

[0102] In summary, some benefits of this disclosure provide processes for depositing or otherwise forming stress-reduced diamond-like carbon films on substrates. Common PE-CVD hard mask films have very low hybridization sp... 3 The percentage of atoms and therefore the low modulus and etch selectivity. In some embodiments described herein, low processing pressure (less than 1 Torr) and bottom-driven plasma enable the fabrication of sp hybrids with approximately 60% or greater. 3 The atomically doped film results in improved etch selectivity compared to previously available hard mask films. Furthermore, some embodiments described herein are performed at low substrate temperatures, enabling the deposition of additional dielectric films at temperatures significantly lower than currently possible, thus opening up applications with low thermal budgets that cannot currently be addressed by CVD. Additionally, some embodiments described herein can be used as the underlayer in EUV lithography processes.

[0103] While the foregoing relates to embodiments of this disclosure, other and further embodiments of this disclosure may be designed without departing from its essential scope, which is determined by the following claims. All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, provided that they do not contradict this document. As will be apparent from the foregoing general description and specific embodiments, various modifications may be made to this disclosure without departing from its spirit and scope, although the form of this disclosure has been shown and described. Consequently, this disclosure is not intended to be limiting. Likewise, for purposes of U.S. law, the term “comprising” is considered synonymous with the term “including.” Similarly, whenever a composition, element, or group of elements precedes the conjunction “comprising,” it is understood that the same composition or group of elements is contemplated by the conjunction “substantially constitutes,” “consisting of,” “selected from a group of,” or “is,” and vice versa, preceding the description of the composition, element, or multiple elements.

[0104] A set of upper limits and a set of lower limits have been used to describe certain embodiments and features. It should be understood that, unless otherwise specified, a range is contemplated to include any combination of two values, such as any lower limit value combined with any upper limit value, any combination of two lower limits, and / or any combination of two upper limits. Certain lower limits, upper limits, and ranges appear in one or more of the appended claims.

Claims

1. A method for processing a substrate, comprising the following steps: A deposition gas containing hydrocarbons is flowed into a processing volume of a processing chamber having a substrate positioned on an electrostatic chuck, wherein the processing volume is maintained at a pressure of 0.5 mTorr to 10 Torr. Plasma is generated above the substrate in the processing volume by applying a first RF bias to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate, wherein the stressed diamond-like carbon film has a compressive stress of -500 MPa to -1000 MPa. as well as The stressed diamond-like carbon film is heated to a temperature of 200°C to 600°C for 15 seconds to 60 minutes to produce a stress-reduced diamond-like carbon film during a thermal annealing process, wherein the stress-reduced diamond-like carbon film has a compressive stress of -100 MPa to -400 MPa and a density greater than 1.5 g / cc.

2. The method of claim 1, further comprising the following steps: Remove the substrate containing the stressed diamond-like carbon film from the processing chamber; The substrate containing the stressed diamond-like carbon film is positioned in a heat annealing chamber, wherein the stressed diamond-like carbon film is heated to produce a stress-reduced diamond-like carbon film during the heat annealing process; and Remove the substrate containing the stress-reduced diamond-like carbon film from the heat annealing chamber.

3. The method of claim 2, wherein the stressed diamond-like carbon film is heated at a temperature of 300°C to 500°C for 2 to 15 minutes during the thermal annealing process to produce the stress-reduced diamond-like carbon film.

4. The method of claim 2, wherein the hot annealing chamber is maintained at a pressure of 10 mTorr to 100 Torr during the hot annealing process.

5. The method of claim 2, wherein the stressed diamond-like carbon film is heated during the thermal annealing process to produce the stress-reduced diamond-like carbon film in a gas-containing environment, wherein the gas comprises nitrogen (N2), argon, helium, neon, or any combination thereof.

6. The method of claim 1, wherein the compressive stress of the stress-reduced diamond-like carbon film is less than 40% to 90% of the compressive stress of the stressed diamond-like carbon film.

7. The method of claim 1, wherein the stressed diamond-like carbon film has a compressive stress of -600 MPa to -1000 MPa, and wherein the stress-reduced diamond-like carbon film has a compressive stress of -150 MPa to -400 MPa.

8. The method of claim 1, wherein the stress-reduced diamond-like carbon film has an elastic modulus of 65 GPa to 200 GPa.

9. The method of claim 1, wherein the stress-reduced diamond-like carbon film has a density of 1.55 g / cc to 1.8 g / cc.

10. The method of claim 1, wherein when the plasma is generated on the substrate and the stressed diamond-like carbon film is deposited, the processing volume is maintained at a pressure of 5 mTorr to 100 mTorr and the substrate is maintained at a temperature of 0°C to 50°C.

11. The method of claim 1, wherein the stress-reducing diamond-like carbon film comprises 50 atomic percent to 90 atomic percent sp. 3 Hybridized carbon atoms.

12. The method of claim 1, wherein the hydrocarbon comprises acetylene, propylene, methane, butene, 1,3-dimethyladamantane, bicyclo[2.2.1]hept-2,5-diene, adamantane, norbornene, or any combination thereof.

13. The method of claim 1, wherein the deposition gas further comprises helium, argon, xenon, neon, hydrogen (H2), or any combination thereof.

14. The method of claim 1, wherein the step of generating the plasma at the substrate further comprises the steps of: applying a second RF bias to the electrostatic chuck, wherein the electrostatic chuck has a clamping electrode and an RF electrode separate from the clamping electrode, and wherein a first RF bias is applied to the RF electrode and a second RF bias is applied to the clamping electrode.

15. The method of claim 1, wherein the step of generating the plasma at the substrate further comprises the steps of: applying a second RF bias to the electrostatic chuck, wherein the first RF bias is provided at a frequency of 350 kHz to 100 MHz at a power of 10 watts to 3000 watts, and wherein the second RF bias is provided at a frequency of 350 kHz to 100 MHz at a power of 10 watts to 3000 watts.

16. A method for processing a substrate, comprising the following steps: A deposition gas containing hydrocarbons is flowed into a processing volume of a plasma processing chamber having a substrate positioned on an electrostatic chuck, wherein the processing volume is maintained at a pressure of 0.5 mTorr to 10 Torr. Plasma is generated above the substrate in the processing volume by applying a first RF bias voltage to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate, wherein the stressed diamond-like carbon film comprises 50 atomic percent to 90 atomic percent sp. 3 Hybridized carbon atoms and have compressive stress of -500 MPa to -1000 MPa and density greater than 1.5 g / cc; The substrate containing the stressed diamond-like carbon film is transferred from the plasma processing chamber to the thermal annealing chamber; and The stressed diamond-like carbon film is heated to a temperature of 200°C to 600°C for 15 seconds to 60 minutes to produce a stress-reduced diamond-like carbon film during a thermal annealing process, wherein the stress-reduced diamond-like carbon film comprises 50 atomic percent to 90 atomic percent sp. 3 It consists of hybrid carbon atoms and has a compressive stress of -100 MPa to -400 MPa and a density greater than 1.5 g / cc.

17. The method of claim 16, wherein the compressive stress of the stress-reduced diamond-like carbon film is less than 40% to 90% of the compressive stress of the stressed diamond-like carbon film.

18. The method of claim 16, wherein the stressed diamond-like carbon film has a compressive stress of -600 MPa to -1000 MPa and a density of 1.55 g / cc to 1.9 g / cc, and wherein the stress-reduced diamond-like carbon film has a compressive stress of -150 MPa to -400 MPa and a density of 1.55 g / cc to 1.8 g / cc.

19. The method of claim 16, wherein the stress-reduced diamond-like carbon film has an elastic modulus of 65 GPa to 200 GPa.

20. A method for processing a substrate, comprising the following steps: A deposition gas containing hydrocarbons is flowed into a processing volume of a processing chamber having a substrate positioned on an electrostatic chuck. Plasma is generated above the substrate in the processing volume by applying a first RF bias to the electrostatic chuck to deposit a stressed diamond-like carbon film on the substrate, wherein the stressed diamond-like carbon film has a compressive stress of -500 MPa to -1000 MPa. as well as The stressed diamond-like carbon film is heated to a temperature of 200°C to 600°C for 15 seconds to 60 minutes to produce a stress-reduced diamond-like carbon film during a thermal annealing process. The stress-reduced diamond-like carbon film has a compressive stress of -100 MPa to -400 MPa and a density of 1.55 g / cc to 2.1 g / cc. The compressive stress of the stress-reduced diamond-like carbon film is less than 40% to 90% of the compressive stress of the stressed diamond-like carbon film. A patterned photoresist layer is formed over the stress-reduced diamond-like carbon film; The stress-reduced diamond-like carbon film is etched in a pattern corresponding to the patterned photoresist layer; and The pattern is etched into the substrate.

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