TW202200826A - Methods for producing high-density carbon films for hardmasks and other patterning applications - Google Patents

Abstract

Embodiments of the present disclosure generally relate to the fabrication of integrated circuits. More particularly, the embodiments described herein provide methods for producing reduced-stress diamond-like carbon films for patterning applications. In one or more embodiments, a method includes flowing a deposition gas containing a hydrocarbon compound into a processing volume of a process 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 reduced-stress diamond-like carbon film during a thermal annealing process. The reduced-stress diamond-like carbon film has a compressive stress of less than -500 MPa.

Description

Method for producing high density carbon films for hardmask and other patterning applications

Embodiments of the present disclosure generally relate to the fabrication of integrated circuits. More particularly, the embodiments described and discussed herein provide techniques for depositing high density films for patterning applications

Integrated circuits have evolved to complex components that can include millions of transistors, capacitors, and resistors on a single wafer. Advances in chip design continue to require faster circuit systems and greater circuit density. The need for faster circuits with greater circuit density places corresponding demands on the materials used to manufacture such integrated circuits. In particular, as the size of integrated circuit components decreases to the sub-micron scale, it is now necessary to use low resistivity conductive materials as well as low dielectric constant insulating materials to obtain suitable electrical performance from such components.

The need for greater integrated circuit density also places demands on the process sequences used in the manufacture of integrated circuit components. For example, in a fabrication sequence using conventional photolithography techniques, an energy-sensitive resist layer is formed over a stack of material layers disposed on a substrate. The energy sensitive resist layer is exposed to the patterned image to form a photoresist mask. Thereafter, an etching process is used to transfer the mask pattern to the stacked one or more material layers. The chemical etchant used in the etch process is selected to have greater etch selectivity to the stacked layers of material compared to the mask of energy sensitive resist. That is, the chemical etchant etches one or more layers of the material stack at a much faster rate than the energy sensitive resist. The etch selectivity of the stacked one or more material layers over the resist prevents consumption of the energy-sensitive resist before pattern transfer is complete.

As the pattern size is reduced, the thickness of the energy sensitive resist is correspondingly reduced in order to control the pattern resolution. Due to attack by the chemical etchant, such a thin resist layer may not be sufficient to mask the underlying material layer during the pattern transfer step. Due to greater resistance to chemical etchants, intermediate layers called hard masks (eg, silicon oxynitride, silicon carbide, or carbon films) are often used between the energy-sensitive resist layer and the underlying material layer to facilitate Pattern transfer. Hardmask materials with both high etch selectivity and high deposition rates are desirable. Due to critical dimension (CD) reduction, current hard mask materials lack the desired etch selectivity relative to underlying materials (eg, oxides and nitrides) and are often difficult to deposit.

Thus, there is a need in the art for improved hard mask layers and methods for depositing improved hard mask layers.

Embodiments of the present disclosure generally relate to the fabrication of integrated circuits. More particularly, 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 flowing a deposition gas containing a hydrocarbon compound into a processing volume of a processing chamber in which the substrate is positioned on an electrostatic chuck, wherein the processing volume is maintained at about 0.5 mTorr to about 0.5 mTorr. under pressure of about 10 Torr. The method also includes generating a plasma over 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- Compressive stress of 500 MPa or more. 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 the 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, the nitrogen-doped diamond-like carbon film has a density of greater than 1.5 g/cc to about 2.1 g/cc and a compressive stress of about -20 MPa to about -400 MPa.

In some embodiments, a method of processing a substrate includes flowing a deposition gas containing a hydrocarbon compound into a processing volume of a plasma processing chamber having a substrate positioned on an electrostatic chuck, wherein the processing volume is maintained at about 0.5 mTorr to about 10 Torr pressure. The method also includes generating a plasma over the substrate in the process volume by applying the first RF bias 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 sp3 ^- hybridized carbon atoms and has a compressive stress of -500 MPa or greater and a density greater than 1.5 g/cc. The method also includes transferring the substrate containing the stressed diamond-like carbon film from the plasma processing chamber to the thermal annealing chamber, and 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 the thermal annealing process. The stress-reduced diamond-like carbon film contains about 50 atomic percent to about 90 atomic percent sp hybridized carbon atoms and has a compressive stress ^of about -20 MPa to less than -500 MPa and greater than 1.5 g/cc to about 2.1 g /cc density.

In other embodiments, a method of processing a substrate includes flowing a deposition gas containing a hydrocarbon compound into a processing volume of a processing chamber having a substrate positioned on an electrostatic chuck, and by applying a first RF bias to the electrostatic The chuck generates a plasma over the substrate in the processing volume to deposit a stressed diamond-like carbon film on the substrate. Stressed diamond-like carbon films have a compressive stress of -500 MPa or more. The method also 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 the 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. Furthermore, the compressive stress of the stress-reduced diamond-like carbon film is about 40% to about 90% less than the compressive stress of the stressed diamond-like carbon film. The method further includes forming a patterned photoresist layer over the stress-reduced diamond-like carbon film, etching the stress-reduced diamond-like carbon film in a pattern corresponding to the patterned photoresist layer, and etching the pattern into the substrate .

In one or more embodiments, a stress-reduced diamond-like carbon film for use as an underlying layer in an extreme ultraviolet ("EUV") lithography process is provided 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 hybridized carbon atoms. The stress-reduced diamond-like carbon film has a density of 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, greater than 60 GPa to about 150 GPa or about 65 GPa to about 80 GPa elastic modulus, and about -20 MPa to less than -600 MPa, about -200 MPa to about -500 MPa, or about -250 MPa to about -400 MPa compressive stress.

Embodiments provided herein relate to stress-reduced diamond-like carbon films and methods for depositing or otherwise forming stress-reduced diamond-like carbon films on substrates. Certain details are set forth in the following description and FIGS. 1-5 to provide a thorough understanding of various embodiments of the present disclosure. Additional 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.

The numerous details, dimensions, angles and other features illustrated in the figures are merely illustrative of particular embodiments. As such, other embodiments may have other details, components, dimensions, angles and features without departing from the spirit or scope of the present disclosure. Additionally, further embodiments of the present disclosure may be practiced without several of the details described below.

Embodiments described herein include the fabrication of stress-reduced classes with high density (eg, >1.5 g/cc), high elastic modulus (eg, >60 GPa), and low compressive stress (eg, <-500 MPa). Improved method of diamond carbon film. The stress-reduced diamond-like carbon films fabricated in accordance with embodiments described herein are amorphous in nature and have greater etch selectivity along with lower stress than current patterned films. The stress-reduced diamond-like carbon films made according to the embodiments described herein have not only low compressive stress, but also high ^sp3 carbon content. In general, the deposition and annealing processes described herein are also fully compatible with current integration schemes for hard mask applications.

In one or more embodiments, fabricating or otherwise producing a stress-reduced diamond-like carbon film includes depositing on a substrate or otherwise during a deposition process, such as a chemical vapor deposition (CVD) process. A stressed diamond-like carbon film is formed in this way, and then the stressed diamond-like carbon film is converted to a stress-reduced diamond-like carbon film by annealing the substrate, such as during a thermal annealing process. For example, a method may include flowing a deposition gas containing a hydrocarbon compound into a processing volume of a processing chamber in which a substrate is positioned on an electrostatic chuck and by applying a first RF bias to the electrostatic chuck between the substrates in the processing volume A plasma is generated on the substrate to deposit a stressed diamond-like carbon film on the substrate. Stressed diamond-like carbon films generally have a compressive stress of -500 MPa or greater, such as from about -600 MPa to about -1,000 MPa. The method also 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 the thermal annealing process.

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

Exemplary hydrocarbon compounds may be or include ethyne or acetylene (C ₂ H ₂ ), propylene (C ₃ H ₆ ), methane (CH ₄ ), butene (C ₄ H ₈ ), 1,3 - Dimethyladamantane, bicyclo[2.2.1]hept-2,5-diene (2,5-norbornadiene), adamantane (C ₁₀ H ₁₆ ), norbornene (C ₇ H ₁₀ ) ), derivatives thereof, isomers thereof, or any combination thereof. Deposition gases may further include one, two, or more diluent gases, carrier gases, and/or purge 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 (Cl ₂ ), carbon tetrafluoride (CF ₄ ), and/or nitrogen trifluoride (NF ₃ ) to improve film quality.

The substrate and/or processing volume can be heated and maintained at independent temperatures during the deposition process. The substrate and/or processing volume can be heated to 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 °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, about -40°C to about 0°C, about 0°C to about 600°C, about 0°C to about 450°C, about 0°C to about 350°C, about 0°C to about 200°C, about 0°C to about 120°C, about 0°C to about 100°C, about 0°C to about 80°C, about 0°C to about 50°C , about 0°C to about 25°C, about 10°C to about 600°C, about 10°C to about 450°C, about 10°C to about 350°C, about 10°C to about 200°C, about 10°C to about 100°C, or A temperature of about 10°C to about 50°C.

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

Plasma (eg, capacitively coupled plasma) can be formed from the top and bottom electrodes or the side electrodes. Electrodes can be powered from a single electrode, dual powered electrodes, or have 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 with any or all of the reactant gases listed herein to deposit stressed films of diamond-like carbon.

In one or more embodiments, the stressed diamond-like carbon film is deposited in a processing chamber with a substrate susceptor maintained at about 10°C and a pressure of about 2 mTorr, wherein the plasma is deposited by applying about 2,500 watts ( A bias voltage of about 13.56 MHz) was applied to the electrostatic chuck at or above the substrate level. In other embodiments, about 1,000 watts of additional RF at about 2 MHz are also delivered to the electrostatic chuck, thus creating a dual bias plasma at the substrate level.

Embodiments described and discussed herein will be discussed with reference to a plasma-enhanced chemical vapor deposition (PE-CVD) process that can be performed using any suitable thin film deposition system. Examples of suitable systems include the CENTURA® system that can use the DXZ® processing chamber, the PRECISION 5000® system, the PRODUCER® system, the PRODUCER® GT ^™ system, the PRODUCER® XPPrecision ^™ system, the PRODUCER® SE ^™ system, the Sym3® processing chamber, and Mesa ^™ processing chambers, all of which are available from Applied Materials, Inc., Santa Clara, CA. Other tools capable of performing PE-CVD processes may also be adapted to benefit from the embodiments described herein. Furthermore, any system that implements the PE-CVD process described herein can be advantageously used. The device descriptions described herein are illustrative and should not be construed or construed as limiting the scope of the embodiments described herein.

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

In other embodiments, the substrate containing the stressed diamond-like carbon film is transferred from a first processing chamber (eg, a plasma processing chamber) to a second processing chamber (eg, a thermal annealing chamber) and subsequently exposed In a thermal annealing process to convert the stressed diamond-like carbon film into a stress-reduced diamond-like carbon film. For example, the fabrication process may include removing the substrate containing the stressed diamond-like carbon film from the first processing chamber, positioning the substrate containing the stressed diamond-like carbon film in a thermal annealing chamber, heating the stressed diamond-like carbon film carbon film to produce a stress-reduced diamond-like carbon film during a thermal annealing process, and subsequent removal of the substrate containing the stress-reduced diamond-like carbon film from the thermal annealing chamber.

Stressed diamond-like carbon film, substrate, and/or processing chamber at 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, Heating at a temperature of 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 reduction during the thermal annealing process diamond-like carbon film. For example, the stressed diamond-like carbon film, substrate, and/or processing chamber may be heated at about 200°C to about 800°C, about 200°C to about 700°C, about 200°C to about 600°C, about 200°C to about 500°C , about 200°C to about 450°C, about 200°C to about 400°C, about 200°C to about 350°C, about 200°C to about 300°C, about 300°C to about 600°C, about 300°C to about 500°C, about 300°C to about 450°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 Heating at a temperature of 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 stress relief during the thermal annealing process Small diamond-like carbon film.

heating the stressed diamond-like carbon film, substrate, and/or processing chamber 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 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 the 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 minute to about 30 minutes, about 1 minute to about 20 minutes, about 1 minute to about 10 minutes, about 1 minute to about 5 minutes, about 1 minute to about 3 minutes, about 3 minutes to about 90 minutes, about 3 minutes to about 75 minutes, about 3 minutes to about 60 minutes, about 3 minutes to about 45 minutes, about 3 minutes to about 30 minutes, about 3 minutes to about 20 minutes, about 3 minutes to about 10 minutes, about 3 minutes to about 8 minutes, about 3 minutes to about 5 minutes, about 4 minutes to about 8 minutes, or about 4 minutes to about 6 minutes to produce a stress-reduced diamond-like carbon film during the thermal annealing process.

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

The substrate containing the stressed diamond-like carbon film is positioned or otherwise positioned within the processing chamber during the thermal annealing process. The processing chamber may be or include a plasma processing chamber, a thermal annealing processing chamber, a vacuum chamber, a deposition chamber (eg, a CVD chamber), or other types of chambers that may be used to thermally heat a substrate. During the thermal annealing process, the processing volume within the processing chamber may be under a vacuum and/or an environment containing a processing gas or annealing gas. Exemplary process or annealing gases may be or include nitrogen ( _N2 ), argon, helium, neon, or any combination thereof.

During the thermal annealing process, the processing volume within the processing chamber may have 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 pressure. For example, during the thermal annealing process, the processing volume within the processing chamber may have about 5 mTorr to about 100 Torr, about 10 mTorr to about 100 Torr, about 100 mTorr to about 100 Torr, about 500 mTorr to about 100 Torr, about 1 Torr to about 100 Torr, about 5 Torr to about 100 Torr, about 10 Torr to about 100 Torr, about 25 Torr to about 100 Torr, about 50 Torr to about 100 Torr, about 0.5 mTorr to about 20 Torr, about 5 mTorr to about 20 Torr, about 10 mTorr to about 20 Torr, about 100 mTorr to about 20 Torr, about 500 mTorr to about 20 Torr, about 1 Torr to about 20 Torr, about 5 Torr to about 20 Torr, about 10 Torr to about A pressure of 20 Torr, about 0.5 mTorr to about 1 Torr, about 5 mTorr to about 1 Torr, about 10 mTorr to about 1 Torr, about 100 mTorr to about 1 Torr, or about 500 mTorr to about 1 Torr.

The thermal annealing process greatly reduces the compressive stress from the diamond-like carbon film, so that once converted to a stress-reduced diamond-like carbon film, most of the compressive stress of the stressed diamond-like carbon film relaxes, relieves, or otherwise shifts. remove. Numerous other properties of the stressed diamond ^- like carbon film, such as density, elastic modulus, sp hybridized carbon atomic concentration, and hydrogen concentration, remain the same or substantially the same as the stress-reduced diamond-like carbon film produced thereby similar.

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 produced. In some examples, the compressive stress of the stress-reduced diamond-like carbon film is about 25%, about 30%, about 35%, about 40%, about 45%, about 50% less than the compressive stress of the stressed diamond-like carbon film , 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 about 25% to about 95%, about 25% to about 90%, about 25% to about 80%, about 25% less than the compressive stress of the stressed diamond-like carbon film % to about 75%, about 25% to about 70%, about 25% to about 60%, about 25% to about 55%, about 25% to about 50%, about 25% to about 40%, about 40% to About 95%, about 40% to about 90%, about 40% 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%.

The stressed diamond-like carbon film may have -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 -1,000 MPa, about -1,100 MPa, about - 1,200 MPa, or greater compressive stress. For example, the stressed diamond-like carbon film may have -500 MPa to about -1,200 MPa, -500 MPa to about -1,000 MPa, -500 MPa to about -900 MPa, -500 MPa to about -850 MPa, -500 MPa To about -800 MPa, -500 MPa to about -750 MPa, -500 MPa to about -725 MPa, -500 MPa to about -700 MPa, -500 MPa to about -675 MPa, -500 MPa to about -650 MPa , -500 MPa to about -625 MPa, -500 MPa to about -600 MPa, about -600 MPa to about -1,200 MPa, about -600 MPa to about -1,000 MPa, about -600 MPa to about -900 MPa, about -600 MPa to about -850 MPa, about -600 MPa to about -800 MPa, about -600 MPa to about -750 MPa, about -600 MPa to about -725 MPa, about -600 MPa to about -700 MPa, about -600 MPa to about -675 MPa, about -600 MPa to about -650 MPa, about -600 MPa to about -625 MPa, about -650 MPa to about -1,200 MPa, about -650 MPa to about -1,000 MPa, about -650 MPa to about -900 MPa, about -650 MPa to about -850 MPa, about -650 MPa to about -800 MPa, about -650 MPa to about -750 MPa, about -650 MPa to about -725 MPa, or Compressive stress from about -650 MPa to about -700 MPa.

The stress-reduced diamond-like carbon film may have 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 Compressive stress of MPa, about -425 MPa, about -450 MPa, about -475 MPa, about -490 MPa, about -495 MPa, -499 MPa or less than -500 MPa. For example, the stress-reduced diamond-like carbon film may have about -20 MPa to less than -500 MPa, about -50 MPa to less than -500 MPa, about -80 MPa to less than -500 MPa, about -100 MPa to less than -500 MPa MPa, about -150 MPa to less than -500 MPa, about -200 MPa to less than -500 MPa, about -225 MPa to less than -500 MPa, about -250 MPa to less than -500 MPa, about -275 MPa to less than -500 MPa, about -300 MPa to less than -500 MPa, about -325 MPa to less than -500 MPa, about -350 MPa to less than -500 MPa, about -375 MPa to less than -500 MPa, about -400 MPa to less than -500 MPa, about -450 MPa to less than -500 MPa, about -20 MPa to about -400 MPa, about -50 MPa to about -400 MPa, about -80 MPa to about -400 MPa, about -100 MPa to about -400 MPa, about -150 MPa to about -400 MPa, about -200 MPa to about -400 MPa, about -225 MPa to about -400 MPa, about -250 MPa to about -400 MPa, about -275 MPa to about -400 MPa, about -300 MPa to about -400 MPa, about -325 MPa to about -400 MPa, about -350 MPa to about -400 MPa, about -375 MPa to about -400 MPa, about -20 MPa to about -300 MPa, about -50 MPa to about -300 MPa, about -80 MPa to about -300 MPa, about -100 MPa to about -300 MPa, about -150 MPa to about -300 MPa, about -200 MPa to about -300 MPa, about -225 MPa to about -300 MPa, about -250 MPa to about -300 MPa, or about -275 MPa to about -300 MPa compressive stress.

In one or more examples, the stressed diamond-like carbon film has a compressive stress of about -600 MPa to about -1,000 MPa, and once converted, 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 compressive stress. In some examples, the stressed diamond-like carbon film has a compressive stress of about -650 MPa to about -900 MPa, and once converted, the stress-reduced diamond-like carbon film has about -50 MPa to about -350 MPa or about - Compressive stress from 200 MPa to about -350 MPa. In other examples, the stressed diamond-like carbon film has a compressive stress of -700 MPa to about -850 MPa, and once converted, the stress-reduced diamond-like carbon film has a compressive stress of about -100 MPa to about -325 MPa or about - Compressive stress from 250 MPa to about -325 MPa.

In some embodiments, hydrogen radicals are fed via the RPS, which results in selective etching of sp ² hybridized carbon atoms, thus further increasing the sp ³ hybridized carbon atom fraction of the film, thus further increasing the etch selectivity. The high etch selectivity of the stress-reduced diamond-like carbon film is achieved by having a larger density and modulus compared to current generation films. Without being bound by theory, it is believed that the larger density and modulus are due to the high content ^of sp hybridized carbon atoms in the stress-reduced diamond-like carbon film, which in turn can be achieved by low pressure and plasma power combination to achieve.

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have at least 40 atomic percent (at %), about 45 atomic percent (at %), based on the total amount of carbon atoms in the corresponding diamond-like carbon film. 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% of the concentration or percentage ^of sp hybridized carbon atoms ⁽ eg, sp hybridized carbon atom content). For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have at least 40 at % to about 95 at % based on the total amount of carbon atoms in the corresponding diamond-like carbon film , 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 60 at%, about 60 at% to about 80 at%, about 60 at% to about 75 at%, about 60 at% to about 70 at% , about 60 at% to about 65 at%, about 65 at% to about 95 at%, about 65 at% to about 90 at%, about 65 at% to about 85 at%, about 65 at% to about 80 at% , about 65 at% to about 75 at%, about 65 at% to about 70 at%, about 65 at% to about 68 at%, about 75 at% to about 95 at%, about 75 at% to about 90 at% , about 75 at% to about 85 at%, about 75 at% to about 80 at%, or about 75 at% to about 78 at% of the concentration or percentage ^of sp hybridized carbon atoms.

In some embodiments, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have an sp impurity of less ^than 60 at%, such as less than 55 at% or less than 50 at% The concentration or percentage of carbon atoms that are hybridized ⁽ eg, the content of sp hybridized carbon atoms). Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have about 5 at %, about 10 at %, about 10 at %, based on the total amount of carbon atoms in the corresponding diamond-like carbon film about 15 at%, about 20 at%, about 25 at%, about 28 at%, or about 30 at% to about 32 at%, about 35 at%, about 36 at%, about 38 at%, about 40 at% , about 45 at%, about 50 at%, about 55 at%, or about 60 at ^% of the concentration or percentage of sp hybridized carbon atoms. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have from about 5 at % to about 60 at % based on the total amount of carbon atoms in the corresponding diamond-like carbon film %, about 5 at% to about 50 at%, about 5 at% to about 45 at%, about 5 at% to about 40 at%, about 5 at% to about 38 at%, about 5 at% to about 36 at% %, about 5 at% to about 35 at%, about 5 at% to about 32 at%, about 5 at% to about 30 at%, about 5 at% to about 25 at%, about 5 at% to about 20 at% %, about 5 at% to about 15 at%, about 5 at% to about 10 at%, about 20 at% to about 60 at%, about 20 at% to about 50 at%, about 20 at% to about 45 at% %, about 20 at% to about 40 at%, 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 the concentration or percentage of sp ² hybridized carbon atoms from about 34 at% to about 36 at%.

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film independently has a density greater than 1.5 g/cc (grams per cubic centimeter (cm ³ )), such as about 1.55 g/cc, about 1.6 g/cc, about 1.65 g/cc, or about 1.68 g/cc to about 1.7 g/cc, about 1.72 g/cc, about 1.75 g/cc, about 1.78 g/cc, about 1.8 g/cc, about 1.85 g/cc, about 1.9 g/cc, about 1.95 g/cc, about 1.98 g/cc, about 2 g/cc, about 2.05 g/cc, about 2.1 g/cc, or more. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film independently has 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, greater than 1.5 g/cc to about 1.7 g/cc, greater than 1.5 g/cc cc to about 1.68 g/cc, greater than 1.5 g/cc to about 1.65 g/cc, greater than 1.5 g/cc to about 1.6 g/cc, about 1.6 g/cc to about 2.1 g/cc, about 1.6 g/cc to About 2.05 g/cc, about 1.6 g/cc to about 2 g/cc, about 1.6 g/cc to about 1.9 g/cc, about 1.6 g/cc to about 1.85 g/cc, about 1.6 g/cc to about 1.8 g/cc, about 1.6 g/cc to about 1.78 g/cc, about 1.6 g/cc to about 1.75 g/cc, about 1.6 g/cc to about 1.72 g/cc, about 1.6 g/cc to about 1.7 g/cc cc, about 1.6 g/cc to about 1.68 g/cc, about 1.6 g/cc to about 1.65 g/cc, about 1.68 g/cc to about 2.1 g/cc, about 1.68 g/cc to about 2.05 g/cc, About 1.68 g/cc to about 2 g/cc, about 1.68 g/cc to about 1.9 g/cc, about 1.68 g/cc to about 1.85 g/cc, about 1.68 g/cc to about 1.8 g/cc, about 1.68 g/cc to about 1.78 g/cc, about 1.68 g/cc to about 1.75 g/cc, about 1.68 g/cc to about 1.72 g/cc, about 1.68 g/cc to about 1.7 g/cc, about 1.7 g/cc cc to about 1.75 g/cc, about 1.7 g/cc to about 1.72 g/cc, about 1.55 g/cc to less than 2 g/cc, about 1.6 g/cc to less than 2 g/cc, about 1.65 g/cc to Less than 2 g/cc, about 1.68 g/cc to less than 2 g/cc, about 1.7 g/cc to less than 2 g/cc, about 1.72 g/cc to less than 2 g/cc, about 1.75 g/cc to less than 2 g/cc, or a density of about 1.8 g/cc to less than 2 g/cc.

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have about 5 Å, about 10 Å, about 50 Å, about 100 Å, about 150 Å, about 200 Å, or ~300 Å to ~400 Å, ~500 Å, ~600 Å, ~700 Å, ~800 Å, ~1,000 Å, ~2,000 Å, ~3,000 Å, ~5,000 Å, ~6,000 Å, ~8,000 Å, ~10,000 Å, about 15,000 Å, about 20,000 Å, or thicker. For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have about 5 Å to about 20,000 Å, about 5 Å to about 10,000 Å, about 5 Å to about 5,000 Å , about 5 Å to about 3,000 Å, about 5 Å to about 2,000 Å, about 5 Å to about 1,000 Å, about 5 Å to about 500 Å, about 5 Å to about 200 Å, about 5 Å to about 100 Å, about 5 Å to about 50 Å, about 200 Å to about 20,000 Å, about 200 Å to about 10,000 Å, about 200 Å to about 6,000 Å, about 200 Å to about 5,000 Å, about 200 Å to about 3,000 Å, about 200 Å to about 2,000 Å, about 200 Å to about 1,000 Å, about 200 Å to about 500 Å, about 600 Å to about 3,000 Å, about 600 Å to about 2,000 Å, about 600 Å to about 1,500 Å, about 600 Å to about 600 Å to about 1,000 Å, about 600 Å to about 800 Å, about 1,000 Å to about 20,000 Å, about 1,000 Å to about 10,000 Å, about 1,000 Å to about 5,000 Å, about 1,000 Å to about 3,000 Å, about 1,000 Å to about 2,000 Å , about 2,000 Å to about 20,000 Å, or about 2,000 Å to about 3,000 Å thick.

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have 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 Refractive index or n value (n (at 633 nm)) of 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 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 a refractive index or n value ( n (at 633 nm)).

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have an extinction coefficient or k-value (K( at 633 nm)). For example, each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may independently have 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 , an extinction coefficient or k value (K (at 633 nm)) of about 0.2 to about 0.3, or about 0.2 to about 0.25.

Each of the stressed diamond-like carbon film and the stress-reduced diamond-like carbon film may 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 may independently have 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, about 65 GPa to about 300 GPa, about 65 GPa to about 250 GPa, about 65 GPa to about 200 GPa, about 65 GPa to about 150 GPa, about 65 GPa to about 125 GPa, about 65 GPa to about 100 GPa, about 65 GPa to about 80 GPa, about 80 GPa to about 400 GPa, about 80 GPa to about 350 GPa, about 80 GPa to about 300 GPa, about 80 GPa to about An elastic modulus of 250 GPa, about 80 GPa to about 200 GPa, about 80 GPa to about 150 GPa, about 80 GPa to about 125 GPa, or about 80 GPa to about 100 GPa.

In some embodiments, the stress-reduced diamond-like carbon film may be used as an underlayer in an extreme ultraviolet ("EUV") lithography process. In some examples, the stress-reduced diamond-like carbon film is used in an underlying layer of an EUV lithography process and has from about 40% to about 90% sp hybridized carbon atoms based ^on the total amount of carbon atoms in the film, greater than A density of 1.5 g/cc to about 1.9 g/cc, and an elastic modulus of greater than or about 60 GPa to about 150 GPa or about 200 GPa.

FIG. 1A depicts a schematic diagram of a substrate processing system 132 that may be used to perform stressed diamond-like carbon film deposition in accordance with embodiments described herein. Substrate processing system 132 includes processing chamber 100 coupled to gas panel 130 and controller 110 . The processing chamber 100 generally includes a top wall 124 , side walls 101 , and a bottom wall 122 that define a processing volume 126 . A substrate support assembly 146 is provided in 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 generally fabricated from aluminum, ceramic, and other suitable materials. The electrostatic chuck 150 may be moved in a vertical direction inside the processing chamber 100 using a displacement mechanism (not shown).

The vacuum pump 102 is coupled to a port formed in the bottom of the processing chamber 100 . A vacuum pump 102 is used to maintain the desired gas pressure in the process chamber 100 . The vacuum pump 102 also evacuates the process gases and by-products from the process chamber 100 .

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

A gas distribution assembly 120 with a plurality of holes 128 is provided on top of the processing chamber 100 above the electrostatic chuck 150 . The holes 128 of the gas distribution assembly 120 are used to introduce process gases (eg, deposition gases, dilution gases, carrier gases, purge gases) into the processing chamber 100 . The holes 128 may have different sizes, numbers, distributions, shapes, designs, and diameters to facilitate the flow of various process gases for different process needs. The gas distribution assembly 120 is connected to a gas control panel 130 that allows various gases to be supplied to the processing volume 126 during processing. A plasma is formed from the process gas mixture exiting the gas distribution assembly 120 to enhance thermal decomposition of the process gas, resulting in deposition of material on the surface 191 of the substrate 190 .

Gas distribution assembly 120 and electrostatic chuck 150 may form a pair of spaced electrodes in process volume 126 . One or more RF power sources 140 provide a bias potential to gas distribution assembly 120 via 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 , electrostatic chuck 150 , to both gas distribution assembly 120 and electrostatic chuck 150 , or external to process chamber 100 Set up the antenna (not shown). In one or more examples, RF power supply 140 may generate power at a frequency of 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 RF power supply 140 may provide about 100 watts to about 3,000 watts of power at a frequency of about 50 kHz to about 13.6 MHz. In other examples, the RF power supply 140 may provide about 500 watts to about 1,800 watts of power at a frequency of about 50 kHz to about 13.6 MHz.

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

FIG. 1B depicts a schematic cross-sectional view of another substrate processing system 180 that may be used to practice embodiments described herein. Substrate processing system 180 is similar to substrate processing system 132 of FIG. 1A except that substrate processing system 180 is configured to flow process gas from gas panel 130 across surface 191 of substrate 190 via sidewall 101 . Additionally, the gas distribution assembly 120 depicted in FIG. 1A is replaced with an electrode 182 . Electrode 182 may be configured for secondary electron generation. In one or more embodiments, electrode 182 is a silicon-containing electrode.

FIG. 2 depicts a schematic cross-sectional view of a substrate support assembly 146 used in the processing system of FIGS. 1A and 1B that may be used to practice embodiments described herein. Referring to FIG. 2 , the electrostatic chuck 150 may include a heater element 170 adapted to control the temperature of the 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 . Electrostatic chuck 150 may be resistively heated by applying current from heater power supply 106 to heater element 170 . Heater power supply 106 may be coupled via RF filter 216 . RF filter 216 may be used to protect heater power supply 106 from RF energy. The heater element 170 may be made of nichrome wire encapsulated in a nickel-iron-chromium alloy (eg, ^INCOLOY® alloy) sheath. The current supplied from heater power supply 106 is adjusted by controller 110 to control the heat generated by heater element 170, thus maintaining substrate 190 and 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.

Referring to FIG. 1, a temperature sensor 172, such as a thermocouple, may be embedded in the electrostatic chuck 150 to monitor the temperature of the electrostatic chuck 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.

The electrostatic chuck 150 includes a gripping electrode 210, which may be a mesh of conductive material. The clamping electrodes 210 may be embedded in the electrostatic chuck 150 . The chuck electrodes 210 are coupled to a chuck power source 212 which, when energized, electrostatically clamps the substrate 190 to the upper surface 192 of the electrostatic chuck 150 .

The gripping electrode 210 may be configured as a monopolar or bipolar electrode, or have another suitable arrangement. Chuck electrode 210 may be coupled via RF filter 214 to chuck power supply 212 , which provides direct current (DC) power to electrostatically secure substrate 190 to upper surface 192 of electrostatic chuck 150 . The RF filter 214 prevents the RF power used to form the plasma within the processing chamber 100 from damaging electrical equipment or creating electrical hazards outside the chamber. The electrostatic chuck 150 may be fabricated from a ceramic material, such as aluminum nitride or aluminum oxide (eg, aluminum oxide). Alternatively, electrostatic chuck 150 may be fabricated from a polymer such as polyimide, polyetheretherketone (PEEK), polyaryletherketone (PAEK), and the like.

The power application system 220 is coupled to the 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 . The power application system 220 may additionally include the controller 110 , and a sensor element 250 in communication with the controller 110 and both the first RF power source 230 and the second RF power source 240 . The controller 110 can also be used to control the plasma from the process gas by applying RF power from the first RF power source 230 and the second RF power source 240 to deposit a layer of material on the substrate 190 .

As described above, the electrostatic chuck 150 includes a gripping electrode 210, which in one aspect may be used to grip the substrate 190 while also serving as a first RF electrode. The electrostatic chuck 150 may also include a second RF electrode 260, and along with the clamp electrode 210, RF power may be applied to tune the plasma. The first RF power source 230 may be coupled to the second RF electrode 260 , and the second RF power source 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. Alternatively, the second RF electrode 260 may be a grid of conductive material.

The first RF power supply 230 and the second RF power supply 240 may generate power at the same frequency or at different frequencies. In one or more embodiments, one or both of the first RF power supply 230 and the second RF power supply 240 may operate at from about 350 KHz to about 100 MHz (eg, 350 KHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, or 100 MHz) to generate power independently. In one or more embodiments, the first RF power supply 230 may generate power at a frequency of 13.56 MHz, and the second RF power supply 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 supply 230 and the second RF power supply 240 can be varied in order to tune the plasma. For example, sensor element 250 may be used to monitor RF energy from one or both of first RF power source 230 and second RF power source 240 . Data from sensor element 250 can be communicated to controller 110 , and controller 110 can be used to vary the power applied by first RF power source 230 and second RF power source 240 .

In one or more embodiments, electrostatic chuck 150 has grip electrodes 210a and RF electrodes separated from each other, and a first RF bias can be applied to RF electrodes 260 and a second RF voltage can be applied to grip electrodes 210 . In one or more examples, the first RF bias is provided at a power of about 10 watts to about 3,000 watts at a frequency of about 350 KHz to about 100 MHz, and the second RF bias is provided at about 350 KHz to about 100 It is available at a frequency of about 10 watts to about 3,000 watts at a frequency of MHz. In other examples, the first RF bias is provided at a power of about 2,500 watts to about 3,000 watts at a frequency of about 13.56 MHz, and the second RF bias is provided at a frequency of about 2 MHz at about 800 watts to about 1,200 watts available at watts of power.

In one or more embodiments, a deposition gas containing one or more hydrocarbon compounds may be flowed or otherwise introduced into the processing volume of a processing chamber, such as a PE-CVD chamber. The hydrocarbon compound and diluent gas (if used) can be independently flowed or introduced into the process volume. In some examples, one or more substrates are positioned on an electrostatic chuck in a 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 (eg, substrate level) by applying a first RF bias to the RF electrodes and a second RF bias to the clamp 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 a stressed diamond-like carbon film etched or otherwise formed in a pattern corresponding to the patterned photoresist layer. is otherwise formed, and the pattern is etched or otherwise formed into the substrate. In other embodiments, the stressed diamond-like carbon film is converted to a stress-reduced diamond-like carbon film, and then a patterned photoresist layer may be deposited or otherwise formed over the stress-reduced diamond-like carbon film, the stress The reduced diamond-like carbon film is etched or otherwise formed in a pattern corresponding to the patterned photoresist layer, and the pattern is etched or otherwise formed into the substrate.

In general, 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 (eg, 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 a chamber pressure of about 0.5 mTorr to about 10 Torr (eg, about 2 mTorr to about 50 mTorr; or about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may be about 20 sccm to about 5,000 sccm (eg, about 50 sccm to about 1,000 sccm, about 100 sccm to about 200 sccm, or about 150 sccm to about 200 sccm). The flow rate of the dilution gas or purge gas (eg, He) can be about 1 sccm to about 3,00 sccm (eg, about 5 sccm to about 500 sccm, about 10 sccm to about 150 sccm, or about 20 sccm to about 100 sccm sccm). Stressed diamond-like carbon films can be deposited to thicknesses of about 200 Å and about 6,000 Å (eg, about 300 Å to about 5,000 Å; about 400 Å to about 800 Å; about 2,000 Å to about 3,000 Å, or about 5 Å to about 200 Å - depending on 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. of Santa Clara, California.

FIG. 3 depicts a flow diagram of a method 300 for forming a stress-reduced diamond-like carbon film on a film stack disposed on a substrate in accordance with one 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. FIGS. 4A-4B are schematic cross-sectional views illustrating a sequence for forming a stress-reduced diamond-like carbon film on a film stack disposed on a substrate in accordance with method 300 . Although the method 300 is described below with reference to the formation of a hard mask layer on the film stack for fabricating a stair-like structure in a film stack of three-dimensional semiconductor devices, the method 300 may also be advantageously used in other device fabrication applications. In addition, it should also be understood that the operations depicted in FIG. 3 may be performed concurrently and/or in a different order than the order depicted in FIG. 3 .

Method 300 begins at operation 310 by positioning a substrate, such as substrate 402 depicted in Figure 4A, into a processing volume of a processing chamber, such as processing chamber 100 depicted in Figure 1A or 1B. The substrate 402 may be the substrate 190 depicted in FIGS. 1A , 1B, and 2 . Substrate 402 may be positioned on an electrostatic chuck (eg, upper surface 192 of electrostatic chuck 150 ). As desired, the substrate 402 may be a silicon-based material or any suitable insulating or conductive material on which the substrate 402 is provided with the film stack 404, which may be used to form the structure 400 in the film stack 404, such as a step-like structure.

As shown in the embodiment depicted in Figure 4A, the substrate 402 may have a substantially flat surface, a non-uniform surface, or a substantially flat surface with structures formed thereon. Film stack 404 is formed on substrate 402 . In one or more embodiments, the film stack 404 may be used to form gate structures, contact structures, or interconnect structures in front-end or back-end processes. The method 300 may be performed on the film stack 404 to form therein a staircase-like structure used in a memory structure, such as a NAND structure. In one or more embodiments, the substrate 402 may be a material such as crystalline silicon (eg, Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped silicon Heterogeneous or undoped silicon substrates and patterned or unpatterned substrates silicon on insulator (SOI), carbon doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass ,sapphire. Substrate 402 may be of various sizes, such as 200 mm, 300 mm, 450 mm, or other diameter substrates, as well as rectangular or square panels. Unless otherwise mentioned, the embodiments and examples described herein were performed on substrates having 200 mm diameter, 300 mm diameter, or 450 mm diameter substrates. In embodiments in which SOI structures are used for substrate 402, substrate 402 may include a buried dielectric layer disposed on a silicon crystalline substrate. In one or more embodiments described herein, substrate 402 may be a crystalline silicon substrate.

In one or more embodiments, the film stack 404 disposed on the substrate 402 may have several vertically stacked layers. The film stack 404 may contain a first layer (illustrated as 408a ₁ , 408a ₂ , 408a ₃ , . . . , _408an ) and a second layer (illustrated as 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n ). The pair includes repeated formation of alternating first layers (illustrated as 408a ₁ , 408a ₂ , 408a ₃ , ..., _408an ) and second layers (illustrated as 408b ₁ , 408b ₂ , 408b ₃ , ..., _408bn ) until the desired number of first and second layer pairs are reached.

Film stack 404 may be part of a semiconductor wafer, such as a three-dimensional memory wafer. Although the _first layer (shown as _{408a 1} , _{408a 2} , _{408a 3} , . , . . . , 408b _n ) three repeating layers, noting that any desired number of repeating pairs of the first and second layers may be utilized as desired.

In one or more embodiments, the film stack 404 may be used to form multiple gate structures of a three-dimensional memory chip. _{The first layers 408a1} , _408a2 , _{408a3 , .} It can be a second dielectric layer. Suitable dielectric layers may be used to form the first layers 408a ₁ , 408a ₂ , 408a ₃ , . . . , _408an and the second layers _{408b 1} , 408b ₂ , 408b ₃ , . , silicon oxynitride, silicon carbide, silicon oxycarbide, titanium nitride, composites of oxides and nitrides, at least one or more oxide layers sandwiched between nitride layers, combinations thereof, and the like. 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 oxide silicon or zirconium silicate, tantalum oxide, aluminum oxide, aluminum doped Miscellaneous hafnium dioxide, bismuth strontium titanium (BST), and platinum zirconium titanium (PZT), dopants thereof, or any combination thereof.

In one or more examples, the first layers 408a ₁ , 408a ₂ , 408a ₃ , . . . , _408an are silicon oxide layers and the second layers 408b ₁ , 408b ₂ , _{408b 3} , . A silicon nitride layer or a polysilicon layer disposed on one layer 408a ₁ , 408a ₂ , 408a ₃ , . . . , _408an . In one or more embodiments, the thickness of the first layers 408a ₁ , 408a ₂ , 408a ₃ , . . . , _408an can be controlled to be about 50 Å to about 1,000 Å, such as about 500 Å, and each second layer The thickness of 408b ₁ , 408b ₂ , 408b ₃ , ..., _408bn can be controlled to be about 50 Å to about 1,000 Å, such as about 500 Å. The membrane stack 404 may have a total thickness of about 100 Å to about 2,000 Å. In one or more embodiments, the total thickness of film stack 404 is about 3 microns to about 10 microns and may vary as technology advances.

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

At operation 320, a clamping voltage is applied to the electrostatic chuck, and the substrate 402 is clamped or otherwise disposed on the electrostatic chuck. In one or more embodiments, wherein the substrate 402 is positioned on the upper surface 192 of the electrostatic chuck 150, the upper surface 192 provides support and grips the substrate 402 during processing. The electrostatic chuck 150 planarizes the substrate 402 tightly against the upper surface 192, thereby preventing backside deposition. An electrical bias is provided to the substrate 402 via the clamp electrodes 210 . The gripping electrodes 210 may be in electronic communication with a gripping power source 212 that supplies a bias voltage to the gripping electrodes 210 . In one or more embodiments, the clamping voltage is about 10 watts to about 3,000 watts, about 100 watts to about 2,000 watts, or about 200 watts to about 1,000 watts.

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

In one or more embodiments, a constant clamping voltage is applied to the substrate 402 . In some embodiments, the clamping voltage may be pulsed to the electrostatic chuck 150 . In other embodiments, the backside gas may be applied to the substrate 402 when a clamping voltage is applied to control the temperature of the substrate. The backside gas may be or include helium, argon, neon, nitrogen ( _N2 ), hydrogen ( _H2 ), or any combination thereof.

At operation 330, plasma is generated at the substrate by applying a first RF bias to the electrostatic chuck, such as adjacent to or near the substrate level. The plasma generated at the substrate can be generated in the plasma region between the substrate and the electrostatic chuck. The first RF bias may be at a frequency of about 350 KHz to about 100 MHz (eg, about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz) line from about 10 watts to about 3,000 watts. In one or more embodiments, the first RF bias is provided at a power of about 2,500 watts to about 3,000 watts at a frequency of about 13.56 MHz. In one or more embodiments, the first RF bias is provided to the electrostatic chuck 150 via the second RF electrode 260 . The second RF electrode 260 may be in electronic communication with the first RF power source 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 3,000 watts, about 2,000 watts to about 3,000 watts, or about 2,500 watts to about 3,000 watts. The first RF power source 230 may be generated at a frequency of about 350 KHz to about 100 MHz (eg, about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz) power.

In one or more embodiments, operation 330 further includes applying a second RF bias to the electrostatic chuck. At a frequency of about 350 KHz to about 100 MHz (eg, about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz), the second RF bias may be From about 10 watts to about 3,000 watts. In some examples, the second RF bias is provided at a power of about 800 watts to about 1,200 watts at a frequency of about 2 MHz. In other examples, the second RF bias is provided to the substrate 402 via the chuck electrode 210 . The clamp electrode 210 may be in electronic communication with a second RF power source 240 that supplies a bias voltage to the clamp electrode 210 . In one or more examples, the bias power is about 10 watts to about 3,000 watts, about 500 watts to about 1,500 watts, or about 800 watts to about 1,200 watts. The second RF power source 240 may be generated at a frequency of about 350 KHz to about 100 MHz (eg, about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz) power. In one or more embodiments, the clamping voltage supplied in operation 320 is maintained during operation 330 .

In some embodiments, during operation 330 , a first RF bias is provided to the substrate 402 via the clamp electrode 210 , and a second RF bias may be provided to the substrate 402 via the second RF electrode 260 . In one or more examples, the first RF bias is about 2,500 watts (about 13.56 MHz) and the second RF bias is about 1,000 watts (about 2 MHz).

During operation 340, deposition gas is flowed into the process volume 126 to form a stressed diamond-like carbon film on the film stack. Deposition gas may flow from gas panel 130 into process volume 126 through gas distribution assembly 120 or via sidewall 101 . The deposition gas contains one or more hydrocarbon compounds. A hydrocarbon compound may be or include one, two, or more than one hydrocarbon compound in any state of matter. The hydrocarbon compound can be any liquid or gas, but if any precursor is a vapor at room temperature, some advantages can be realized to simplify material metering, control, and the hardware required for delivery to the processing volume.

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 process conditions established during operation 320 and the plasma formed during operation 330 are maintained during operation 340 .

In one or more embodiments, the hydrocarbon compound is a gaseous or liquid hydrocarbon. The hydrocarbons 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 compound has the general formula _CxHy , wherein _x has a range of 1 to about 20 and y has a range of 1 to about 20. Suitable hydrocarbon compounds 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 (C ₇ H ₁₀ ), or any combination thereof. In one or more examples, this allows for greater surface mobility due to the formation of a more stable intermediate species with acetylene.

The hydrocarbon compound may be or include one or more alkanes (eg, _CnH2n+2 , where _n ranges from 1 to 20). Suitable hydrocarbon compounds include, for example, alkanes such as methane ( _CH4 ), ethane ( _C2H6 ), propane ( _{C3H8 )} , _{butane ( C4H10} ) and their isomers isobutane, pentane Alkane (C ₅ H ₁₂ ), hexane (C ₆ H ₁₄ ) and its isomers isopentane and neopentane, hexane (C ₆ H ₁₄ ) and its isomers 2-methylpentane, 3 - methylpentane, 2,3-dimethylbutane, and 2,2-dimethylbutane, or any combination thereof.

The hydrocarbon compound may be or include one or more olefins (eg, _CnH2n , where _n ranges from 1 to 20). Suitable hydrocarbon compounds include, for example, olefins such as ethylene, propylene ( _C3H6 ), _butenes and their isomers, pentenes and their isomers, and the like, dienes such as butadiene, isoprene , pentadiene, hexadiene, or any combination thereof. Additional suitable hydrocarbons include, for example, halogenated olefins such as monofluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, monochloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, or any combination thereof.

The hydrocarbon compound may be or include one or more alkynes (eg, _CnH2n-2 , where _n ranges from 1 to 20). Suitable hydrocarbon compounds include, for example, alkynes such as ethyne or acetylene (C2H2 ₎ , propyne ( _C3H4 ), _butyne ( _{C4H8 )} , _{vinylacetylene} , or the like any combination.

The hydrocarbon compound may be or include one or more aromatic hydrocarbon compounds such as benzene, styrene, toluene, xylene, ethylbenzene, acetophenone, methyl benzoate, phenyl acetate, phenol, cresol, furan, and the like, alpha-terpinene, cymene, 1,1,3,3-tetramethylbutylbenzene, tertiary butyl ether, tertiary butyl ethylene, methyl meth-acrylate , and tertiary butyl furan ether, compounds of formula C ₃ H ₂ and C ₅ H ₄ , halogenated aromatic compounds, including monofluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene, or any combination thereof .

In one or more embodiments, the deposition gas further contains one or more dilution gases, one or more carrier gases, and/or one or more purge gases. Suitable diluent, carrier, and/or purge gases such as helium (He), argon (Ar), xenon (Xe), hydrogen ( _H2 ), nitrogen ( _N2 ), ammonia ( _NH3 ), Nitric oxide (NO), or any combination thereof, or the like may be co-flowed with the deposition gas or otherwise supplied into the process volume 126 . Argon, helium, and/or nitrogen can 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 N ₂ and/or NH ₃ can be used to control the hydrogen ratio of the stressed diamond-like carbon film. Alternatively, the diluent gas may not be used during deposition.

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 sp hybridized carbon atoms from the film, thus increasing the fraction ^of sp hybridized carbon atoms in the film, which increases the stress of the stressed diamond-like carbon film 412. Etch selectivity.

In one or more embodiments, after depositing or otherwise forming the stressed diamond-like carbon film 412 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 treatment area. Without being bound by theory, it is believed that exposing a stressed diamond-like carbon film to ^hydrogen radicals results in selective etching of sp hybridized carbon atoms, thus increasing the sp hybridized carbon atom fraction ^of the film, and thus increasing etch selectivity .

At operation 350, after the 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 gases are turned off and optionally purged from the processing chamber. In one or more embodiments, during operation 350, the RF power is reduced (eg, about 200 watts). Optionally, 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 gases are purged from the processing chamber. The processing chamber is evacuated and the substrate is moved up on the lift pins and passed out of the processing chamber.

In some alternative embodiments, prior to releasing the substrate at operation 350, the substrate containing the stressed diamond-like carbon film 412 may be heated to produce a stress-reduced diamond-like carbon film during a thermal annealing process within the same processing chamber.

In one or more embodiments, following operation 350, the substrate containing the stressed diamond-like carbon film 412 is moved up on lift pins and passed out of 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 a 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.

5 depicts a flow diagram of a method 500 of using a stress-reduced diamond-like carbon film in accordance with one or more embodiments described and discussed herein. After the stress-reduced diamond-like carbon film 412 is formed on the substrate, the stress-reduced diamond-like carbon film 412 can be used as a patterning mask in an etching process to form three-dimensional structures, such as a staircase-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) may be formed over the stress-reduced diamond-like carbon film 412 . At operation 520 , the stress-reduced diamond-like carbon carbide 412 may be etched in a pattern corresponding to the patterned photoresist layer, followed by etching the pattern into the substrate 402 at operation 530 . At operation 540 , material may be deposited into the etched portion of the substrate 402 . At operation 550, the stress-reduced diamond-like carbon film 412 may be removed using a solution containing hydrogen peroxide and sulfuric acid. An exemplary solution known to contain hydrogen peroxide and sulfuric acid is Piranha solution or Piranha etchant. The stress-reduced diamond-like carbon film 412 can also be removed using etching chemistries containing oxygen and halogens (eg, fluorine or chlorine), such as Cl ₂ /O ₂ , CF ₄ /O ₂ , Cl ₂ /O ₂ /CF ₄ . The stress-reduced diamond-like carbon film 412 can be removed by a chemical mechanical polishing (CMP) process. Extreme Ultraviolet (“EUV”) Patterning Solutions

When metal-containing photoresists are used in extreme ultraviolet ("EUV") patterning schemes, the selection of underlying layers is critical to prevent nano-failures (eg, bridging defects and spacer defects) in semiconductor devices. A conventional underlayer for EUV patterning (lithography) schemes is spin on carbon (SOC) material. However, during patterning, metals, such as tin, diffuse through the SOC material, for example, causing nano-failure in the semiconductor element. Such nano-failures result in reduced, degraded, and compromised semiconductor performance.

On the other hand, the high density carbon films described herein have excellent film qualities, such as improved hardness and density. This hardness and density allows the high density carbon film to act as a stronger barrier to metal infiltration and to prevent and minimize nano-failure to a greater extent than conventional SOC films. In one or more embodiments, a stress-reduced diamond-like carbon film is provided for use as an underlying layer in an extreme ultraviolet ("EUV") lithography process.

In one or more embodiments, the stress-reduced diamond-like carbon film used as the underlying layer of the EUV lithography process can be any of the films described herein. The stress-reduced diamond-like carbon film may have an sp hybridized carbon atom content ^of about -20 MPa to less than -20 MPa to about 90% based on the total amount of carbon atoms in the stress-reduced diamond-like carbon film 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) compressive stress, greater than Elastic modulus of 60 GPa to about 200 GPa or greater than 60 GPa to about 150 GPa, and 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).

Accordingly, methods and apparatus are provided for forming a hard mask layer (which is or contains a stress-reduced diamond-like carbon film) that can be used to form a three-dimensional stacked ladder-like structure for the fabrication of semiconductor elements . By utilizing a stress-reduced diamond-like carbon film as a hard mask layer with desirable robust film properties and etch selectivity, improved size and profile control of the resulting structures formed in the film stack can be obtained, and in semiconductor The application of three-dimensional stacking of components can enhance the electrical performance of wafer components.

In summary, some of the benefits of the present disclosure provide processes for depositing or otherwise forming stress-reduced diamond-like carbon films on substrates. Common PE-CVD hardmask films have a very low percentage of hybrid ^sp3 atoms and thus low modulus and etch selectivity. In some embodiments described herein, low process pressures (less than 1 Torr) and bottom-driven plasma enable the fabrication of doped films with about 60% or more hybrid sp atoms, which results in ^rigidity relative to previously available Improvement in etch selectivity of mask films. Furthermore, some of the embodiments described herein are performed at low substrate temperatures, which enables deposition of other dielectric films at temperatures much lower than what is currently possible, opening up applications with low thermal budgets that cannot currently be addressed by CVD . Furthermore, some of the embodiments described herein can be used as an underlayer for an EUV lithography process.

Although the foregoing relates to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from its essential scope, which is determined by the scope of the following claims. All documents described herein are incorporated herein by reference, including any priority documents and/or test procedures, so long as they are not inconsistent with this document. As will be apparent from the foregoing general description and specific examples, although forms of the present disclosure have been shown and described, various modifications may be made without departing from the spirit and scope of the present disclosure. Thus, the present disclosure is not intended to be limited thereby. Likewise, for the purposes of United States law, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, element, or group of elements is preceded by the linking phrase "comprising," it will be understood that the phrase "consisting essentially of" precedes the recited composition, element, or group of elements , "consisting of," "selected from the group consisting of," or "the same composition or group of elements of" and vice versa, are contemplated.

Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that, unless otherwise indicated, ranges that include any combination of two values are contemplated, for example, any combination of a lower value and any upper value, a combination of any two lower values, and/or any two upper values combination of values. Certain lower limits, upper limits and ranges appear in one or more of the claims below.

100: Process Chamber 101: Sidewalls 102: Vacuum Pump 106: Heater Power Supply 110: Controller 112: Central Processing Unit (CPU) 114: Support Circuitry 116: Memory 118: Signal Bus 120: Gas Distribution Assembly 122: Bottom Wall 124: Top Wall 126: Process Volume 128: Holes 130: Gas Control Board 132: Substrate Handling System 138: Matching Network 140: RF Power Supply 146: Substrate Support Assembly 150: Electrostatic Chuck 160: Rod 170: Heater Element 172: temperature sensor 180: substrate processing system 182: electrode 190: substrate 191: surface 192: upper surface 210: clamping electrode 212: clamping power supply 214: RF filter 216: RF filter 220: power application system 230: first a radio frequency (RF) power source 240: second RF power source 250: sensor element 260: second RF electrode 300: method 310: operation 320: operation 330: operation 340: operation 350: operation 360: operation 400: structure 402: Substrate 404: film stack 408-a ₁ : first layer 408-a ₂ : first layer 408-a ₃ : first layer 408-a _n : first layer 408-b ₁ : second layer 408-b ₂ : second layer 408 _- b3: second layer 408- _bn : second layer 412: stressed diamond-like carbon film 500: method 510: operation 520: operation 530: operation 540: operation 550: operation

In order to enable a detailed understanding of the manner in which the above-described features of the present disclosure are used, a more specific description of the present disclosure, briefly summarized above, may be made with reference to embodiments, some of which are illustrated in the accompanying drawings. It is to be noted, however, that the appended drawings illustrate only common embodiments of the present disclosure and are therefore not to be considered limiting of its scope, for the present disclosure may admit to other equally effective embodiments.

Figure 1A depicts a schematic cross-sectional view of a deposition system that may be used to practice a process according to one or more embodiments described and discussed herein.

FIG. 1B depicts a schematic cross-sectional view of another deposition system that may be used to practice processes in accordance with one or more embodiments described and discussed herein.

FIG. 2 depicts a schematic cross-sectional view of an electrostatic chuck that may be used in the apparatus of FIGS. 1A-1B in accordance with one or more embodiments described and discussed herein.

3 depicts a flow diagram of a method for forming a stress-reduced diamond-like carbon film on a film stack disposed on a substrate in accordance with one or more embodiments described and discussed herein.

4A-4B depict a sequence for forming a stress-reduced diamond-like carbon film on a film stack formed on a substrate in accordance with one or more embodiments described and discussed herein.

5 depicts a flow diagram of a method of using a stress-reduced diamond-like carbon film in accordance with one or more embodiments described and discussed herein.

To facilitate understanding, the same reference numerals have been used, where possible, to identify the same elements that are common to the figures. It is contemplated that elements and features of one embodiment may be advantageously incorporated in other embodiments without elaboration.

Domestic storage information (please note in the order of storage institution, date and number) none Foreign deposit information (please note in the order of deposit country, institution, date and number) none

300: Method

310: Operation

320: Operation

330: Operation

340: Operation

350: Operation

360: Operation

Claims (20)

A method of processing a substrate, comprising the steps of: flowing a deposition gas comprising a hydrocarbon compound into a processing volume of a processing chamber with 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; A plasma is generated over the substrate in the process 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 is The diamond carbon film has a compressive stress of -500 MPa or more; and 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, wherein the stress The reduced diamond-like carbon film has a compressive stress of less than -500 MPa and a density of greater than 1.5 g/cc. The method according to claim 1, further comprising the following steps: removing the substrate containing the stressed diamond-like carbon film from the processing chamber; positioning the substrate containing the stressed diamond-like carbon film in a thermal annealing chamber, wherein the stressed diamond-like carbon film is heated to produce the stress-reduced diamond-like carbon film during the thermal annealing process; as well as The substrate containing the stress-reduced diamond-like carbon film is removed from the thermal annealing chamber. The method of claim 2, wherein the stressed diamond-like carbon film is heated at a temperature of about 300°C to about 500°C for about 2 minutes to about 15 minutes during the thermal annealing process to produce the stress reduction Small diamond-like carbon film. The method of claim 2, wherein the thermal anneal chamber is maintained at a pressure of about 10 mTorr to about 100 Torr during the thermal anneal process. 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 an environment comprising a gas, wherein the gas comprises nitrogen ( _N2 ), argon, helium, neon, or any combination thereof. The method of claim 1, wherein the compressive stress of the stress-reduced diamond-like carbon film is about 40% to about 90% less than the compressive stress of the stressed diamond-like carbon film. The method of claim 1, wherein the stressed diamond-like carbon film has a compressive stress of about -600 MPa to about 1,000 MPa, and wherein the stress-reduced diamond-like carbon film has about -150 MPa to about A compressive stress of -400 MPa. The method of claim 1, wherein the stress-reduced diamond-like carbon film has an elastic modulus of greater than 60 GPa to about 200 GPa. The method of claim 1, wherein the stress-reduced diamond-like carbon film has a density of about 1.55 g/cc to less than 2 g/cc. The method of claim 1, wherein when the plasma is generated and the stressed diamond-like carbon film is deposited on the substrate, the process volume is maintained at a pressure of about 5 mTorr to about 100 mTorr and the The substrate is maintained at a temperature of about 0°C to about 50°C. The method of claim 1, wherein the stress-reduced diamond-like carbon film comprises about 50 atomic percent to about 90 atomic percent sp ³ hybridized carbon atoms. The method of claim 1, wherein the hydrocarbon compound comprises acetylene, propylene, methane, butene, 1,3-dimethyladamantane, bicyclo[2.2.1]hept-2,5-diene, adamantine alkane, norbornene, or any combination thereof. . The method of claim 1, wherein the deposition gas further comprises helium, argon, xenon, neon, hydrogen ( _H2 ), or any combination thereof. 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 gripping electrode and wherein the first RF bias is applied to the RF electrode and the second RF bias is applied to the gripping electrode. The method of claim 1, wherein the step of generating the plasma at the substrate further comprises the step of: applying a second RF bias to the electrostatic chuck, wherein the first RF bias is at about 350 KHz provided at a power of about 10 watts to about 3,000 watts at a frequency to about 100 MHz, and wherein 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 3,000 watts available under one power. A method of processing a substrate comprising the steps of: flowing a deposition gas comprising a hydrocarbon compound into a processing volume of a plasma processing chamber positioned on an electrostatic chuck with a substrate, wherein the processing volume is maintained at at a pressure of about 0.5 mTorr to about 10 Torr; generating a plasma over the substrate in the process volume by applying a first RF bias to the electrostatic chuck to deposit a stressed on the substrate A diamond-like carbon film, wherein the stressed diamond-like carbon film comprises about 50 atomic percent to about 90 atomic percent sp hybridized carbon atoms and has a compressive stress ^of -500 MPa or greater and greater than 1.5 g/cc a density of ; transferring the substrate containing the stressed diamond-like carbon film from the plasma processing chamber to a thermal annealing chamber; and heating the stressed diamond-like carbon film to about 200° C. to about 600° C. a temperature of ℃ for about 15 seconds to about 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 about 50 atomic percent to about 90 atomic percent of sp ³ hybridized carbon atoms and has a compressive stress of about -20 MPa to less than -500 MPa and a density of greater than 1.5 g/cc. The method of claim 16, wherein the compressive stress of the stress-reduced diamond-like carbon film is about 40% to about 90% less than the compressive stress of the stressed diamond-like carbon film. The method of claim 16, wherein the stressed diamond-like carbon film has a compressive stress of about -600 MPa to about -1,000 MPa and a density of about 1.55 g/cc to less than 2 g/cc, and wherein The stress-reduced diamond-like carbon film has a compressive stress of about -150 MPa to about -400 MPa and a density of about 1.55 g/cc to less than 2 g/cc. The method of claim 16, wherein the stress-reduced diamond-like carbon film has an elastic modulus of greater than 60 GPa to about 200 GPa. A method of processing a substrate, comprising the steps of: flowing a deposition gas comprising a hydrocarbon compound into a processing volume of a processing chamber positioned on an electrostatic chuck with a substrate; A plasma is generated over 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 is The diamond carbon film has a compressive stress of -500 MPa or more; and 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, wherein the stress The reduced diamond-like carbon film has a compressive stress of less than -500 MPa and a density of greater than 1.5 g/cc to about 2.1 g/cc, wherein the compressive stress of the reduced stress diamond-like carbon film is less than the stressed The compressive stress of the diamond-like carbon film is about 40% to about 90%; forming a patterned photoresist layer over the stress-reduced diamond-like carbon film; etching the stress-reduced diamond-like carbon film in a pattern corresponding to the patterned photoresist layer; and The pattern is etched into the substrate.

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