JP7678830B2 - Method for producing dense carbon films for hardmasks and other patterning applications - Patents.com - Google Patents

Description

[0001] Embodiments of the present disclosure relate generally to integrated circuit manufacturing. More specifically, embodiments described and illustrated herein provide techniques for the deposition of dense films for patterning applications.

Description of the Related Art [0002] Integrated circuits have evolved into complex devices that may contain millions of transistors, capacitors, and resistors on a single chip. Evolution in chip design continually requires faster circuits and greater circuit density. The demand for faster circuits with greater circuit density places corresponding demands on the materials used in the fabrication of such integrated circuits. In particular, as the dimensions of integrated circuit components shrink to sub-micron scale, it is now necessary to use not only conductive materials with low resistivity, but also insulating materials with low dielectric constants to obtain adequate electrical performance from such components.

[0003] The demand for greater integrated circuit density also places demands on the process sequences used to manufacture integrated circuit components. For example, in a process sequence using conventional photolithography techniques, a layer of energy sensitive resist is formed over a material layer of a stack disposed on a substrate. The energy sensitive resist layer is exposed to an image of a pattern to form a photoresist mask. An etching process is then used to transfer the mask pattern to one or more material layers of the stack. A chemical etchant used in the etching process is selected to have a higher etch selectivity for the material layer of the stack than for the energy sensitive resist mask. That is, the chemical etchant etches the one or more layers of the material stack at a much faster rate than the energy sensitive resist. The etch selectivity for one or more material layers of the stack over the resist prevents the energy sensitive resist from being worn out before the pattern transfer is complete.

[0004] As pattern dimensions shrink, the thickness of the energy sensitive resist is correspondingly reduced to control pattern resolution. Such thin resist layers may be insufficient to mask the underlying material layer during the pattern transfer process due to erosion by chemical etchants. An intermediate layer called a hard mask (e.g., silicon oxynitride, silicon carbide, or carbon film) is often used between the energy sensitive resist layer and the underlying material layer to facilitate pattern transfer by being more resistant to chemical etchants. Hard mask materials that have both high etch selectivity and fast deposition rates are needed. As critical dimensions (CDs) shrink, existing hard mask materials lack the desired etch selectivity compared to the underlying materials (e.g., oxides and nitrides) and are often difficult to deposit.

[0005] Thus, there is a need in the art for improved hardmask layers and methods for depositing improved hardmask layers.

[0006] Embodiments of the present disclosure generally relate to integrated circuit manufacturing. More specifically, the embodiments described and illustrated herein provide techniques for the deposition of dense films, such as reduced-stress diamond-like carbon films for patterning applications. In one or more embodiments, a method of processing a substrate includes flowing a deposition gas including a hydrocarbon compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, the processing space being maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes applying a first RF bias to the electrostatic chuck to generate a plasma above the substrate in the processing space and depositing a stressed diamond-like carbon film on the substrate, the stressed diamond-like carbon film having a compressive stress of 500 MPa or more. The method further includes heating the stressed diamond-like carbon film during a thermal annealing process at a temperature of about 200° C. to about 600° C. for about 15 seconds to about 60 minutes to produce a reduced-stress diamond-like carbon film. The low stress diamond-like carbon film has a compressive stress of less than 500 MPa and a density greater than 1.5 g/cc. In some embodiments, 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.

[0007] In some embodiments, a method of processing a substrate includes flowing a deposition gas including a hydrocarbon compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, the processing space being maintained at a pressure between about 0.5 mTorr and about 10 Torr. The method also includes generating a plasma above the substrate in the processing space 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 includes between about 50 atomic % and about 90 atomic % sp ³ hybridized carbon atoms and has a compressive stress of 500 MPa or more and a density greater than 1.5 g/cc. The method also includes transferring the substrate including the stressed diamond-like carbon film from the plasma processing chamber to a thermal annealing chamber during a thermal annealing process, and heating the stressed diamond-like carbon film at a temperature between about 200° C. and about 600° C. for between about 15 seconds and about 60 minutes to produce a low stress diamond-like carbon film. The low stress diamond-like carbon film contains about 50 atomic % to about 90 atomic % sp ³ hybridized carbon atoms, has a compressive stress of about 20 MPa to less than 500 MPa, and a density of greater than 1.5 g/cc to about 2.1 g/cc.

[0008] In another embodiment, a method for processing a substrate includes flowing a deposition gas including a hydrocarbon compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, and applying a first RF bias to the electrostatic chuck to generate a plasma above the substrate in the processing space and deposit a stressed diamond-like carbon film on the substrate. The stressed diamond-like carbon film has a compressive stress of 500 MPa or more. The method also includes heating the stressed diamond-like carbon film at a temperature of about 200° C. to about 600° C. for about 15 seconds to about 60 minutes during a thermal annealing process to produce a low-stress diamond-like carbon film. The low-stress diamond-like carbon film has a compressive stress of less than 500 MPa and a density of greater than 1.5 g/cc. The compressive stress of the low-stress 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 low-stress diamond-like carbon film, etching the low-stress diamond-like carbon film in a pattern corresponding to the patterned photoresist layer, and etching the pattern into the substrate.

[0009] In one or more embodiments, a low stress diamond-like carbon film for use as an underlayer in extreme ultraviolet ("EUV") lithography processing is provided and includes about 50 atomic % to about 90 atomic %, or about 60 atomic % to about 70 atomic % ^sp3 hybridized carbon atoms. The low stress doped 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, an elastic modulus of 60 GPa to about 150 GPa, or about 65 GPa to about 80 GPa, and a compressive stress of about 20 MPa to less than about 600 MPa, or about 200 MPa to about 500 MPa, or about 250 MPa to about 400 MPa.

[0010] In order that the features of the present disclosure may be understood in detail, a more particular description of the present disclosure briefly summarized above may be obtained by reference to implementations, some of which are illustrated in the accompanying drawings. It should be noted, however, that the present disclosure may admit of other equally effective embodiments, and therefore, the accompanying drawings depict only typical embodiments of the present disclosure, and are not to be considered as limiting the scope of the present invention.

FIG. 1 shows a schematic cross-sectional view of a deposition system that can be used to practice processes according to one or more embodiments described and illustrated herein. FIG. 1 shows a schematic cross-sectional view of another deposition system that can be used to practice processes according to one or more embodiments described and illustrated herein. FIG. 2 shows a schematic cross-sectional view of an electrostatic chuck that may be used in the apparatus of FIGS. 1A and 1B according to one or more embodiments described and illustrated herein. 1 illustrates a flow diagram of a method for forming a low stress diamond-like carbon film on a film stack disposed on a substrate according to one or more embodiments described and illustrated herein. 1 illustrates a sequence for forming a low stress diamond-like carbon film on a film stack formed on a substrate according to one or more embodiments described and illustrated herein. 1 illustrates a sequence for forming a low stress diamond-like carbon film on a film stack formed on a substrate according to one or more embodiments described and illustrated herein. 1 illustrates a flow diagram of a method of using a low stress diamond-like carbon film according to one or more embodiments described herein.

[0017] For ease of understanding, identical reference numbers have been used, where possible, to designate identical elements common to the figures. It is believed that elements and features of one embodiment may be beneficially incorporated in other embodiments without further description.

[0018] Embodiments provided herein relate to low stress diamond-like carbon films and methods for depositing or forming low stress diamond-like carbon films on substrates. Specific details are presented in the following description and in Figures 1A-5 to provide a thorough understanding of various embodiments of the present disclosure. Other details describing well-known structures and systems often associated with plasma processing and deposition of diamond-like carbon films are not set forth in the following disclosure to avoid unnecessarily obscuring the description of the various implementations.

[0019] Many of the details, dimensions, angles, and other features shown in the drawings are merely illustrative of particular embodiments. Thus, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the present disclosure. In addition, further embodiments of the present disclosure may be practiced without some of the details described below.

[0020] The embodiments described herein include an improved method for producing low stress diamond-like carbon films with high density (e.g., >1.5 g/cc), high modulus (e.g., >60 GPa), and low compressive stress (e.g., <500 MPa). The low stress diamond-like carbon films produced by the embodiments described herein are amorphous and have lower stress than current patterned films as well as higher etch selectivity. The low stress diamond-like carbon films produced by the embodiments described herein not only have low compressive stress, but also have high sp ³ carbon content. In general, the deposition and annealing processes described herein are also fully compatible with current integration schemes for hardmask applications.

[0021] In one or more embodiments, the creation or manufacture of a low stress diamond-like carbon film includes depositing or forming a stressed diamond-like carbon film on a substrate during a deposition process, such as a chemical vapor deposition (CVD) process, and then converting the stressed diamond-like carbon film to a low stress diamond-like carbon film by annealing the substrate, such as during a thermal annealing process. For example, the method includes flowing a deposition gas including a hydrocarbon compound into a process space of a process chamber having a substrate disposed on an electrostatic chuck, and applying a first RF bias to the electrostatic chuck to generate a plasma above the substrate to deposit a stressed diamond-like carbon film on the substrate. The stressed diamond-like carbon film typically has a compressive stress of 500 MPa or more, for example, a compressive stress of 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 during a thermal annealing process to produce a low stress diamond-like carbon film.

[0022] In some embodiments, the stressed diamond-like carbon films described herein may be formed by CVD, such as, for example, plasma enhanced CVD and/or thermal CVD processes, using one or more hydrocarbon compounds. In one or more examples, a deposition gas including one or more hydrocarbon compounds and, optionally, one or more dilution gases, may be flowed or introduced into a processing space of a processing chamber. The substrate is positioned on or on an electrostatic chuck in the processing space, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode. The method further includes generating a plasma on and/or above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit the stressed diamond-like carbon film on the substrate.

[0023] Exemplary hydrocarbon compounds may be or _include ethylene or acetylene ( _C2H2 ), propene _{( C3H6} ), methane ( _CH4 ), butene _{( C4H8} ), 1,3-dimethyladamantane, bicyclo[2.2.1]hepta-2,5-diene (2,5-norbornadiene), adamantine ( _C10H16 ), norbornene ( _C7H10 ), derivatives thereof, isomers thereof _, or any combination thereof. The deposition gas may further include one, two, or more diluent _, carrier, and/or purge gases, such as, for example, helium, argon, xenon, neon, nitrogen ( _N2 ), hydrogen ( _H2 ), or any combination thereof. In some embodiments, the deposition gas may further include an etchant gas, such as chlorine (Cl ₂ ), carbon tetrafluoride (CF ₄ ), and/or nitrogen trifluoride (NF ₃ ), to improve film quality.

[0024] The substrate and/or the processing space can be heated and maintained at a particular temperature during the deposition process. The substrate and/or the processing space 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 space may be heated to a temperature between about 50° C. and about 600° C., between about 50° C. and about 450° C., between about 50° C. and about 350° C., between about 50° C. and about 200° C., between about 50° C. and about 100° C., between about 50° C. and about 50° C., between about 50° C. and about 0° C., between about 40° C. and about 200° C., between about 40° C. and about 100° C., between about 40° C. and about 80° C., between about 40° C. and about 50° C., between about 40° C. and about 25° C., between about 40° C. and about 10° C., between about 40° C. and about 0° C., between about It may be heated to a temperature of 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 about 10°C to about 50°C.

[0025] The process space of the processing chamber is maintained at a subatmospheric pressure during the deposition process. The process space of the processing chamber is maintained at a pressure of 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 1 Torr, about 5 Torr, about 10 Torr, about 20 Torr, about 50 Torr, or about 100 Torr. For example, the processing space of the processing chamber may be from about 0.1 mTorr to about 10 Torr, from about 0.1 mTorr to about 5 Torr, from about 0.1 mTorr to about 1 Torr, from about 0.1 mTorr to about 500 mTorr, from about 0.1 mTorr to about 100 mTorr, from about 0.1 mTorr to about 10 mTorr, from about 1 mTorr to about 10 Torr, from about 1 mTorr to about 5 Torr, from about 1 mTorr to about 1 Torr, about 1 mTorr to about 500 mTorr, about 1 mTorr to about 100 mTorr, about 1 mTorr to about 10 mTorr, about 5 mTorr to about 10 Torr, about 5 mTorr to about 5 Torr, about 5 mTorr to about 1 Torr, about 5 mTorr to about 500 mTorr, about 5 mTorr to about 100 mTorr, or about 5 mTorr to about 10 mTorr. In one or more embodiments, the process space is maintained at a pressure of about 0.5 mTorr to about 10 Torr, about 1 mTorr to about 500 mTorr, or about 5 mTorr to about 100 mTorr when generating a plasma and depositing a stressed diamond-like carbon film on a substrate maintained at a temperature of about 0° C. to about 50° C.

[0026] Plasmas (e.g., capacitively coupled plasmas) can be formed from either top and bottom electrodes or side electrodes. These electrodes may be formed from a single powered electrode, from dual powered electrodes, or from more electrodes with 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) and used alternatively or simultaneously in a CVD system with any or all of the reactive gases listed herein to deposit thin stressed diamond-like carbon films.

[0027] In one or more embodiments, the stressed diamond-like carbon film is deposited in a process chamber having a substrate pedestal maintained at about 10° C., a pressure maintained at about 2 mTorr, and a plasma generated at or above the substrate level by applying a bias of about 2,500 Watts (about 13.56 MHz) to the electrostatic chuck. In other embodiments, an additional RF power of about 1,000 Watts at about 2 MHz is also supplied to the electrostatic chuck to generate a dual bias plasma at the substrate level.

[0028] The embodiments described and illustrated herein are described below with reference to plasma enhanced chemical vapor deposition (PE-CVD) processes that may be performed using any suitable thin film deposition system. Examples of suitable systems include the DXZ® processing chamber, the PRECISION5000® system, the PRODUCER® system, the PRODUCER® GT™ system, the PRODUCER® XP Precision™ system, the PRODUCER® SE™ system, the Sym3® processing chamber, and the CENTURA® system that may use the Mesa™ processing chamber, all of which are available from Applied Materials Inc., Santa Clara, Calif. Other tools capable of performing PE-CVD processes may also be adapted to benefit from the embodiments described herein. Additionally, any system that enables the CVD processes described herein may be used to advantage. Any apparatus descriptions described herein are exemplary and should not be understood or construed as limiting the scope of the embodiments described herein.

[0029] In one or more embodiments, the substrate including the stressed diamond-like carbon film is further exposed to one or more thermal annealing treatments to convert the stressed diamond-like carbon film to a low stress diamond-like carbon film, as described and illustrated herein. In some embodiments, the substrate including the stressed diamond-like carbon film can be thermally annealed in the same processing chamber (e.g., plasma processing chamber) in which it was deposited. That is, the stressed diamond-like carbon film can be deposited and then annealed in the same processing chamber to produce a low stress diamond-like carbon film.

[0030] In another embodiment, the substrate including the stressed diamond-like carbon film is transferred from a first processing chamber (e.g., a plasma processing chamber) to a second processing chamber (e.g., a thermal annealing chamber) and exposed to a thermal annealing process to convert the stressed diamond-like carbon film to a low stress diamond-like carbon film. For example, the manufacturing process may include removing the substrate including the stressed diamond-like carbon film from the first processing chamber, placing the substrate including the stressed diamond-like carbon film in the thermal annealing chamber, heating the stressed diamond-like carbon film during the thermal annealing process to produce a low stress diamond-like carbon film, and then removing the substrate including the low stress diamond-like carbon film from the thermal annealing chamber.

[0031] The stressed diamond-like carbon film, substrate, and/or processing chamber are heated to about 200°C, about 250°C, about 300°C, about 350°C, about 375°C, about 390°C, or about 400°C to about 410°C, about 425°C, about 450°C, about 475°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, or about 800°C during a thermal annealing process to produce a low stress diamond-like carbon film. For example, the stressed diamond-like carbon film, substrate, and/or processing chamber may be thermally annealed at temperatures between about 200° C. and about 800° C., between about 200° C. and about 700° C., between about 200° C. and about 600° C., between about 200° C. and about 500° C., between about 200° C. and about 450° C., between about 200° C. and about 400° C., between about 200° C. and about 350° C., between about 200° C. and about 300° C., between about It is heated at a temperature of 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 to about 420°C, about 350°C to about 400°C, about 350°C to 380°C, about 380°C to about 420°C, or about 390°C to about 410°C.

[0032] The stressed diamond-like carbon film, substrate, and/or processing chamber are heated for about 15 seconds, about 30 seconds, about 1 minute, about 1.5 minutes, about 2 minutes, about 3 minutes, about 4 minutes, or about 5 minutes to about 6 minutes, about 8 minutes, about 10 minutes, about 12 minutes, about 15 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 60 minutes, about 75 minutes, about 90 minutes, or more during a thermal annealing process to produce a low stress diamond-like carbon film. For example, the stressed diamond-like carbon film, substrate, and/or processing chamber may be thermally annealed for a period of time between about 15 seconds and about 90 minutes, between about 15 seconds and about 75 minutes, between about 15 seconds and about 60 minutes, between about 15 seconds and about 45 minutes, between about 15 seconds and about 30 minutes, between about 15 seconds and about 20 minutes, between about 15 seconds and about 10 minutes, between about 15 seconds and about 5 minutes, between about 15 seconds and about 3 minutes, between about 15 seconds and about 1 minute, between about 15 seconds and about 30 seconds, between about 1 minute and about 20 minutes, between about 15 seconds and about 5 minutes, between about 15 seconds and about 3 minutes, between about 15 seconds and about 1 minute, between about 15 seconds and about 30 seconds, between about 1 minute and about 20 minutes, between about 15 seconds and about 5 minutes, between about 15 seconds and about 5 minutes, between about 15 seconds and about 20 ...30 minutes, between about 1 minute and about 20 minutes, between about 15 seconds and about 5 minutes, between about 15 seconds and about 30 minutes, between about 1 minute and about 20 minutes, between about 15 seconds and about 5 minutes, between about 15 It is heated for 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.

[0033] In one or more embodiments, the stressed diamond-like carbon film, the substrate, and/or the processing chamber are heated to a temperature of about 200° C. to about 600° C. for about 15 seconds to about 60 minutes during a thermal annealing process to produce a low stress diamond-like carbon film. In some embodiments, the stressed diamond-like carbon film, the substrate, and/or the processing chamber are heated to a temperature of about 300° C. to about 500° C. for about 2 minutes to about 15 minutes during a thermal annealing process to produce a low stress diamond-like carbon film. In other embodiments, the stressed diamond-like carbon film, the substrate, and/or the processing chamber are heated to a temperature of about 350° C. to about 450° C. for about 3 minutes to about 8 minutes during a thermal annealing process to produce a low stress diamond-like carbon film.

[0034] The substrate including the stressed diamond-like carbon film is located or disposed in a 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 (e.g., a CVD chamber), or other type of chamber that can be used to thermally heat the substrate. The processing space within the processing chamber may be under vacuum and/or under an environment that includes a processing or annealing gas during the thermal annealing process. Exemplary processing or annealing gases may be or include nitrogen ( _N2 ), argon, helium, neon, or any combination thereof.

[0035] The processing space within the processing chamber may have a pressure of about 0.5 mTorr, about 1 mTorr, about 5 mTorr, about 10 mTorr, about 50 mTorr, about 100 mTorr, 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 during the thermal annealing process. For example, the processing space within the processing chamber may be between about 5 mTorr and about 100 Torr, between about 10 mTorr and about 100 Torr, between about 100 mTorr and about 100 Torr, between about 500 mTorr and about 100 Torr, between about 1 Torr and about 100 Torr, between about 5 Torr and about 100 Torr, between about 10 Torr and about 100 Torr, between about 25 Torr and about 100 Torr, between about 50 Torr and about 100 Torr, between about 0.5 mTorr and about 20 Torr, between about 5 mTorr ... The pressure may be 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 20 Torr, about 0.5 mTorr to about 1 Torr, about 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.

[0036] The annealing process significantly reduces the compressive stress from the diamond-like carbon film, so that much of the compressive stress in the stressed diamond-like carbon film is relaxed, reduced or eliminated once it is converted to a low stress diamond-like carbon film. Many other properties of the stressed diamond-like carbon film, such as density, elastic modulus, ^sp3 hybridized carbon atom concentration, hydrogen concentration, etc., are the same or substantially similar to the low stress diamond-like carbon film produced therefrom.

[0037] The compressive stress of the low stress diamond-like carbon film is less than the compressive stress of the stressed diamond-like carbon film from which it is made. In some embodiments, the compressive stress of the low stress diamond-like carbon film is about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, or about 55% to about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% less than the compressive stress of the stressed diamond-like carbon film. For example, the compressive stress of a low stress diamond-like carbon film may be about 25% to about 95%, about 25% to about 90%, about 25% to about 80%, about 25% 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 45%, about 40% to about 40%. It is reduced by 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%.

[0038] The stressed diamond-like carbon film may have a compressive stress of 500 MPa or more, e.g., 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 more. For example, the stressed diamond-like carbon film may have a stress of 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 It may have a compressive stress of 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 about 650 MPa to about 700 MPa.

[0039] The low stress diamond-like carbon film may have a compressive stress of less than 500 MPa, e.g., about 10 MPa, about 20 MPa, about 50 MPa, about 80 MPa, about 100 MPa, about 125 MPa, about 150 MPa, about 175 MPa, about 200 MPa, about 225 MPa, about 250 MPa, about 275 MPa, or about 300 MPa to about 325 MPa, about 350 MPa, about 375 MPa, about 400 MPa, about 425 MPa, about 450 MPa, about 475 MPa, about 490 MPa, about 495 MPa, about 499 MPa, or less than -500 MPa. For example, low stress diamond-like carbon films may have a stress of 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, 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, or less than 500 MPa. Pa 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 less than 400 MPa, about 50 MPa to about 400 MPa, about 80 MPa to about 400 MPa a, 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 40 It may have a compressive stress of 0 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.

[0040] In one or more embodiments, the stressed diamond-like carbon film has a compressive stress of about 600 MPa to about 1,000 MPa, and once converted to a low stress diamond-like carbon film, has a compressive stress of about 20 MPa to about 400 MPa, or about 150 MPa to about 400 MPa. In some embodiments, the stressed diamond-like carbon film has a compressive stress of about 650 MPa to about 900 MPa, and once converted to a low stress diamond-like carbon film, has a compressive stress of about 50 MPa to about 350 MPa, or about 200 MPa to about 350 MPa. In other embodiments, the stressed diamond-like carbon film has a compressive stress of about 700 MPa to about 850 MPa, and once converted to a low stress diamond-like carbon film, has a compressive stress of about 100 MPa to about 325 MPa, or about 250 MPa to about 325 MPa.

[0041] In one or more embodiments, hydrogen radicals are provided through the RPS, which leads to selective etching of sp ² hybridized carbon atoms, which in turn further increases the fraction of sp ³ hybridized carbon atoms in the film, thereby further increasing the etch selectivity. The high etch selectivity of the low stress diamond-like carbon film is achieved by having a higher density and modulus than previously produced films. Without being bound by theory, it is believed that the improved density and modulus result from an increased content of sp ³ hybridized carbon atoms in the low stress diamond-like carbon film, which may be achieved by a combination of low pressure and plasma power.

[0042] Each of the stressed diamond-like carbon films and the low stress diamond-like carbon films may individually have a concentration or percentage of sp3 hybridized carbon atoms (e.g., sp3 hybridized carbon atom content) that is at least 40 atomic % (at%), about 45 at%, about 50 at%, about 55 at%, or about 58 at% to about 60 at%, about 65 at%, about 70 at%, about 75 at%, about 80 at%, about 85 at%, about 88 at%, about 90 at%, about 92 at%, or about 95 at%, based on the total amount of carbon atoms ⁱⁿ the respective diamond- ^like carbon film. For example, the stressed diamond-like carbon film and the low stress diamond-like carbon film each have at least 40 at% to about 95 at%, about 45 at% to about 95 at%, about 50 at% to about 95 at%, about 50 at% to about 90 at%, about 50 at% to about 85 at%, about 50 at% to about 80 at%, about 50 at% to about 75 at%, about 50 at% to about 70 at%, about 50 at% to about 65 at%, about 55 at% to about 75 at%, about 55 at% to about 70 at%, about 55 at% to about 65 at%, about 5 at% to about ... In some embodiments, the SiO 2 nanotube may have a concentration or percentage of sp 3 hybridized carbon atoms that is between 5 at% and about 60 at%, between about 60 at% and about 80 at%, between about 60 at% and about 75 at%, between about 60 at% and about 70 at%, between about 60 at% and about 65 at%, between about 65 at% and about 95 at%, between about 65 at% and about 90 at%, between about 65 at% and about 85 at%, between about 65 at% and about 80 at%, between about 65 at% and about 75 at%, between about 65 at% and about 70 at%, between about 65 at% and about 68 at%, between about 75 at% and about 95 at%, between about 75 at% and about 90 at% ^, between about 75 at% and about 85 at%, between about 75 at% and about 80 at%, or between about 75 at% and about 78 at%.

[0043] In some embodiments, the stressed diamond-like carbon film and the low stress diamond-like carbon film may each have an individual concentration or percentage of ^sp2 hybrid carbon atoms (e.g., sp2 hybrid carbon atom content) of less than 60 at%, e.g., less than 55 at% or less than 50 at%. The stressed diamond-like carbon film and the low stress diamond-like carbon film may each have an individual concentration or percentage of ^sp2 hybrid carbon atoms that is about 5 at%, about 10 at%, about 15 at%, about 20 at%, about 25 at%, about 28 at%, about 30 at%, 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%, based on the total amount of carbon atoms in the ^respective diamond-like carbon film. For example, the stressed diamond-like carbon film and the low stress diamond-like carbon film each have a carbon content of about 5 at% to about 60 at%, 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 4 0at%, about 20at% to about 38at%, about 20at% to about 36at%, about 20at% to about 35at%, about 20at% to about 32at%, about 20at% to about 30a t%, about 20 at% to about 25 at%, about 20 at% to about 22 at%, about 30 at% to about 60 at%, about 30 at% to about 50 at%, about 30 at% to about 45 at% , about 30 at% to about 40 at%, about 30 at% to about 38 at%, about 30 at% to about 36 at%, about 30 at% to about 35 at%, about 30 at% to about 32 at%, about 32 at% to about 38 at%, about 32 at% to about 36 at%, about 32 at% to about 34 at%, about 34 at% to about 38 at%, or about 34 ^at % to about 36 at%.

[0044] The stressed doped diamond-like carbon film and the low stress diamond-like carbon film each individually have a density greater than 1.5 g/cc (grams per cubic centimeter (cm ³ )), for example, 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, the stressed doped diamond-like carbon film and the low stress diamond-like carbon film each have a viscosity of from greater than 1.5 g/cc to about 2.1 g/cc, from greater than 1.5 g/cc to about 2.05 g/cc, from greater than 1.5 g/cc to about 2 g/cc, from greater than 1.5 g/cc to about 1.9 g/cc, from greater than 1.5 g/cc to about 1.85 g/cc, from greater than 1.5 g/cc to about 1.8 g/cc, from greater than 1.5 g/cc to about 1.78 g/cc, from greater than 1.5 g/cc to about 1.75 g/cc, from greater than 1.5 g/cc to about 1.72 g/cc, from greater than 1.5 g/cc to about 1.7 g/cc, cc, more than 1.5 g/cc to about 1.68 g/cc, more than 1.5 g/cc to about 1.65 g/cc, more 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 c, 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 cc, about 1.6 g/cc to about 1.7 g/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/c and individually have a density of from about 1.72 g/cc, from about 1.68 g/cc to about 1.7 g/cc, from about 1.7 g/cc to about 1.75 g/cc, from about 1.7 g/cc to about 1.72 g/cc, from about 1.55 g/cc to less than 2 g/cc, from about 1.6 g/cc to less than 2 g/cc, from about 1.65 g/cc to less than 2 g/cc, from about 1.68 g/cc to less than 2 g/cc, from about 1.7 g/cc to less than 2 g/cc, from about 1.72 g/cc to less than 2 g/cc, from about 1.75 g/cc to less than 2 g/cc, or from about 1.8 g/cc to less than 2 g/cc.

[0045] The stressed doped diamond-like carbon film and the low stress diamond-like carbon film may each individually have a thickness of about 5 Å, about 10 Å, about 50 Å, about 100 Å, about 150 Å, about 200 Å, or about 300 Å to about 400 Å, about 500 Å, about 600 Å, about 700 Å, about 800 Å, about 1,000 Å, about 2,000 Å, about 3,000 Å, about 5,000 Å, about 6,000 Å, about 8,000 Å, about 10,000 Å, about 15,000 Å, about 20,000 Å, or more. For example, the stressed doped diamond-like carbon film and the low stress diamond-like carbon film may each have a thickness of 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 It may have a thickness of 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 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.

[0046] The stressed doped diamond-like carbon film and the low stressed diamond-like carbon film may each have an index of refraction or n value (n at 633 nm) greater than 2, for example, about 2.1, about 2.2, about 2.3, about 2.4 or about 2.5 to about 2.6, about 2.7, about 2.8, about 2.9, or about 3. For example, the stressed doped diamond-like carbon film and the low stressed diamond-like carbon film may each have an index of refraction or n value (n at 633 nm) greater than 2 to about 3, greater than 2 to about 2.8, greater than 2 to about 2.5, greater than 2 to about 2.3, about 2.1 to about 3, about 2.1 to about 2.8, about 2.1 to about 2.5, about 2.1 to about 2.3, about 2.3 to about 3, about 2.3 to about 2.8, or about 2.3 to about 2.5.

[0047] The stressed doped diamond-like carbon film and the low stressed diamond-like carbon film may each have an extinction coefficient or k value (k at 633 nm) greater than 0.1, e.g., about 0.15, about 0.2, about 0.25, or about 0.3. For example, the stressed doped diamond-like carbon film and the low stressed diamond-like carbon film may each have an extinction coefficient or k value (k at 633 nm) greater than 0.1 to about 0.3, greater than 0.1 to about 0.25, greater than 0.1 to about 0.2, greater than 0.1 to about 0.15, about 0.2 to about 0.3, about 0.2 to about 0.25.

[0048] The stressed doped diamond-like carbon film and the low stress diamond-like carbon film may each individually have an elastic modulus of greater than 50 GPa or greater than 60 GPa, for example, 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, the stressed doped diamond-like carbon film and the low stress diamond-like carbon film each have a stress of 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 Each of the polymeric materials may individually have a modulus of elasticity of from 65 GPa to about 250 GPa, from about 65 GPa to about 200 GPa, from about 65 GPa to about 150 GPa, from about 65 GPa to about 125 GPa, from about 65 GPa to about 100 GPa, from about 65 GPa to about 80 GPa, from about 80 GPa to about 400 GPa, from about 80 GPa to about 350 GPa, from about 80 GPa to about 300 GPa, from about 80 GPa to about 250 GPa, from about 80 GPa to about 200 GPa, from about 80 GPa to about 150 GPa, from about 80 GPa to about 125 GPa, or from about 80 GPa to about 100 GPa. In one or more embodiments, the stressed doped diamond-like carbon film and the low stress diamond-like carbon film each have the aforementioned elastic modulus and may individually have a thickness of about 600 Å.

[0049] In some embodiments, the low stress diamond-like carbon film is an underlayer for extreme ultraviolet ("EUV") lithography processing. In some embodiments, the low stress diamond-like carbon film is an underlayer for EUV lithography processing and has a content of ^sp3 hybridized carbon atoms of about 40% to about 90%, based on the total amount of carbon atoms in the film, a density of greater than 1.5 g/cc to about 1.9 g/cc, and an elastic modulus of about 60 GPa to about 150 GPa, or about 200 GPa or greater.

1A shows a schematic diagram of a substrate processing system 132 that may be used to perform deposition of stressed diamond-like carbon films according to embodiments described herein. The substrate processing system 132 includes a processing chamber 100 coupled to a gas panel 130 and a controller 110. The processing chamber 100 generally includes a top wall 124, a side wall 101, and a bottom wall 122 that define a processing space 126. A substrate support assembly 146 is provided within the processing space 126 of the processing chamber 100. The substrate support assembly 146 generally includes an electrostatic chuck 150 supported by a stem 160. The electrostatic chuck 150 may typically be fabricated from aluminum, ceramic, and other suitable materials. The electrostatic chuck 150 may be moved vertically within the processing chamber 100 using a displacement mechanism (not shown).

[0051] The vacuum pump 102 is connected to a port formed in the bottom of the processing chamber 100. The vacuum pump 102 is used to maintain a desired gas pressure within the processing chamber 100. The vacuum pump 102 evacuates post-processing gases and processing by-products from the processing chamber 100.

[0052] The substrate processing system 132 may further include additional devices for controlling the chamber pressure, such as valves (such as throttle valves or isolation valves), positioned between the processing chamber 100 and the vacuum pump 102 to control the chamber pressure.

[0053] A gas distribution assembly 120 having a plurality of apertures 128 is disposed at the top of the processing chamber 100 above the electrostatic chuck 150. The apertures 128 of the gas distribution assembly 120 are utilized to introduce processing gases (e.g., deposition gas, dilution gas, carrier gas, purge gas) into the processing chamber 100. The apertures 128 may have different sizes, quantities, distribution patterns, shapes, designs, and diameters to facilitate the flow of various processing gases for different processing requirements. The gas distribution assembly 120 is connected to a gas panel 130, which allows the supply of various gases to the processing space 126 during processing. A plasma is formed from the processing gas mixture exiting the gas distribution assembly 120 to enhance the pyrolysis of the processing gases resulting in the deposition of material on the surface 191 of the substrate 190.

[0054] The gas distribution assembly 120 and the electrostatic chuck 150 may form a spaced apart electrode pair within the process space 126. To facilitate the generation of a plasma between the gas distribution assembly 120 and the electrostatic chuck 150, one or more RF power sources 140 provide a bias potential to the gas distribution assembly 120 through a matching network 138 (which is optional). Alternatively, the RF power sources 140 and the matching network 138 may be coupled to the gas distribution assembly 120, to the electrostatic chuck 150, or to both the gas distribution assembly 120 and the electrostatic chuck 150, or may be coupled to an antenna (not shown) located outside the process chamber 100. In one or more embodiments, the RF power sources 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 embodiments, the RF power source 140 can provide a power of about 100 watts to about 3,000 watts at a frequency of about 50 kHz to about 13.6 MHz. In other examples, the RF power source 140 can provide a power of about 500 watts to about 1,800 watts at a frequency of about 50 kHz to about 13.6 MHz.

[0055] The controller 110 includes a central processing unit (CPU) 112, memory 116, and support circuits 114, which are utilized to control the processing sequence and regulate the gas flow from the gas panel 130. The CPU 112 may be any form of general-purpose computer processor available for use in an industrial setting. Software routines may be stored in the memory 116, for example, in random access memory, read-only memory, floppy or hard disk drives, or other forms of digital storage. The support circuits 114 are conventionally connected to the CPU 112 and may include cache, clock circuits, input/output systems, power supplies, and the like. Bidirectional communication between the controller 110 and the various components of the substrate processing system 132 is handled through a number of signal cables, collectively referred to as signal buses 118, some of which are shown in FIG. 1A.

[0056] FIG. 1B illustrates a schematic cross-sectional view of another substrate processing system 180 that can be used to practice embodiments described herein. The substrate processing system 180 is similar to the substrate processing system 132 of FIG. 1A, except that the substrate processing system 180 is configured to flow process gases from the gas panel 130 through the sidewall 101 across the surface 191 of the substrate 190. In addition, the gas distribution assembly 120 shown in FIG. 1A is replaced with an electrode 182. The electrode 182 can be configured as a secondary charge generating device. In one or more embodiments, the electrode 182 is a silicon-containing electrode.

[0057] FIG. 2 shows 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 in practicing embodiments described herein. Referring to FIG. 2, the electrostatic chuck 150 may include a heater element 170 adapted to control the temperature of a substrate 190 supported on a top surface 192 of the electrostatic chuck 150. The heater element 170 may be embedded in the electrostatic chuck 150. The electrostatic chuck 150 may be resistively heated by applying a current from a heater power supply 106 to the heater element 170. The heater power supply 106 may be coupled through an RF filter 216. The RF filter 216 may be used to protect the heater power supply 106 from RF energy. The heater element 170 may be made of a nickel-chromium wire enclosed in a sheath tube of a nickel-iron-chromium alloy (e.g., INCOLOY®). The current supplied by the heater power supply 106 is regulated by the controller 110 to control the heat generated by the heater element 170 and thus maintain the substrate 190 and electrostatic chuck 150 at a substantially constant temperature during film deposition. The current supplied can be adjusted to selectively control the temperature of the electrostatic chuck 150 from about 50° C. to about 600° C.

[0058] Referring to FIG. 1, in a conventional manner, 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. The measured temperature is used by the controller 110 to control the power supplied to the heater element 170 to maintain the substrate at a desired temperature.

[0059] The electrostatic chuck 150 includes a chucking electrode 210, which may be a mesh of conductive material. The chucking electrode 210 may be embedded in the electrostatic chuck 150. The chucking electrode 210 is coupled to a chucking power supply 212 and, when energized, electrostatically clamps the substrate 190 to the upper surface 192 of the electrostatic chuck 150.

[0060] The chucking electrode 210 may be configured as a monopolar or bipolar electrode, or may have another suitable configuration. The chucking electrode 210 may be coupled through an RF filter 214 to a chucking power supply 212, which provides direct current (DC) power to electrostatically clamp the substrate 190 to the upper surface 192 of the electrostatic chuck 150. The RF filter 214 prevents RF power utilized to form the plasma in the processing chamber 100 from damaging electrical equipment or causing electrical disturbances outside the chamber. The electrostatic chuck 150 may be fabricated from a ceramic material, such as aluminum nitride or aluminum oxide (e.g., alumina). Alternatively, the electrostatic chuck 150 may be fabricated from a polymer, such as polyimide, polyetheretherketone (PEEK), polyaryletherketone (PAEK), etc.

[0061] A power application system 220 is coupled to the substrate support assembly 146. The power application system 220 may include a heater power supply 106, a chucking power supply 212, a first radio frequency (RF) power supply 230, and a second RF power supply 240. The power application system 220 may include a controller 110 and a sensor device 250 in communication with the controller 110 and both the first RF power supply 230 and the second RF power supply 240. The controller 110 may further be utilized to control a plasma from the process gas by applying RF power from the first RF power supply 230 and the second RF power supply 240 to deposit a layer of material on the substrate 190.

[0062] As described above, the electrostatic chuck 150:
In one aspect, the electrostatic chuck 150 includes a chucking electrode 210 that functions to chuck the substrate 190 and can also function as a first RF electrode. The electrostatic chuck 150 may also include a second RF electrode 260, which, in conjunction with the chucking electrode 210, may apply RF power to condition the plasma. The first RF power source 230 may be coupled to the second RF electrode 260, while the second RF power source 240 may be coupled to the chucking electrode 210. A first matching network and a second matching network may be provided for each of the first RF power source 230 and the second RF power source 240. The second RF electrode 260 may be a solid metal plate of a conductive material as shown. Alternatively, the second RF electrode 260 may be a mesh of a conductive material.

[0063] The first RF power source 230 and the second RF power source 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 source 230 and the second RF power source 240 may individually generate power at a frequency between about 350 KHz and about 100 MHz (e.g., 350 KHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, or 100 MHz). In one or more embodiments, the first RF power source 230 may generate power at a frequency of 13.56 MHz and the second RF power source 240 may generate power at a frequency of 2 MHz, or vice versa. The RF power from one or both of the first RF power source 230 and the second RF power source 240 may be varied to tune the plasma. For example, the sensor device 250 may be used to monitor RF energy from one or both of the first RF power source 230 and the second RF power source 240. Data from the sensor device 250 may be transmitted to the controller 110, which may be utilized to modify the power applied by the first RF power source 230 and the second RF power source 240.

[0064] In one or more embodiments, the electrostatic chuck 150 may separate the chucking electrode 210 and the RF electrode from one another and may apply a first RF bias to the RF electrode 260 and a second RF bias to the chucking electrode 210. In one or more examples, the first RF bias is provided at a frequency of about 350 KHz to about 100 MHz and at a power of about 10 Watts to about 3,000 Watts, and the second RF bias is provided at a frequency of about 350 KHz to about 100 MHz and at a power of about 10 Watts to about 3,000 Watts. In other examples, the first RF bias is provided at a frequency of about 13.56 MHz and at a power of about 2,500 Watts to about 3,000 Watts, and the second RF bias is provided at a frequency of about 2 MHz and at a power of about 800 Watts to about 1,200 Watts.

[0065] In one or more embodiments, a deposition gas containing one or more hydrocarbon compounds may be flowed or introduced into a processing space of a processing chamber, such as a PE-CVD chamber. The hydrocarbon compounds and dilution gases may be flowed or introduced into the processing space separately. In some examples, one or more substrates are placed on an electrostatic chuck in the processing chamber. The electrostatic chuck may have a separate chucking electrode and an RF electrode. A plasma may be ignited or generated at or near the substrate (e.g., at the substrate level) by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode. A stressed diamond-like carbon film is deposited or formed on the substrate. In some embodiments, a patterned photoresist layer may be deposited or formed on the stressed diamond-like carbon film, the stressed diamond-like carbon film is etched or formed in a pattern corresponding to the patterned photoresist layer, and the pattern is etched or formed in the substrate. In other embodiments, the stressed diamond-like carbon film may be converted to a low stress diamond-like carbon film, then a patterned photoresist layer may be deposited or formed on the low stress diamond-like carbon film, the low stress diamond-like carbon film is etched or formed with a pattern corresponding to the patterned photoresist layer, and the pattern is etched or formed into the substrate.

[0066] In general, the following exemplary deposition process parameters may be used to form stressed diamond-like carbon films: The substrate temperature may range from about 50° C. to about 350° C. (e.g., from about 40° C. to about 100° C., from about 10° C. to about 100° C., or from about 10° C. to about 50° C.). The chamber pressure may range from about 0.5 mTorr to about 10 Torr (e.g., from about 2 mTorr to about 50 mTorr, or from about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may range from about 20 sccm to about 5,000 sccm (e.g., from about 50 sccm to about 1,000 sccm, from about 100 sccm to about 200 sccm, or from about 150 sccm to about 200 sccm). The flow rate of the dilution or purge gas (e.g., He) may be from about 1 sccm to about 3,000 sccm (e.g., from about 5 sccm to about 500 sccm, from about 10 sccm to about 150 sccm, or from about 20 sccm to about 100 sccm). The stressed diamond-like carbon film may be deposited to a thickness of from about 200 Å to about 6,000 Å (e.g., from about 300 Å to about 5,000 Å, from about 400 Å to about 800 Å, from about 2,000 Å to about 3,000 Å, or from about 5 Å to about 200 Å, depending on the application). In one or more embodiments, the process parameters provide example process parameters for a 300 mm substrate in a deposition chamber available from Applied Materials, Inc. of Santa Clara, Calif.

[0067] FIG. 3 shows a flow diagram of a method 300 for forming a low stress diamond-like carbon film on a film stack disposed on a substrate according to one embodiment of the present disclosure. The stressed diamond-like carbon film formed on the film stack can be used, for example, as a hard mask for forming a step-like structure in the film stack. FIGS. 4A and 4B are schematic cross-sectional views showing a sequence for forming a low stress diamond-like carbon film on a film stack disposed on a substrate according to the method 300. Although the method 300 is described below in the context of a hard mask layer that can be formed on a film stack used to fabricate a step-like structure in a film stack for a three-dimensional semiconductor device, the method 300 can also be advantageously used in other device manufacturing applications. It should further be understood that the steps shown in FIG. 3 can be performed simultaneously and/or in a different order than that shown in FIG. 3.

[0068] The method 300 begins at step 310 by positioning a substrate (such as the substrate 402 shown in FIG. 4A) in a process chamber (such as the process chamber 100 shown in FIG. 1A or FIG. 1B). The substrate 402 may be the substrate 190 shown in FIGS. 1A, 1B, and 2. The substrate 402 may be positioned on an electrostatic chuck (e.g., the upper surface 192 of the electrostatic chuck 150). The substrate 402 may be a silicon-based material, or any suitable insulating or conductive material as desired, with a film stack 404 disposed thereon, which may be utilized to form a structure 400 (e.g., a stepped structure) in the film stack 404.

[0069] As shown in the embodiment depicted in FIG. 4A, the substrate 402 may have a substantially planar surface, a non-planar surface, or a substantially planar surface with structures formed thereon. A film stack 404 is formed on the substrate 402. In one or more embodiments, the film stack 404 may be utilized to form gate structures, contact structures, or interconnect structures in front-end or back-end processing. The method 300 may be performed on the film stack 404 to form stepped structures used in memory structures (such as NAND structures) in the film stack 404. In one or more embodiments, the substrate 402 may be a material such as crystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon substrate, patterned or unpatterned substrate silicon-on-insulator (SOI), carbon doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, etc. The substrate 402 may have various dimensions, for example, 200 mm, 300 mm, 450 mm, or other diameters, and may be a rectangular or square panel. Unless otherwise specified, the embodiments and examples described herein are performed on substrates with a diameter of 200 mm, 300 mm, or 450 mm. In embodiments in which the substrate 402 utilizes an SOI structure, the substrate 402 may include a buried dielectric layer disposed on a silicon crystalline substrate. In one or more embodiments described herein, the substrate 402 may be a crystalline silicon substrate.

[0070] In one or more embodiments, the film stack 404 disposed on the substrate 402 may have multiple vertically stacked layers. The film stack 404 may include pairs including a first layer (shown as _408a1 , _408a2 , _408a3 , ..., 408a _n ) and a second layer (shown as _408b1 , _408b2 , _408b3 , ..., 408b _n ) that are repeated in the film stack 404. These pairs include alternating first layers (shown as _408a1 , _408a2 , _408a3 , ..., _408an ) and second layers (shown as _408b1 , _408b2 , _408b3 , ..., _408bn ), and are repeatedly formed until a target number of pairs of first and second layers is reached.

[0071] The film stack 404 may be part of a semiconductor chip, such as a three-dimensional memory chip. It should be noted that although three repeating layers of a first layer (shown as _408a1 , _408a2 , _408a3 , ..., 408a _n ) and a second layer (shown as _408b1 , _408b2 , _408b3 , ..., 408b _n ) are shown in Figures 4A-B, any desired number of repeating pairs of first and second layers may be utilized as desired.

[0072] In one or more embodiments, the film stack 404 may be utilized to form multiple gate structures for a three-dimensional memory chip. The first layers _408a1 , _408a2 , _408a3 ,..., _408an formed in the film stack 404 may be first dielectric layers, and the second layers _408b1 , _408b2 , _408b3 ,..., _408bn may be second dielectric layers. The first layers _408a1 , _408a2 , _408a3 ,..., _408an and the second layers _408b1 , _408b2 , _408b3 ,... , 408b _n may include, among others, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, titanium nitride, composites of oxide and nitride, at least one or more oxide layers sandwiching a nitride layer, and combinations thereof. In one or more embodiments, the dielectric layer may be a high-k material having a dielectric constant greater than 4. Suitable examples of high-k materials include hafnium oxide, zirconium oxide, titanium oxide, hafnium silicon oxide or hafnium silicate, hafnium aluminum oxide or hafnium aluminate, zirconium silicon oxide or zirconium silicate, tantalum oxide, aluminum oxide, aluminum doped hafnium dioxide, bismuth strontium titanium (BST), and platinum zirconium titanium (PZT), dopants thereof, or any combination thereof.

[0073] In one or more examples, the first layers _408a1 , _408a2 , _408a3 ,..., _408an are silicon oxide layers and the second layers _408b1 , 408b2, _{408b3,..., 408bn are silicon nitride layers or polysilicon layers disposed on the first layers 408a1, 408a2 , 408a3} ,..., 408an. In one or more embodiments, the first layers _408a1 , _408a2 , _408a3 ,..., _408an are silicon oxide layers and the second layers 408b1, 408b2, 408b3,..., 408bn are silicon nitride layers or polysilicon layers disposed on the first layers _408a1 , _408a2 , _408a3 ,..., 408an. , 408a _n may be controlled in thickness from about 50 Å to about 1,000 Å (e.g., about 500 Å) and the thickness of each of the second layers 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n may be controlled in thickness from about 50 Å to about 1,000 Å (e.g., about 500 Å). The film stack 404 may have a total thickness from about 100 Å to about 2,000 Å. In one or more embodiments, the total thickness of the film stack 404 is from about 3 microns to about 10 microns, and will vary as technology advances.

[0074] It should be noted that a low stress diamond-like carbon film may be formed on any surface or any portion of the substrate 402, regardless of whether or not a film stack 404 is present on the substrate 402.

[0075] In step 320, a chucking voltage is applied to the electrostatic chuck to clamp or place the substrate 402 on the electrostatic chuck. In one or more embodiments in which the substrate 402 is positioned on the top surface 192 of the electrostatic chuck 150, the top surface 192 supports and clamps the substrate 402 during processing. The electrostatic chuck 150 seals the substrate 402 to the top surface 192 to prevent backside deposition. An electrical bias is provided to the substrate 402 via the chucking electrode 210. The chucking electrode 210 may be in electrical communication with a chucking power supply 212 that provides a bias voltage to the chucking electrode 210. In one or more embodiments, the chucking voltage is from about 10 volts to about 3,000 volts, from about 100 volts to about 2,000 volts, or from about 200 volts to about 1,000 volts.

[0076] In step 320, several process parameters may be adjusted for processing. In one or more embodiments suitable for processing a 300 mm substrate, the process pressure in the process space may be maintained between about 0.1 mTorr and about 10 Torr (e.g., between about 2 mTorr and about 50 mTorr, or between about 5 mTorr and about 20 mTorr). In some embodiments suitable for processing a 300 mm substrate, the process temperature and/or substrate temperature may be maintained between about 50° C. and about 350° C. (e.g., between about 0° C. and about 50° C., or between about 10° C. and about 20° C.).

[0077] In one or more embodiments, a constant chucking voltage is applied to the substrate 402. In some embodiments, the chucking voltage may be pulsed to the electrostatic chuck 150. In other embodiments, a backside gas may be applied to the substrate 402 while the chucking 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.

[0078] In step 330, a plasma is generated at the substrate, for example adjacent to the substrate or near the substrate level, by applying a first RF bias to the electrostatic chuck. The plasma generated at the substrate can be generated in a plasma region between the substrate and the electrostatic chuck. The first RF bias can be from about 10 watts to about 3,000 watts at a frequency of about 350 KHz to about 100 MHz (e.g., 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In one or more embodiments, the first RF bias is provided at a frequency of about 13.56 MHz and with a power of about 2,500 watts to about 3,000 watts. 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 electrical communication with the first RF power source 230, which provides a bias voltage to the second RF electrode 260. In one or more embodiments, the bias power is from about 10 watts to about 3,000 watts, from about 2,000 watts to about 3,000 watts, or from about 2,500 watts to about 3,000 watts. The first RF power source 230 may generate power at a frequency of from about 350 KHz to about 100 MHz (e.g., about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz).

[0079] In one or more embodiments, step 330 further includes applying a second RF bias to the electrostatic chuck. The second RF bias can be from about 10 watts to about 3,000 watts at a frequency of about 350 KHz to about 100 MHz (e.g., about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In some embodiments, the second RF bias is provided at a frequency of about 2 MHz and with a power of about 800 watts to about 1,200 watts. In other examples, the second RF bias is provided to the substrate 402 via the chucking electrode 210. The chucking electrode 210 can be in electrical communication with a second RF power source 240 that provides a bias voltage to the chucking electrode 210. In one or more embodiments, the bias power is between about 10 watts and about 3,000 watts, between about 500 watts and about 1,500 watts, or between about 800 watts and about 1,200 watts. The second RF power source 240 may generate power at a frequency between about 350 KHz and about 100 MHz (e.g., about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz). In one or more embodiments, the chucking voltage provided during step 320 is maintained during step 330.

[0080] In some embodiments, during step 330, a first RF bias may be supplied to the substrate 402 via the chucking electrode 210 and a second RF bias may be supplied to the substrate 402 via the second RF electrode 260. In one or more embodiments, 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).

[0081] In step 340, deposition gas is flowed into the process space 126 to form a stressed diamond-like carbon film on the film stack. The deposition gas may be flowed into the process space 126 from the gas panel 130, through the gas distribution assembly 120, or through the sidewall 101. The deposition gas includes one or more nitrogen dopant compounds. The hydrocarbon compound may be or include one, two, or more hydrocarbon compounds in any state of matter. The hydrocarbon compound may be either a liquid or a gas, although some advantages may be realized if any of the precursors are vapors at room temperature to simplify the hardware required to meter, control, and deliver the materials to the process space.

[0082] The deposition gas may further include an inert gas, a diluent gas, an etchant gas, or a combination thereof. In one or more embodiments, the chucking voltage provided during step 320 is maintained during step 340. In some embodiments, the process conditions established during step 320 and the plasma formed during step 330 are maintained during step 340.

[0083] In one or more embodiments, the hydrocarbon compound is a gaseous hydrocarbon or a liquid hydrocarbon. The hydrocarbon can be or include one or more alkanes, one or more alkenes, one or more alkynes, one or more aromatics, or any combination thereof. In some embodiments, the hydrocarbon compound is represented by the general formula _CxHy , where x has a range from 1 to 20 and _y has a range from 1 to 20. Suitable hydrocarbon compounds include, for example, _C2H2 , _C3H6 , _CH4 , _C4H8 , 1,3 _{- dimethyladamantane} , bicyclo[2.2.1 _] hepta-2,5-diene (2,5-norbornadiene), _adamantine ( _C10H16 ), _norbornene ( _C7H10 ), or any combination thereof. In one or more embodiments, ethyne is utilized to form a more stable intermediate species that allows for enhanced surface mobility.

[0084] The hydrocarbon compound can be or include one or more alkanes (e.g., C _n H _2n+2 , where n is 1 to 20). Suitable hydrocarbon compounds include alkanes (e.g., methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ) and its isomers isopentane, pentane (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 combinations thereof).

[0085] The hydrocarbon compound can be or include one or more alkenes (e.g., C _n H _2n , where n is 1 to 20). Suitable hydrocarbon compounds include, for example, alkenes such as ethylene, propylene (C ₃ H ₆ ), butylene and its isomers, pentene and its isomers, dienes such as butadiene, isoprene, pentadiene, hexadiene, or combinations thereof. Further suitable hydrocarbons include, for example, halogenated alkenes (e.g., monofluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, monochloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, or any combination thereof).

[0086] The hydrocarbon compound can be or include one or more alkynes (e.g., C _n H _2n2 , where n is 1 to 20). Suitable hydrocarbons include, for example, alkynes (e.g., acetylene (C ₂ H ₄ ), propyne (C ₃ H ₄ ), butylene (C ₄ H ₈ ), vinyl acetylene, or combinations thereof).

[0087] The hydrocarbon compound may be or include one or more aromatic hydrocarbon compounds (e.g., benzene, styrene, toluene, xylene, ethylbenzene, acetophenone, methyl benzoate, phenyl acetate, phenol, cresol, furan, etc.), alpha-terpinene, cymene, 1,1,3,3-tetramethylbutylbenzene, t-butyl ether, t-butyl ethylene, methyl methacrylate, and t _- butyl furfuryl ether, compounds having the chemical formulas _C3H2 and _{C5H4 ,} halogenated aromatic compounds (including monofluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene, or any combination thereof).

[0088] In one or more embodiments, the deposition gas further comprises one or more dilution gases, one or more carrier gases, and/or one or more purge gases. Suitable dilution gases, carrier gases, 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, among others, may be co-flowed or otherwise supplied to the process space 126 with the deposition gas. Argon, helium, and nitrogen may be used to control the density and deposition rate of the stressed diamond-like carbon film. In some cases, the addition of _N2 and/or _NH3 may be used to control the hydrogen ratio in the stressed diamond-like carbon film, as described below. Alternatively, no dilution gas may be used during deposition.

[0089] In some embodiments, the deposition gas further comprises an etchant gas. Suitable etchant gases are or include chlorine ( _Cl2 ), fluorine ( _F2 ), hydrogen fluoride (HF), carbon tetrafluoride ( _CF4 ), nitrogen trifluoride ( _NF3 ), or combinations thereof. Without being bound by theory, it is believed that the etchant gas selectively etches ^sp2 hybridized carbon atoms from the film, thus increasing the fraction of ^sp3 hybridized carbon atoms in the film, thereby increasing the etch selectivity of the stressed diamond-like carbon film 412.

[0090] In one or more embodiments, after the stressed diamond-like carbon film 412 is deposited or formed on the substrate in step 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 in step 340. In other embodiments, the hydrogen radicals are formed in the RPS and supplied to the process region. Without being bound by theory, it is believed that exposing the stressed diamond-like carbon film to hydrogen radicals leads to selective etching of ^sp2 hybridized carbon atoms, thereby increasing the fraction of ^sp3 hybridized carbon atoms in the film, thereby increasing the etch selectivity.

[0091] In step 350, after the stressed diamond-like carbon film 412 is formed on the substrate, the substrate is dechucked. During step 350, the chucking voltage is turned off. The reactive gases are also turned off and, optionally, purged from the processing chamber. In one or more embodiments, the RF power is reduced (e.g., about 200 watts) during step 350. Optionally, the controller 110 monitors the impedance change to determine if the electrostatic charge has dissipated through the RF path to ground. Once the substrate is dechucked from the electrostatic chuck, residual gas is purged from the processing chamber. The processing chamber is pumped down and the substrate is lifted on lift pins and transported out of the chamber.

[0092] In some alternative embodiments, the substrate including the stressed diamond-like carbon film 412 can be heated in a thermal annealing process in the same processing chamber to produce a low stress diamond-like carbon film prior to dechucking the substrate in operation 350.

[0093] In one or more embodiments, after operation 350, the substrate including the stressed diamond-like carbon film 412 is lifted by lift pins and transferred out of the plasma processing chamber. In operation 360, the substrate is introduced into another processing chamber, such as a thermal annealing chamber, a vacuum chamber, a deposition chamber, or other type of processing chamber that can be used to perform a thermal annealing process. The substrate including 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 during the thermal annealing process to produce a low stress diamond-like carbon film.

[0094] Figure 5 shows a flow diagram of a method 500 of using a low stress diamond-like carbon film according to one or more embodiments described and illustrated herein. After the low stress diamond-like carbon film 412 is formed on a substrate, it can be used as a patterning mask in an etching process to form three-dimensional structures (such as staircase structures). The low stress diamond-like carbon film 412 can be patterned using standard photoresist patterning techniques. In step 510, a patterned photoresist (not shown) can be formed on the low stress diamond-like carbon film 412. In step 520, the low stress diamond-like carbon film 412 can be etched with a pattern corresponding to the patterned photoresist layer, which is then etched into the substrate 402 in step 530. In step 540, material can be deposited into the etched portions of the substrate 402. The low stress diamond-like carbon film 412 can be removed using a solution containing hydrogen peroxide and sulfuric acid. One exemplary solution that includes hydrogen peroxide and sulfuric acid is known as piranha solution or piranha etchant. The low stress diamond-like carbon film 412 may also be removed using an etching chemistry that contains oxygen and a halogen (e.g., fluorine or chlorine) (e.g., _Cl2 / _O2 , _CF4 / _O2 , _Cl2 / _O2 / _CF4 ). The low stress diamond-like carbon film 412 may also be removed by a chemical mechanical polishing (CMP) process.

Extreme Ultraviolet (EUV) Patterning Schemes [0095] When using metal-containing photoresists in extreme ultraviolet (EUV) patterning schemes, the selection of underlayers becomes important to prevent nanofailures (e.g., bridging and spacing defects) in semiconductor devices. The traditional underlayer for EUV patterning (lithography) schemes is a spin-on-carbon (SOC) material. However, during patterning, metals such as tin, for example, diffuse through the SOC material, leading to nanofailures in semiconductor devices. Such nanofailures act to degrade, degrade, and impede semiconductor performance.

[0096] On the other hand, the dense carbon films described herein have superior film quality (e.g., improved hardness and density). Such hardness and density enable the dense carbon films to act as a much stronger barrier to metal intrusion and prevent (or at least reduce) micro defects than conventional SOC films. In one or more embodiments, a low stress diamond-like carbon film is provided for use as an underlayer for extreme ultraviolet (EUV) lithography processing.

[0097] In one or more embodiments, the low stress diamond-like carbon film used as an underlayer for EUV lithography processing can be any film described herein. The low stress diamond-like carbon film has from about 40% to about 90% sp and a compressive stress of from about -20 ^MPa to less than about -600 MPa, from about -150 MPa to less than about -600 MPa, or from about -200 MPa to less than about -600 MPa (e.g., from about 225 MPa to about 500 MPa, or from about 250 MPa to about 400 MPa); a modulus of elasticity from greater than 60 GPa to about 200 GPa, or from greater than 60 GPa to about 150 GPa; and a density from greater than about 1.5 g/cc to about 2.1 g/cc, from about 1.55 g/cc to less than 2 g/cc (e.g., from about 1.6 g/cc to about 1.8 g/cc, from about 1.65 g/cc to about 1.75 g/cc, or from about 1.68 g/cc to about 1.72 g/cc).

[0098] Thus, methods and apparatus are provided for forming a hard mask layer that is or includes a low stress diamond-like carbon film that can be used to form stepped structures for manufacturing three-dimensional stacks of semiconductor devices. By utilizing a low stress diamond-like carbon film as a hard mask layer with the desired robust film properties and etch selectivity, improved dimensional and profile control of the resulting structures formed in the film stack can be obtained, enhancing the electrical performance of chip devices in applications for three-dimensional stacks of semiconductor devices.

[0099] Thus, some of the advantages of the present disclosure provide a process for depositing or forming low stress diamond-like carbon films on a substrate. Typical PE-CVD hardmask films have a very low percentage of hybrid sp ³ atoms and therefore low modulus and etch selectivity. Some of the embodiments described herein allow for the production of doped films with about 60% or more hybrid sp ³ atoms using low process pressures (less than 1 Torr) and bottom driven plasma, which provides improved etch selectivity compared to previously available hardmask films. In addition, some of the embodiments described herein are performed at low substrate temperatures, which allows for the deposition of other dielectric films at much lower temperatures than currently possible, opening up applications with low thermal budgets that could not previously be addressed by CVD. In addition, some of the embodiments described herein may be used as underlayers for EUV lithography processing.

[00100] The above is directed to embodiments of the present disclosure, however, other and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure, the scope of which is determined by the following claims. All documents described herein are incorporated by reference, including any priority documents and/or test procedures, to the extent not inconsistent with this text. As is apparent from the summary and specific embodiments above, forms of the present disclosure have been shown and described, but various modifications may be made without departing from the spirit and scope of the present disclosure. Thus, no limitation of the present disclosure is intended. Similarly, the word "comprising" is considered to be synonymous with the word "including" under US law. Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" prior to the recitation of the composition, one or more elements is also contemplated, and vice versa.

[00101] Certain embodiments and features are described using a set of upper numerical limits and a set of lower numerical limits. It should be recognized that ranges including combinations of any two values (e.g., any lower value with any upper value, any two lower values, and/or any two upper values) are envisioned unless otherwise indicated. Certain lower limits, upper limits, and ranges are set forth in one or more claims below.

Claims (20)

1. A method for processing a substrate, comprising:
flowing a deposition gas comprising a hydrocarbon compound into a process space of a process chamber having a substrate disposed on an electrostatic chuck, the process space being maintained at a pressure between 0.5 mTorr and 10 Torr;
generating a plasma above the substrate in the processing space by applying a first RF bias to the electrostatic chuck, and depositing a stressed diamond-like carbon film having a compressive stress of 500 MPa or more on the substrate;
heating the stressed diamond-like carbon film during a thermal annealing process at a temperature between 200 ° C. and 600° C. for a period between 15 seconds and 60 minutes to produce a low stress diamond-like carbon film having a compressive stress of less than 500 MPa and a density greater than 1.5 g/cc;
The method includes: removing the substrate containing the stressed diamond-like carbon film from the processing chamber;
placing the substrate including the stressed diamond-like carbon film in a thermal annealing chamber to heat the stressed diamond-like carbon film during the thermal annealing process to produce the low stress diamond-like carbon film;
removing the substrate containing the low stress diamond-like carbon film from the thermal annealing chamber;
The method of claim 1 further comprising: 3. The method of claim 2, wherein during the thermal annealing process, the stressed diamond-like carbon film is heated at a temperature between 300 ° C. and 500° C. for a time between 2 minutes and 15 minutes to produce the low stress diamond-like carbon film. The method of claim 2 , wherein the thermal annealing chamber is maintained at a pressure between 10 mTorr and 100 Torr during the thermal annealing process. 3. The method of claim 2, wherein during the thermal annealing process, the stressed diamond-like carbon film is heated in an environment comprising a gas comprising nitrogen ( _N2 ), argon, helium, neon, or any combination thereof to produce the low stress diamond-like carbon film. The method of claim 1 , wherein the compressive stress of the low-stress diamond-like carbon film is between 40% and 90 % less than the compressive stress of the stressed diamond-like carbon film. 2. The method of claim 1, wherein the stressed diamond-like carbon film has a compressive stress of 600 MPa to 1,000 MPa and the low stress diamond-like carbon film has a compressive stress of 150 MPa to 400 MPa. The method of claim 1 , wherein the low stress diamond-like carbon film has an elastic modulus of greater than 60 GPa to 200 GPa. 2. The method of claim 1, wherein the low stress diamond-like carbon film has a density of from 1.55 g/cc to less than 2 g/cc. 2. The method of claim 1 , wherein the process space is maintained at a pressure between 5 mTorr and 100 mTorr and the substrate is maintained at a temperature between 0 ° C. and 50 ° C. when generating the plasma to deposit the stressed diamond-like carbon film on the substrate. 2. The method of claim 1, wherein the low stress diamond-like carbon film comprises between 50 atomic % and 90 atomic % ^sp3 hybridized carbon atoms. The method of claim 1, wherein the hydrocarbon compound comprises ethylene, propene, methane, butene, 1,3-dimethyladamantane, bicyclo[2.2.1]hepta-2,5-diene, adamantine, norbornene, or any combination thereof. The method of claim 1 , wherein the deposition gas further comprises helium, argon, xenon, neon, hydrogen (H ₂ ), or any combination thereof. The method of claim 1, wherein generating the plasma at the substrate further comprises applying a second RF bias to the electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separate from the chucking electrode, the first RF bias being applied to the RF electrode and the second RF bias being applied to the chucking electrode. 10. The method of claim 1, wherein generating the plasma at the substrate further comprises applying a second RF bias to the electrostatic chuck, the first RF bias being supplied at a frequency between 350 KHz and 100 MHz and at a power between 10 Watts and 3,000 Watts, and the second RF bias being supplied at a frequency between 350 KHz and 100 MHz and at a power between 10 Watts and 3,000 Watts. 1. A method for processing a substrate, comprising:
flowing a deposition gas comprising a hydrocarbon compound into a process space of a plasma processing chamber having a substrate disposed on an electrostatic chuck, the process space being maintained at a pressure between 0.5 mTorr and 10 Torr;
generating a plasma in the process space above the substrate by applying a first RF bias to the electrostatic chuck and depositing a stressed diamond-like carbon film on the substrate , the stressed diamond-like carbon film comprising 50 atomic % to 90 atomic % ^sp3 hybridized carbon atoms, a compressive stress of 500 MPa or greater, and a density greater than 1.5 g/cc;
transferring the substrate including the stressed diamond-like carbon film from the plasma processing chamber to a thermal annealing chamber;
heating said stressed diamond-like carbon film at a temperature between 200 ° C. and 600° C. for 15 seconds to 60 minutes during a thermal annealing process to produce a low stress diamond-like carbon film containing 50 atomic % to 90 atomic % ^sp3 hybridized carbon atoms, having a compressive stress between 20 MPa and less than 500 MPa, and a density greater than 1.5 g / cc;
The method includes: The method of claim 16, wherein the compressive stress of the low stress diamond-like carbon film is between 40% and 90 % less than the compressive stress of the stressed diamond-like carbon film. 17. The method of claim 16, wherein the stressed diamond-like carbon film has a compressive stress of 600 MPa to 1,000 MPa and a density of 1.55 g/cc to less than 2 g/cc, and the low stress diamond-like carbon film has a compressive stress of 150 MPa to 400 MPa and a density of 1.55 g/cc to less than 2 g/cc. The method of claim 16, wherein the low stress diamond-like carbon film has an elastic modulus of greater than 60 GPa to 200 GPa. 1. A method for processing a substrate, comprising:
flowing a deposition gas comprising a hydrocarbon compound into a process space of a process chamber having a substrate disposed on an electrostatic chuck;
generating a plasma above the substrate in the processing space by applying a first RF bias to the electrostatic chuck, and depositing a stressed diamond-like carbon film on the substrate, the stressed diamond-like carbon film having a compressive stress of 500 MPa or more;
heating the stressed diamond-like carbon film during a thermal annealing process at a temperature between 200°C and 600 °C for 15 seconds to 60 minutes to produce a low stress diamond-like carbon film having a compressive stress of less than 500 MPa and a density of greater than 1.5 g/cc to 2.1 g/cc, wherein the compressive stress of the low stress diamond-like carbon film is 40% to 90 % less than the compressive stress of the stressed diamond-like carbon film;
forming a patterned photoresist layer on the low stress diamond-like carbon film;
Etching the low stress diamond-like carbon film in a pattern corresponding to the patterned photoresist layer;
Etching the pattern into the substrate;
The method includes:

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