Method for producing densely doped carbon films for hard masks and other patterning applications

Abstract

FIELD OF THE DISCLOSURE [0002] Embodiments of the present disclosure relate generally to integrated circuit manufacturing. More specifically, embodiments described herein provide techniques for the deposition of dense films for patterning applications. In one or more embodiments, a method for processing a substrate is provided, comprising flowing a deposition gas comprising a hydrocarbon compound and a dopant 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 at the substrate by applying a first RF bias to the electrostatic chuck to deposit a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density greater than 2 g / cc and a compressive stress less than 500 MPa.

Description

[Technical Field]

[0001]

[0001] Embodiments of this disclosure generally relate to the manufacture of integrated circuits. More specifically, embodiments described herein provide techniques for depositing high-density films for patterning applications. [Background technology]

[0002] Description of related technologies

[0002] Integrated circuits have evolved into complex devices that can house millions of transistors, capacitors, and resistors on a single chip. The evolution of chip design constantly requires faster circuits and higher circuit density. The demand for faster circuits with higher circuit density places corresponding demands on the materials used to manufacture such integrated circuits. Specifically, as the dimensions of integrated circuit components become smaller to the submicron level, it is now necessary to use not only low-resistivity conductive materials but also low-dielectric-constant insulating materials to obtain appropriate electrical performance from these components.

[0003]

[0003] The demand for higher integrated circuit densities also imposes requirements on the processing sequences used to manufacture integrated circuit components. For example, in a processing sequence using conventional photolithography techniques, a layer of energy-sensitive resist is formed on top of the material layers of a laminate placed on a substrate. This energy-sensitive resist layer is exposed to an image of a pattern to form a photoresist mask. The mask pattern is then transferred to one or more material layers of the laminate using an etching process. The chemical etchant used in this etching process is selected to have higher etching selectivity for the material layers of the laminate than for the energy-sensitive resist mask. In other words, the chemical etchant etches one or more layers of the material laminate at a much faster rate than the energy-sensitive resist. The etching selectivity for one or more material layers of the laminate on the resist prevents the energy-sensitive resist from being consumed before the pattern transfer is complete.

[0004]

[0004] As the pattern dimensions decrease, the thickness of the energy-sensitive resist also decreases accordingly in order to control the 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 and facilitates pattern transfer because it has higher resistance to chemical etchants. There is a need for hard mask materials that have both high etching selectivity and fast deposition rates. Because the critical dimension (CD) is small, existing hard mask materials lack the desirable etching selectivity compared to the underlying material (e.g., oxides and nitrides) and are often difficult to deposit.

[0005]

[0005] Therefore, in the art there is a need for improved hard mask layers and methods for depositing improved hard mask layers. [Overview of the project]

[0006]

[0006] Embodiments of the present disclosure generally relate to the manufacture of integrated circuits. More specifically, embodiments described herein provide techniques for depositing high-density films for patterning applications. In one or more embodiments, a method for processing a substrate includes flowing a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing space of a processing chamber having a substrate placed 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 generating a plasma on the substrate by applying a first RF bias to the electrostatic chuck in order to deposit a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density greater than 2 g / cc and a compressive stress of less than 500 MPa.

[0007]

[0007] In some embodiments, a method for processing a substrate includes flowing a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing space of a processing chamber having a substrate placed on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode, and the processing space being maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating plasma on the substrate by applying a first RF bias to the RF electrode and a second RF bias to the electrostatic chuck in order to deposit a doped diamond-like carbon film on the substrate. The doped diamond-like carbon film has a density of about 2 g / cc to about 12 g / cc and a stress of about 600 MPa to about 300 MPa. The doped diamond-like carbon film has about 50 atomic percent (at%) to about 90 at% sp 3 Contains hybrid carbon atoms.

[0008]

[0008] In other embodiments, a method for processing a substrate includes injecting a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing space of a processing chamber having a substrate placed on an electrostatic chuck. The electrostatic chuck has a chucking electrode and an RF electrode separated from the chucking electrode, and the processing space is maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating plasma on the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density of more than 2 g / cc to about 12 g / cc and a stress of about 500 MPa to about 300 MPa. The method further includes forming a patterned photoresist layer on the doped diamond-like carbon film, etching the doped diamond-like carbon film with a pattern corresponding to the patterned photoresist layer, and etching the pattern onto the substrate.

[0009]

[0009] In one or more embodiments, a film is provided for use as an underlying layer for extreme ultraviolet (EUV) lithography processing, having a content of sp hybrid carbon atoms of about 40% to about 90% based on the total amount of carbon atoms in the film, one or more dopants of about 0.1 at% to about 20 at%, and an elastic modulus of about 150 GPa or more to about 400 GPa. 3

[0010]

[0010] To provide a more detailed understanding of the features of the present disclosure described above, a more specific description of the present disclosure, briefly summarized above, is obtained by reference to its implementation, and some implementations are illustrated in the accompanying drawings. However, it should be noted that since the present disclosure may admit other equally valid embodiments, the accompanying drawings show only typical embodiments of the present disclosure and thus are not to be considered as limiting the scope of the present invention.

Brief Description of the Drawings

[0011] [Figure 1A] A schematic cross-sectional view of a deposition system that can be used to practice the embodiments described herein is shown. [Figure 1B] A schematic cross-sectional view of another deposition system that can be used to practice the embodiments described herein is shown. [Figure 2] A schematic cross-sectional view of an electrostatic chuck that can be used in the apparatus of FIGS. 1A and 1B that can be used to practice the embodiments described herein is shown. [Figure 3] A flowchart of a method for forming a doped diamond-like carbon film on a film stack disposed on a substrate according to one or more embodiments of the present disclosure is shown. [Figure 4A] A sequence for forming a doped diamond-like carbon film on a film stack formed on a substrate according to one or more embodiments of the present disclosure is shown. [Figure 4B] A sequence for forming a doped diamond-like carbon film on a film stack formed on a substrate according to one or more embodiments of the present disclosure is shown. [Figure 5] ​A flowchart illustrating a method using a doped diamond-like carbon film according to one or more embodiments of the present disclosure is shown. [Modes for carrying out the invention]

[0012]

[0017] For ease of understanding, the same reference numerals were used where possible to indicate identical elements common to the figures. It is believed that elements and features of one embodiment can be usefully incorporated into other embodiments without further description.

[0013]

[0018] The embodiments provided herein relate to doped diamond-like carbon films and methods for depositing or forming doped diamond-like carbon films on a substrate. Certain details are presented in the following description and Figures 1A–5 to provide a complete understanding of the various embodiments of this disclosure. To avoid unnecessarily obscuring the description of the various embodiments, other details describing well-known structures and systems often associated with plasma processing and the deposition of doped diamond-like carbon films are not explicitly stated in the following disclosure.

[0014]

[0019] Many of the details, dimensions, angles, and other features shown in the drawings are merely illustrative of specific implementation configurations. Therefore, other implementation configurations may have other details, components, dimensions, angles, and features without departing from the spirit or scope of this disclosure. Furthermore, further embodiments of this disclosure may be implemented without some of the details described below.

[0015]

[0020] The embodiments described herein are described below with reference to chemical vapor deposition (PE-CVD) processes that can be performed using any suitable thin-film deposition system. Examples of suitable systems include the DXZ® processing chamber, PRECISION5000® system, PRODUCER® system, PRODUCER®GT® system, PRODUCER®XP Precision® system, PRODUCER®SE® system, Sym3® processing chamber, and the CENTURA® system which can use the Mesa® processing chamber, all of which are available from Applied Materials Inc., located in Santa Clara, California. Other tools capable of performing PE-CVD processes may also be adapted to benefit from the embodiments described herein. In addition, any system that enables the CVD processes described herein may be advantageously used. The descriptions of any apparatus described herein are illustrative and should not be understood or construed as limiting the scope of the embodiments described herein.

[0016]

[0021] Current hard mask applications for memory and other devices primarily utilize thick carbon films (e.g., approximately 300 nm to 1.5 microns) that are inherently amorphous. However, the etching selectivity of these films is no longer sufficient to meet increasingly stringent requirements and the high aspect ratio etching of future nodes. To achieve higher etching selectivity, the density and Young's modulus of the films need to be improved. One of the main challenges in achieving higher etching selectivity and improved Young's modulus is that the high compressive stress of such films is unsuitable for the application because it results in significant wafer / substrate warping. Therefore, there is a need for films with high etching selectivity and low stress (e.g., <500 MPa), and (e.g., sp 3 A (diamond-like) carbon film is needed that has a higher content and a higher density and elastic modulus (more diamond-like).

[0017]

[0022] The embodiments described herein include improvements to the method for producing doped diamond-like carbon films having high density (e.g., >2 g / cc), high modulus of elasticity (e.g., >150 GPa), and low stress (e.g., <500 MPa). The doped diamond-like carbon films produced by the embodiments described herein are inherently amorphous and have higher etching selectivity with a higher modulus of elasticity (e.g., >150 GPa) along with lower stress than existing patterned films. The doped diamond-like carbon films produced by the embodiments described herein not only have low stress but also high sp 3 It has a carbon content. In general, the deposition processes described herein are also fully compatible with existing deposition schemes for hard mask applications.

[0018]

[0023] In one or more embodiments, the doped diamond-like carbon film described herein may be formed by CVD, such as plasma chemical vapor deposition (CVD) and / or thermal CVD, using a deposition gas comprising one or more hydrocarbon compounds and one or more dopant compounds. Exemplary hydrocarbon compounds include ethylene or acetylene (C2H2), propene (C3H6), methane (CH4), butene (C4H8), 1,3-dimethyladamantane, bicyclo[2.2.1]hepta2,5-diene (2,5-norbornadiene), and adamantine (C 10 H 16 ), Norbornen (C7H 10 ), derivatives thereof, isomers thereof, or any combination thereof, or may include them.

[0019]

[0024] A dopant compound may consist of one or more metallic dopants, one or more nonmetallic dopants, or a combination thereof. A dopant compound may be one or more chemical precursors used in vapor deposition processes such as CVD or ALD. A metallic dopant may consist of one or more of tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof. Thus, a metallic dopant may consist of one or more of tungsten precursors, molybdenum precursors, cobalt precursors, nickel precursors, vanadium precursors, hafnium precursors, zirconium precursors, tantalum precursors, or any combination thereof. Exemplary metal dopants include tungsten hexafluoride, hexacarbonyltungsten, molybdenum pentachloride, cyclopentadienyldicarbonylcobalt, dicobalthexacarbonylbutylacetylene (CCTBA), bis(cyclopentadienyl)cobalt, bis(methylcyclopentadienyl)nickel, vanadium pentachloride, hafnium tetrachloride, tetrakis(dimethylamino)hafnium, tetrakis(diethylamino)hafnium, zirconium tetrachloride, bis(cyclopentadienyl)zirconium dihydrogen, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, tantalum pentachloride, tantalum pentafluoride, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, adducts thereof, derivatives thereof, or any combination thereof, or may include these. Nonmetallic dopants are one or more of boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof, or may include them. Thus, nonmetallic dopants are one or more of boron precursors, silicon precursors, germanium precursors, nitrogen precursors, phosphorus precursors, or any combination thereof, or may include them.Exemplary nonmetallic dopants are disilane, diborane, triethylborane, silane, disilane, trisilane, germane, ammonia, hydrazine, phosphine, their adducts, or any combination thereof, or may include them.

[0020]

[0025] The substrate and / or processing space may be heated and maintained at individual temperatures during the deposition process. The substrate and / or processing space may be heated to temperatures of approximately 50°C, 25°C, 10°C, 5°C, 0°C, 5°C, or 10°C to 15°C, 20°C, 23°C, 30°C, 50°C, 100°C, 150°C, 200°C, 300°C, 400°C, 500°C, or 600°C. For example, the substrate and / or processing space may be heated to a temperature of approximately 50°C to 600°C, approximately 50°C to 450°C, approximately 50°C to 350°C, approximately 50°C to 200°C, approximately 50°C to 100°C, approximately 50°C to 50°C, approximately 50°C to 0°C, approximately 0°C to 600°C, approximately 0°C to 450°C, approximately 0°C to 350°C, approximately 0°C to 200°C, approximately 0°C to 120°C, approximately 0°C to 100°C, approximately 0°C to 80°C, approximately 0°C to 50°C, approximately 0°C to 25°C, approximately 10°C to 600°C, approximately 10°C to 450°C, approximately 10°C to 350°C, approximately 10°C to 200°C, approximately 10°C to 100°C, or approximately 10°C to 50°C.

[0021]

[0026] The processing chamber's processing space is maintained at a pressure below atmospheric pressure during the deposition process. The processing chamber's processing space is maintained at pressures of approximately 0.1 mTorr, 0.5 mTorr, 1 mTorr, 5 mTorr, 10 mTorr, 50 mTorr, or 80 mTorr to 100 mTorr, 250 mTorr, 500 mTorr, 1 Torr, 5 Torr, 10 Torr, 20 Torr, 50 Torr, or 100 Torr. For example, the processing space of the processing chamber is approximately 0.1mTorr to 10Torr, approximately 0.1mTorr to 5Torr, approximately 0.1mTorr to 1Torr, approximately 0.1mTorr to 500mTorr, approximately 0.1mTorr to 100mTorr, approximately 0.1mTorr to 10mTorr, approximately 1mTorr to 10Torr, approximately 1mTorr to 5Torr, approximately 1mTorr to 1 Torr is maintained at pressures of approximately 1 mTorr to 500 mTorr, approximately 1 mTorr to 100 mTorr, approximately 1 mTorr to 10 mTorr, approximately 5 mTorr to 10 mTorr, approximately 5 mTorr to 5 Torr, approximately 5 mTorr to 1 Torr, approximately 5 mTorr to 500 mTorr, approximately 5 mTorr to 100 mTorr, or approximately 5 mTorr to 10 mTorr.

[0022]

[0027] The deposition gas may further contain one or more diluent gases, carrier gases, and / or purge gases, such as helium, argon, xenon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof. The deposition gas may further contain etchant gases such as chlorine (Cl2), carbon tetrafluoride (CF4), and / or nitrogen trifluoride (NF3) to improve film quality. The plasma (e.g., capacitively coupled plasma) may be formed from either the top and bottom electrodes or the side electrodes. These electrodes may be formed from a single power supply electrode, from a dual power supply electrode, or from more electrodes with multiple frequencies (such as, but not limited to, approximately 350 kHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, and 100 MHz) and may be used alternatively or simultaneously in a CVD system with any or all of the reaction gases listed herein to deposit thin films of diamond-like carbon used as hard masks and / or etching stops, or smooth carbon films required for any other application. The high etching selectivity of doped diamond-like carbon films is achieved by having higher density and modulus than existing produced films. While not bound by theory, the improvement in density and modulus is due to sp in the doped diamond-like carbon film. 3 This is thought to be brought about by an increase in the content of hybrid carbon atoms, which can be achieved by combining lower pressure and plasma output.

[0023]

[0028] In one or more embodiments, a doped diamond-like carbon film is deposited in a processing chamber having a substrate pedestal maintained at about 10°C, a pressure maintained at about 2 mTorr, and plasma generated at the substrate level by applying a bias of about 2,500 watts (about 13.56 MHz) to an 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.

[0024]

[0029] In one or more embodiments, hydrogen radicals are supplied through RPS, which leads to the selective etching of sp 2 hybrid carbon atoms, and thus further increases the fraction of sp 3 hybrid carbon atoms in the film, thereby further enhancing the etching selectivity. The doped diamond-like carbon film has at least 40 atomic percent (at%), about 45 at%, about 50 at%, about 55 at%, or about 58 at% to about 60 at%, about 65 at%, about 70 at%, about 75 at%, about 80 at%, about 85 at%, about 88 at%, about 90 at%, about 92 at%, or about 95 at% of sp 3 hybrid carbon atoms, based on the total amount of carbon atoms in the doped diamond-like carbon film. For example, the doped diamond-like carbon film has 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 65 at% to about 95 at%, about 65 at% to about 90 at%, about 65 at% to about 85 at%, about 65 at% to about 80 at%, about 65 at% to about 75 at%, about 65 at% to about 70 at%, about 65 at% to about 68 at%, about 75 at% to about 95 at%, about 75 at% to about 90 at%, about 75 at% to about 85 at%, about 75 at% to about 80 at%, or about 75 at% to about 78 at% of sp 3 hybrid carbon atoms, based on the total amount of carbon atoms in the doped diamond-like carbon film.

[0025]

[0030] ​​The doped diamond-like carbon film may have dopant concentrations or percentages of approximately 0.01 at%, 0.05 at%, 0.1 at%, 0.3 at%, 0.5 at%, 0.8 at%, 1 at%, 1.2 at%, 1.5 at%, 1.8 at%, 2 at%, 2.5 at%, or approximately 2.8 at% to 3 at%, 3.5 at%, 4 at%, 5 at%, 6 at%, 7 at%, 8 at%, 9 at%, 10 at%, 12 at%, 15 at%, 18 at%, 20 at%, 25 at%, 30 at%, or higher, based on the total amount of atoms in the doped diamond-like carbon film.For example, a doped diamond-like carbon film has a total amount of atoms in it, with a range of approximately 0.01 at% to 25 at%, 0.1 at% to 25 at%, 0.5 at% to 25 at%, 1 at% to 25 at%, 2 at% to 25 at%, 3 at% to 25 at%, 5 at% to 25 at%, 7 at% to 25 at%, 10 at% to 25 at%, 12 at% to 25 at%, 15 at% to 25 at%, and 18 at% to 25 at%. t%, about 20 at% to about 25 at%, about 0.1 at% to about 20 at%, about 0.5 at% to about 20 at%, about 1 at% to about 20 at%, about 2 at% to about 20 at%, about 3 at% to about 20 at%, about 5 at% to about 20 at%, about 7 at% to about 20 at%, about 10at% to about 20at%, about 12at% to about 20at%, about 15at% to about 20at%, about 18at% to about 20at%, about 0.1at% to about 18at%, about 0.5at% to about 18at%, about 1at% to about 18at%, about 2at% to Approximately 18at%, approximately 3at% to approximately 18at%, approximately 5at% to approximately 18at%, approximately 7at% to approximately 18at%, approximately 10at% to approximately 18at%, approximately 12at% to approximately 18at%, approximately 15at% to approximately 18at%, approximately 0.1at% to approximately 15at%, approximately 0.5a t%~about 15at%, about 1at%~about 15at%, about 2at%~about 15at%, about 3at%~about 15at%, about 5at%~about 15at%, about 7at%~about 15at%, about 10at%~about 15at%, about 12at%~about 15at%, about 0.01 The dopant may have a concentration or proportion of approximately at% to 10at%, approximately 0.1at% to 10at%, approximately 0.5at% to 10at%, approximately 1at% to 10at%, approximately 2at% to 10at%, approximately 3at% to 10at%, approximately 4at% to 10at%, approximately 5at% to 10at%, approximately 7at% to 10at%, approximately 0.01at% to 5at%, approximately 0.1at% to 5at%, approximately 0.5at% to 5at%, approximately 1at% to 5at%, approximately 2at% to 5at%, or approximately 3at% to 5at%.

[0026]

[0031] The doped diamond-like carbon film has a density greater than 2 g / cc, for example, about 2.1 g / cc, about 2.2 g / cc, about 2.3 g / cc, about 2.4 g / cc, about 2.5 g / cc, about 2.6 g / cc, about 2.7 g / cc, about 2.8 g / cc, about 2.9 g / cc, or about 3 g / cc to about 3.1 g / cc, about 3.2 g / cc, about 3.4 g / cc, about 3.5 g / cc, about 3.6 g / cc, about 3.8 g / cc, about 4 g / cc, about 4.5 g / cc, about 5 g / cc, about 5.5 g / cc, about 6 g / cc, about 6.5 g / cc, about 7 g / cc, about 8 g / cc, about 9 g / cc, about 10 g / cc, about 11 g / cc, about 12 g / cc, or higher. For example, doped diamond-like carbon films have doping levels of over 2 g / cc to approximately 12 g / cc, over 2 g / cc to approximately 10 g / cc, over 2 g / cc to approximately 8 g / cc, over 2 g / cc to approximately 7 g / cc, over 2 g / cc to approximately 5 g / cc, over 2 g / cc to approximately 4 g / cc, over 2 g / cc to approximately 3 g / cc, approximately 2.5 g / cc or more to approximately 12 g / cc, approximately 2.5 g / cc or more to approximately 10 g / cc, approximately 2.5 g / cc or more to approximately 8 g / cc, and approximately 2.5 g / cc or more. ~Approx. 7g / cc, approx. 2.5g / cc or more ~ ​​Approx. 5g / cc, approx. 2.5g / cc or more ~ ​​approx. 4g / cc, approx. 2.5g / cc or more ~ ​​approx. 3g / cc, approx. 3g / cc or more ~ ​​approx. 12g / cc, approx. 3g / cc or more ~ ​​approx. 10g / c c, about 3 g / cc or more to about 8 g / cc, about 3 g / cc or more to about 7 g / cc, about 3 g / cc or more to about 5 g / cc, about 3 g / cc or more to about 4 g / cc, or about 3 g / cc or more to about 3.5 g / cc.

[0027]

[0032] The doped diamond-like carbon film may have thicknesses of approximately 5 Å, 10 Å, 50 Å, 100 Å, 150 Å, 200 Å, or approximately 300 Å to 400 Å, 500 Å, 800 Å, 1,000 Å, 2,000 Å, 3,000 Å, 5,000 Å, 8,000 Å, 10,000 Å, 15,000 Å, 20,000 Å, or greater. For example, doped diamond-like carbon films have a range of approximately 5 Å to 20,000 Å, approximately 5 Å to 10,000 Å, approximately 5 Å to 5,000 Å, approximately 5 Å to 3,000 Å, approximately 5 Å to 2,000 Å, approximately 5 Å to 1,000 Å, approximately 5 Å to 500 Å, approximately 5 Å to 200 Å, approximately 5 Å to 100 Å, approximately 5 Å to 50 Å, approximately 300 Å to 20,000 Å, approximately 300 Å to 10,000 Å, approximately 00 Å to 5,000 Å, approximately 300 Å to 3,000 Å, and approximately 300 It may have a thickness of approximately 2,000 Å, 300 Å to 1,000 Å, 300 Å to 500 Å, 300 Å to 200 Å, 300 Å to 100 Å, 300 Å to 50 Å, 1,000 Å to 20,000 Å, 1,000 Å to 10,000 Å, 1,000 Å to 5,000 Å, 1,000 Å to 3,000 Å, 1,000 Å to 2,000 Å, 2,000 Å to 20,000 Å, or approximately 2,000 Å to 3,000 Å.

[0028]

[0033] A doped diamond-like carbon film may have a refractive index 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, a doped diamond-like carbon film may have a refractive index or n value (n at 633 nm) greater than 2 to about 3, greater than 2 to about 2.8, greater than 2 to about 2.5, greater than 2 to about 2.3, about 2.1 to about 3, about 2.1 to about 2.8, about 2.1 to about 2.5, about 2.1 to about 2.3, about 2.3 to about 3, about 2.3 to about 2.8, or about 2.3 to about 2.5.

[0029]

[0034] Doped diamond-like carbon films may individually have absorption coefficients or k values ​​(k at 633 nm) greater than 0.1, for example, about 0.15, about 0.2, about 0.25, or about 0.3. For example, doped diamond-like carbon films may have absorption coefficients or k values ​​(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, and about 0.2 to about 0.25.

[0030]

[0035] The doped diamond-like carbon film may have stresses of less than 250 MPa, less than -275 MPa, approximately -300 MPa or less, approximately -350 MPa or less, approximately -400 MPa or less, approximately -450 MPa or less, approximately -500 MPa or less, approximately -550 MPa or less, and approximately -600 MPa or less. For example, a doped diamond-like carbon film may have stresses of approximately 600 MPa to 300 MPa, 600 MPa to 350 MPa, 600 MPa to 400 MPa, 600 MPa to 450 MPa, 600 MPa to 500 MPa, 600 MPa to 550 MPa, 550 MPa to 300 MPa, 550 MPa to 350 MPa, 550 MPa to 400 MPa, 550 MPa to 450 MPa, 550 MPa to 500 MPa, 500 MPa to 300 MPa, 500 MPa to 350 MPa, 500 MPa to 400 MPa, or 500 MPa to 450 MPa.

[0031]

[0036] The doped diamond-like carbon film may have an elastic modulus greater than 150 GPa, for example, about 175 GPa, about 200 GPa, or about 250 GPa to about 275 GPa, about 300 GPa, about 325 GPa, about 350 GPa, about 375 GPa, or about 400 GPa. For example, a doped diamond-like carbon film has an elastic modulus of over 150 GPa to about 400 GPa, over 150 GPa to about 375 GPa, over 150 GPa to about 350 GPa, over 150 GPa to about 300 GPa, over 150 GPa to about 250 GPa, about 175 GPa to about 400 GPa, about 175 GPa to about 375 GPa, about 175 GPa to about 350 GPa, about 175 GPa to about 300 GPa, about 175 GPa to about 250 GPa, about 200 GPa to about 400 GPa, about 200 GPa to about 375 GPa, about 200 GPa to about 350 GPa, about 200 GPa to about 300 GPa, or about 200 GPa to about 250 GPa.

[0032]

[0037] In some embodiments, the doped diamond-like carbon film is an underlayer for extreme ultraviolet ("EUV") lithography. In some embodiments, the doped diamond-like carbon film is an underlayer for EUV lithography and contains about 40% to about 90% sp based on the total amount of carbon atoms in the film. 3 It has hybrid carbon atoms, a density of over 2 g / cc to approximately 12 g / cc, and an elastic modulus of approximately 150 GPa to approximately 400 GPa.

[0033]

[0038] Figure 1A shows a schematic diagram of a substrate processing system 132 that may be used to carry out the deposition of a doped diamond-like carbon film according to embodiments described herein. The substrate processing system 132 includes a processing chamber 100 connected to a gas panel 130 and a controller 110. The processing chamber 100 generally includes an upper wall 124, side walls 101, and a bottom wall 122, these walls defining 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 manufactured 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).

[0034]

[0039] The vacuum pump 102 is connected to a port formed at 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 also discharges post-treatment gases and processing by-products from the processing chamber 100.

[0035]

[0040] The substrate processing system 132 may further include additional chamber pressure control devices, 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.

[0036]

[0041] A gas distribution assembly 120 having multiple openings 128 is positioned above the electrostatic chuck 150 and above the processing chamber 100. The openings 128 of the gas distribution assembly 120 are used to introduce process gases (e.g., deposition gas, diluent gas, carrier gas, purge gas) into the processing chamber 100. The openings 128 may have various sizes, quantities, distribution modes, shapes, designs, and diameters to facilitate the flow of various process gases for various processing requirements. The gas distribution assembly 120 is connected to a gas panel 130, which allows various gases to be supplied 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 thermal decomposition of the process gas, which results in the deposition of material onto the surface 191 of the substrate 190.

[0037]

[0042] The gas distribution assembly 120 and the electrostatic chuck 150 may form a pair of spaced electrodes within the processing space 126. To facilitate plasma generation between the gas distribution assembly 120 and the electrostatic chuck 150, one or more RF power supplies 140 provide a bias potential to the gas distribution assembly 120 through a matching network 138 (which is optional). Alternatively, the RF power supplies 140 and the matching network 138 may be connected 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 to an antenna (not shown) located outside the processing chamber 100. In one or more embodiments, the RF power supplies 140 may generate power at frequencies of approximately 350 kHz, approximately 2 MHz, approximately 13.56 MHz, approximately 27 MHz, approximately 40 MHz, approximately 60 MHz, or approximately 100 MHz. In some embodiments, the RF power supply 140 can supply power of approximately 100 watts to approximately 3,000 watts at a frequency of approximately 50 kHz to approximately 13.6 MHz. In other embodiments, the RF power supply 140 can supply power of approximately 500 watts to approximately 1,800 watts at a frequency of approximately 50 kHz to approximately 13.6 MHz.

[0038]

[0043] The controller 110 includes a central processing unit (CPU) 112, memory 116, and support circuits 114, which are used 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 industrial settings. Software routines may be stored in memory 116, for example, in random access memory, read-only memory, floppy disks, hard disk drives, or other forms of digital storage. The support circuits 114 are conventionally connected to the CPU 112 and may include a cache, clock circuits, input / output systems, power sources, etc. Bidirectional communication between the controller 110 and various components of the board processing system 132 is handled through a number of signal cables (collectively referred to as the signal bus 118, some of which are shown in Figure 1A).

[0039]

[0044] Figure 1B shows a schematic cross-sectional view of another substrate processing system 180 that can be used to implement the embodiments described herein. The substrate processing system 180 is similar to the substrate processing system 132 in Figure 1A, except that it is configured to flow processing gas from the gas panel 130 through the side wall 101 to the edge of the surface 191 of the substrate 190. In addition, the gas distribution assembly 120 shown in Figure 1A is replaced by an electrode 182. The electrode 182 may be configured as a secondary charge generator. In one or more embodiments, the electrode 182 is a silicon-containing electrode.

[0040]

[0045] Figure 2 shows a schematic cross-sectional view of a substrate support assembly 146 used in the processing systems of Figures 1A and 1B, which may be used in practicing the embodiments described herein. Referring to Figure 2, the electrostatic chuck 150 may include a heater element 170 suitable for controlling the temperature of a substrate 190 supported on the upper surface 192 of the electrostatic chuck 150. The heater element 170 may be embedded in the electrostatic chuck 150. The electrostatic chuck 150 may be resistively heated by applying current from a heater power supply 106 to the heater element 170. The heater power supply 106 may be connected 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 from a nickel-chromium wire enclosed in a nickel-iron-chromium alloy sheath tube (e.g., INCOLOY®). The current supplied from the heater power supply 106 is adjusted by the controller 110 to control the heat generated by the heater element 170, thereby maintaining the substrate 190 and the electrostatic chuck 150 at a substantially constant temperature during film deposition. The supplied current can be adjusted to selectively control the temperature of the electrostatic chuck 150 between approximately 50°C and approximately 600°C.

[0041]

[0046] Referring to Figure 1, in a conventional configuration, a temperature sensor 172 (such as a thermocouple) may be embedded in the electrostatic chuck 150 to monitor its temperature. 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.

[0042]

[0047] 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 connected to a chucking power supply 212, which, when energized, electrostatically clamps the substrate 190 to the upper surface 192 of the electrostatic chuck 150.

[0043]

[0048] The chucking electrode 210 may be configured as a unipolar or bipolar electrode, or may have another suitable configuration. The chucking electrode 210 may be connected to a chucking power supply 212 via an RF filter 214, which supplies direct current (DC) power to electrostatically fix the substrate 190 to the upper surface 192 of the electrostatic chuck 150. The RF filter 214 prevents the RF power used for plasma formation in the processing chamber 100 from damaging electrical equipment outside the chamber or causing electrical malfunctions. The electrostatic chuck 150 may be manufactured from a ceramic material such as aluminum nitride or aluminum oxide (e.g., alumina). Alternatively, the electrostatic chuck 150 may be manufactured from a polymer such as polyimide, polyetheretherketone (PEEK), or polyaryletherketone (PAEK).

[0044]

[0049] A power supply system 220 is connected to the substrate support assembly 146. The power supply 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 supply system 220 may also include a controller 110 and a sensor device 250 capable of communicating with both the controller 110 and the first and second RF power supplies 230 and 240. The controller 110 may further be used to control plasma from the processing gas by applying RF power from the first and second RF power supplies 230 and 240 to deposit a layer of material onto the substrate 190.

[0045]

[0050] As described above, in one embodiment, 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, together with the chucking electrode 210, can apply RF power to tune the plasma. The first RF power supply 230 may be connected to the second RF electrode 260, while the second RF power supply 240 may be connected to the chucking electrode 210. A first matching network and a second matching network may be provided for the first RF power supply 230 and the second RF power supply 240, respectively. The second RF electrode 260 may be a solid metal plate of a conductive material as shown. Alternatively, the second RF electrode 260 may be a mesh of a conductive material.

[0046]

[0051] The first RF power supply 230 and the second RF power supply 240 may generate power at the same frequency or at different frequencies. In one or more embodiments, one or both of the first RF power supply 230 and the second RF power supply 240 may generate power individually at frequencies from about 350 kHz to about 100 MHz (e.g., 350 kHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, or 100 MHz). In one or more embodiments, the first RF power supply 230 may generate power at a frequency of 13.56 MHz, the second RF power supply 240 may generate power at a frequency of 2 MHz, or vice versa. The RF power from one or both of the first RF power supply 230 and the second RF power supply 240 may be modified to tune the plasma. For example, a sensor device 250 may be used to monitor the RF energy from one or both of the first RF power supply 230 and the second RF power supply 240. Data from the sensor device 250 may be transmitted to the controller 110, which may be used to change the power supplied by the first RF power supply 230 and the second RF power supply 240.

[0047]

[0052] In one or more embodiments, the electrostatic chuck 150 can separate the chucking electrode 210 and the RF electrode from each other, apply a first RF bias to the RF electrode 260, and apply a second RF bias to the chucking electrode 210. In one or more embodiments, the first RF bias is supplied at a frequency of about 350 kHz to about 100 MHz with a power of about 10 watts to about 3,000 watts, and the second RF bias is supplied at a frequency of about 350 kHz to about 100 MHz with a power of about 10 watts to about 3,000 watts. In other embodiments, the first RF bias is supplied at a frequency of about 13.56 MHz with a power of about 2,500 watts to about 3,000 watts, and the second RF bias is supplied at a frequency of about 2 MHz with a power of about 800 watts to about 1,200 watts.

[0048]

[0053] In one or more embodiments, a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds may be flowed or introduced into the processing space of a processing chamber, such as a PE-CVD chamber. The hydrocarbon compounds and dopant compounds may be flowed or introduced into the processing space individually. In some embodiments, one or more substrates are placed on an electrostatic chuck in the processing chamber. The electrostatic chuck may have a chucking electrode and an RF electrode separately. By applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode, plasma can be ignited or generated on or near the substrate (e.g., at the substrate level). The doped 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 doped diamond-like carbon film, the doped diamond-like carbon film being etched or formed in a pattern corresponding to the patterned photoresist layer, and the pattern being etched or formed on the substrate.

[0049]

[0054] Generally, the following exemplary deposition parameters may be used to form a doped diamond-like carbon film: The substrate temperature may be in the range of about 50°C to about 350°C (e.g., about 10°C to about 100°C, or about 10°C to about 50°C). The chamber pressure may be in the range of about 0.5 mTorr to about 10 Torr (e.g., about 2 mTorr to about 50 mTorr, or about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may be about 10 sccm to about 1,000 sccm (e.g., about 100 sccm to about 200 sccm, or about 150 sccm to about 200 sccm). The flow rate of the dopant compound may be about 1 sccm to about 1,000 sccm (e.g., about 10 sccm to about 150 sccm, or about 20 sccm to about 100 sccm). The flow rate of the dilution gas or purge gas may be approximately 50 sccm to approximately 50,000 sccm (for example, approximately 50 sccm to approximately 500 sccm, or approximately 50 sccm to approximately 100 sccm). TIFF2023533711000002.tif73170

[0050]

[0055] The doped diamond-like carbon film may be deposited to a thickness of approximately 5 Å to 20,000 Å (e.g., approximately 300 Å to 5,000 Å, approximately 2,000 Å to 3,000 Å, or approximately 5 Å to 200 Å). The processing parameters shown in Table 1 are examples of processing parameters for 300 mm substrates in a deposition chamber available from Applied Materials, Inc. in Santa Clara, California.

[0051]

[0056] Doped diamond-like carbon films may have a refractive index or n value (n at 633 nm) greater than 2.0, for example, about 2.1 to about 3.0, or 2.3. Doped diamond-like carbon films may have an extinction coefficient or k value (K at 633 nm) greater than 0.1, for example, about 0.2 to about 0.3, or 0.25. Doped diamond-like carbon films may have a stress of less than about 100 MPa (for example, about 1,000 MPa to about 100 MPa, about 600 MPa to about 300 MPa, about 600 MPa to about 500 MPa, about 550 MPa, etc.). Doped diamond-like carbon films may have a density greater than 2 g / cc (for example, about 2.5 g / cc or more, about 2.8 g / cc or more, about 3 g / cc to about 12 g / cc, etc.). Doped diamond-like carbon films can have an elastic modulus exceeding 150 GPa (e.g., approximately 200 GPa to approximately 400 GPa).

[0052]

[0057] Figure 3 shows a flow diagram of Method 300 for forming a doped diamond-like carbon film on a film stack placed on a substrate, according to one embodiment of the present disclosure. The doped diamond-like carbon film formed on the film stack can be used, for example, as a hard mask for forming a stepped structure on the film stack. Figures 4A and 4B are schematic cross-sectional views showing the sequence for forming a doped diamond-like carbon film on a film stack placed on a substrate by Method 300. Although Method 300 is described later in relation to a hard mask layer that can be formed on a film stack used to manufacture a stepped structure on the film stack for three-dimensional semiconductor devices, Method 300 can also be advantageously used in other device manufacturing applications. Furthermore, it should be understood that the steps shown in Figure 3 may be performed simultaneously and / or in an order different from that shown in Figure 3.

[0053]

[0058] Method 300 begins in step 310 by positioning a substrate (such as the substrate 402 shown in Figure 4A) in a processing chamber (such as the processing chamber 100 shown in Figure 1A or Figure 1B). The substrate 402 may be the substrate 190 shown in Figures 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 needed, on which the film laminate 404 is positioned, and these materials may be used to form the structure 400 (e.g., a stepped structure) in the film laminate 404.

[0054]

[0059] As shown in the embodiment in Figure 4A, the substrate 402 may have a substantially planar surface, a non-planar surface, or a substantially planar surface on which a structure is formed. A film stack 404 is formed on the substrate 402. In one or more embodiments, the film stack 404 may be used to form gate structures, contact structures, or interconnect structures in front-end or back-end processing. Method 300 may be performed on the film stack 404 to form a stepped structure used in a memory structure (such as a NAND structure) on the film stack 404. In one or more embodiments, the substrate 402 is crystalline silicon (e.g., Si <100> or Si <111> The substrate may be made of materials such as silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon substrates, patterned or unpatterned substrate silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, or sapphire. The substrate 402 may have various dimensions, e.g., 200 mm, 300 mm, and 450 mm, or other diameters, and may be rectangular or square panels. Unless otherwise specified, the embodiments and examples described herein are performed on substrates of 200 mm, 300 mm, or 450 mm in diameter. In embodiments in which an SOI structure is utilized in the substrate 402, the substrate 402 may include an embedded dielectric layer disposed on a silicon crystalline substrate. In one or more embodiments described herein, the substrate 402 may be a crystalline silicon substrate.

[0055]

[0060] In one or more embodiments, the film laminate 404 disposed on the substrate 402 may have a number of vertically stacked layers. The film laminate 404 has a first layer (408a1, 408a2, 408a3, ..., 408a) which is repeatedly formed in the film laminate 404. n (represented as), and the second layer (408b1, 408b2, 408b3, ..., 408b nThese pairs may include pairs that contain (represented as ). These pairs may include pairs that contain alternating first layers (408a1, 408a2, 408a3, ..., 408a n (shown as) and the second layer (408b1, 408b2, 408b3, ..., 408b n The process includes (as shown) and is repeated until the number of pairs of the first and second layers reaches the target number.

[0056]

[0061] The film stack 404 may be part of a semiconductor chip such as a three-dimensional memory chip. The first layer (408a1, 408a2, 408a3, ..., 408a n (shown as) and the second layer (408b1, 408b2, 408b3, ..., 408b n Three iterative layers (shown as ) are shown in Figures 4A and 4B, but note that any number of iterative pairs of the first and second layers may be used as needed.

[0057]

[0062] In one or more embodiments, the film stack 404 can be used to form multiple gate structures for a three-dimensional memory chip. The first layers 408a1, 408a2, 408a3, ..., 408a n This may be a first dielectric layer, and the second layers 408b1, 408b2, 408b3, ..., 408b n This may be a second dielectric layer. The first layers 408a1, 408a2, 408a3, ..., 408a n , and the second layer 408b1, 408b2, 408b3, ..., 408b nSuitable dielectric layers that can be used to form the dielectric include, in particular, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, titanium nitride, oxide-nitride composites, 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 dielectric constant material having a dielectric constant greater than 4. Suitable examples of high dielectric constant materials include hafnium oxide, zirconium oxide, titanium oxide, hafnium silicon oxide or hafnium silicate, hafnium aluminum oxide or hafnium aluminate, zirconium silicon oxide or zirconium silicate, tantalum oxide, aluminum oxide, aluminum-doped hafnium dioxide, bismuth strontium titanium (BST), and platinum zirconium titanium (PZT), their dopants, or any combination thereof.

[0058]

[0063] In one or more embodiments, the first layers 408a1, 408a2, 408a3, ..., 408a n The first layer is a silicon oxide layer, and the second layer consists of 408b1, 408b2, 408b3, ..., 408b n The first layer consists of 408a1, 408a2, 408a3, ..., 408a n A silicon nitride layer or polysilicon layer disposed on top of the first layer 408a1, 408a2, 408a3, ..., 408a n The thickness of the second layer 408b1, 408b2, 408b3, ..., 408b n The thickness of each layer may be controlled to be approximately 50 Å to approximately 1,000 Å (for example, approximately 500 Å). The film laminate 404 may have a total thickness of approximately 100 Å to approximately 2,000 Å. In one or more embodiments, the total thickness of the film laminate 404 is approximately 3 microns to approximately 10 microns, and will vary as technology advances.

[0059]

[0064] It should be noted that a doped diamond-like carbon film can be formed on any surface or portion of the substrate 402, regardless of whether or not a film laminate 404 is present on the substrate 402.

[0060]

[0065] In step 320, a chucking voltage is applied to the electrostatic chuck, and the substrate 402 is clamped to or placed on the electrostatic chuck. In one or more embodiments, the substrate 402 is positioned on the upper surface 192 of the electrostatic chuck 150, and during processing, the upper surface 192 supports and clamps the substrate 402. The electrostatic chuck 150 ensures that the substrate 402 is in close contact with the upper surface 192, preventing backside deposition. An electrical bias is supplied to the substrate 402 via the chucking electrode 210. The chucking electrode 210 may be electrically communicable with a chucking power supply 212 that supplies a bias voltage to the chucking electrode 210. In one or more embodiments, the chucking voltage is approximately 10 volts to approximately 3,000 volts, approximately 100 volts to approximately 2,000 volts, or approximately 200 volts to approximately 1,000 volts.

[0061]

[0066] In step 320, several processing parameters may be adjusted to suit the processing. In one or more embodiments suitable for processing 300 mm substrates, the processing pressure in the processing space may be maintained at approximately 0.1 mTorr to approximately 10 Torr (e.g., approximately 2 mTorr to approximately 50 mTorr, or approximately 5 mTorr to approximately 20 mTorr). In some embodiments suitable for processing 300 mm substrates, the processing temperature and / or substrate temperature may be maintained at approximately 50°C to approximately 350°C (e.g., approximately 0°C to approximately 50°C, or approximately 10°C to approximately 20°C).

[0062]

[0067] 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 substrate temperature. The backside gas may include, but is not limited to, helium, argon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof.

[0063]

[0068] In step 330, a first RF bias is applied to the electrostatic chuck to generate plasma on the substrate, for example, adjacent to the substrate or near the substrate level. The plasma generated on the substrate may be generated within the plasma region between the substrate and the electrostatic chuck. The first RF bias may be 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 supplied at a frequency of about 13.56 MHz with a power of about 2,500 watts to about 3,000 watts. In one or more embodiments, the first RF bias is supplied to the electrostatic chuck 150 via a second RF electrode 260. The second RF electrode 260 may be electrically communicable with the first RF power supply 230 which supplies a bias voltage to the second RF electrode 260. In one or more embodiments, the bias power is about 10 watts to about 3,000 watts, about 2,000 watts to about 3,000 watts, or about 2,500 watts to about 3,000 watts. The first RF power supply 230 may generate power at frequencies 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).

[0064]

[0069] In one or more embodiments, step 330 further includes applying a second RF bias to the electrostatic chuck. The second RF bias can be 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 supplied at a frequency of about 2 MHz with a power of about 800 watts to about 1,200 watts. In other embodiments, the second RF bias is supplied to the substrate 402 via the chucking electrode 210. The chucking electrode 210 may be electrically communicable to a second RF power supply 240 that supplies a bias voltage to the chucking electrode 210. In one or more embodiments, the bias power is approximately 10 watts to approximately 3,000 watts, approximately 500 watts to approximately 1,500 watts, or approximately 800 watts to approximately 1,200 watts. The second RF power supply 240 can generate power at frequencies of approximately 350 kHz to approximately 100 MHz (e.g., approximately 350 kHz, approximately 2 MHz, approximately 13.56 MHz, approximately 27 MHz, approximately 40 MHz, approximately 60 MHz, or approximately 100 MHz). In one or more embodiments, the chucking voltage supplied during step 320 is also maintained during step 330.

[0065]

[0070] 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 approximately 2,500 watts (approximately 13.56 MHz), and the second RF bias is approximately 1,000 watts (approximately 2 MHz).

[0066]

[0071] In step 340, a deposition gas is introduced into the processing space 126 to form a doped diamond-like carbon film on the film laminate. The deposition gas may be introduced into the processing space 126 from the gas panel 130, through the gas distribution assembly 120, or through the side wall 101. The deposition gas comprises one or more hydrocarbon compounds and one or more dopant compounds. The hydrocarbon compounds may be one, two, or more hydrocarbon compounds in any state of matter, or may include them. Similarly, the dopant compounds may be one, two, or more hydrocarbon compounds in any state of matter, or may include them. The hydrocarbons and / or dopant compounds may be liquids or gases, but some advantages may be realized if either of the precursors is vapor at room temperature to simplify the hardware required for metering, control, and supply of the material to the processing space.

[0067]

[0072] 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 supplied during step 320 is maintained during step 340. In some embodiments, the processing conditions established during step 320 and the plasma formed during step 330 are maintained during step 340.

[0068]

[0073] In one or more embodiments, the hydrocarbon compound is a gaseous hydrocarbon or a liquid hydrocarbon. The hydrocarbon may be 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 of the general formula C x H y It is expressed as follows, where x is in the range of 1 to 20 and y is in the range of 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 (C 10 H 16 ), Norbornen (C7H10 ), or any combination thereof. In one or more embodiments, ethyne is used to form a more stable intermediate species that allows for improved surface mobility.

[0069]

[0074] Hydrocarbon compounds include one or more alkanes (e.g., C n H 2n+2 (where n is 1-20) or may include these. Suitable hydrocarbon compounds include alkanes (e.g., methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H) 10 ) and its isomers isobutane, pentane (C5H 12 ), Hexane (C6H 14 ) and its isomers isopentane and neopentane, hexane (C6H 14 This includes ) and its isomers 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, and 2,2-dimethylbutane, or combinations thereof.

[0070]

[0075] Hydrocarbon compounds include one or more alkenes (e.g., C n H 2n (where n is 1 to 20) or may include these. Suitable hydrocarbon compounds include, for example, alkenes such as ethylene, propylene (C3H6), 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).

[0071]

[0076] Hydrocarbon compounds include one or more alkynes (e.g., C n H 2n2(where n is 1-20) or may include these. Suitable hydrocarbons include, for example, alkynes (e.g., acetylene (C2H4), propyne (C3H4), butylene (C4H8), vinylacetylene, or combinations thereof).

[0072]

[0077] Hydrocarbon compounds are one or more aromatic hydrocarbon compounds (e.g., benzene, styrene, toluene, xylene, ethylbenzene, acetophenone, methyl benzoate, phenyl acetate, phenol, cresol, furan, etc.), α-terpinene, cymene, 1,1,3,3-tetramethylbutylbenzene, t-butyl ether, t-butylethylene, methyl methacrylate, and t-butyl furfuryl ether, compounds having chemical formulas C3H2 and C5H4, and halogenated aromatic compounds (including monofluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene, or any combination thereof), or may include these.

[0073]

[0078] Exemplary tungsten precursors include tungsten hexafluoride, tungsten hexachloride, tungsten hexacarbonyl, bis(cyclopentadienyl)tungsten dihydrogenate, bis(tert-butylimino)bis(dimethylamino)tungsten, or any combination thereof, or may include these. Exemplary molybdenum precursors include molybdenum pentachloride, molybdenum hexacarbonyl, bis(cyclopentadienyl)molybdenum dichloride, or any combination thereof, or may include these. Exemplary cobalt precursors include one or more of cobalt carbonyl compounds, cobalt amidinate compounds, cobaltcene compounds, cobalt dienyl compounds, complexes thereof, or any combination thereof, or may include these. Exemplary cobalt precursors include cyclopentadienyl dicarbonyl cobalt (CpCo(CO)2), dicobalt hexacarbonylbutylacetylene (CCTBA), (cyclopentadienyl)(cyclohexadienyl)cobalt, (cyclobutadienyl)(cyclopentadienyl)cobalt, bis(cyclopentadienyl)cobalt, bis(methylcyclopentadienyl)cobalt, bis(ethylcyclopentadienyl)cobalt, cyclopentadienyl(1,3-hexadienyl)cobalt, (cyclopentadienyl)(5-methylcyclopentadienyl)cobalt, and bis(ethylene)(pentamethylcyclopentadienyl)cobalt, or any combination thereof, or may include these.

[0074]

[0079] Exemplary nickel precursors are bis(cyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel, allyl(cyclopentadienyl)nickel, or any combination thereof, or may include these. Exemplary vanadium precursors are vanadium pentachloride, bis(cyclopentadienyl)vanadium, or any combination thereof, or may include these. Exemplary zirconium precursors are zirconium tetrachloride, bis(cyclopentadienyl)zirconium dihydrogenate, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, or any combination thereof, or may include these.

[0075]

[0080] Hafnium precursors may be one or more hafnium cyclopentadiene compounds, one or more hafnium amino compounds, one or more hafnium alkyl compounds, one or more hafnium alkoxy compounds, substitutes thereof, complexes thereof, adducts thereof, salts thereof, or any combination thereof, or may include these. Exemplary hafnium precursors include bis(methylcyclopentadiene)dimethylhafnium ((MeCp)2HfMe2), bis(methylcyclopentadiene)methylmethoxyhafnium ((MeCp)2Hf(OMe)(Me)), bis(cyclopentadiene)dimethylhafnium ((Cp)2HfMe2), tetra(tert-butoxy)hafnium, hafnium isopropoxide ((iPrO)4Hf), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), their isomers, their complexes, their adducts, their salts, or any combination thereof, or may include these.

[0076]

[0081] Exemplary tantalum-containing compounds include pentakis(ethylmethylamino)tantalum (PEMAT), pentakis(diethylamino)tantalum (PDEAT), pentakis(dimethylamino)tantalum (PDMAT), and any derivatives of PEMAT, PDEAT, and PDMAT, or may include these. Exemplary tantalum-containing compounds also include tert-butyliminotris(diethylamino)tantalum (TBTDET), tert-butyliminotris(dimethylamino)tantalum (TBTDMT), bis(cyclopentadienyl)tantalum trihydride, bis(methylcyclopentadienyl)tantalum trihydride, and tantalum halides, TaX5 (where X is fluorine (F), bromine (Br), or chlorine (Cl), and / or derivatives thereof). Exemplary nitrogen-containing compounds include nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, and derivatives thereof.

[0077]

[0082] Exemplary silicon precursors are silane, disilane, trisilane, tetrasilane, pentasilane, hexasilane, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorosilane, substituted silanes, plasma derivatives thereof, or any combination thereof, or may include them. Exemplary boron precursors are diborane, triborane, tetraborane, triethylborane (Et3B), dimethylaminoborane, or any combination thereof, or may include them.

[0078]

[0083] Nitrogen-containing compounds are, or may include, one or more of pyridine compounds, aliphatic amines, amines, nitriles, and similar compounds. Exemplary nitrogen-containing compounds are, or may include, nitrogen gas, atomic nitrogen, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, and derivatives thereof. Exemplary phosphorus precursors are, or may include, phosphine, triphenylphosphine, trimethylphosphine, triethylphosphine, or any combination thereof. Exemplary germanium precursors are, or may include, germanium, tetramethylgermanium, triethylgermanium hydride, triphenylgermanium hydride, or any combination thereof.

[0079]

[0084] In one or more embodiments, the deposition gas further comprises one or more diluent gases, one or more carrier gases, and / or one or more purge gases. In particular, suitable diluent 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 may be co-circulated or supplied with the deposition gas into the processing space 126. Argon, helium, and / or nitrogen may be used to control the density and deposition rate of the doped diamond-like carbon film. In some cases, the addition of N2 and / or NH3 may be used to control the hydrogen ratio in the doped diamond-like carbon film, as described later. Alternatively, no diluent gas may be used during deposition.

[0080]

[0085] In some embodiments, the deposition gas further comprises an etchant gas. Suitable etchant gases are chlorine (Cl2), fluorine (F2), hydrogen fluoride (HF), carbon tetrafluoride (CF4), nitrogen trifluoride (NF3), or a combination thereof, or comprising these. While not bound by theory, the etchant gas is sp from the membrane. 2Selective etching of hybrid carbon atoms, and consequently sp in the film. 3 It is believed that increasing the fractionation of hybrid carbon atoms will improve the etching selectivity of the film.

[0081]

[0086] In one or more embodiments, after the doped diamond-like carbon film 412 is formed on the substrate in step 340, the doped diamond-like carbon film 412 is exposed to hydrogen radicals. In some embodiments, the doped diamond-like carbon film is exposed to hydrogen radicals during the deposition process of step 340. In other embodiments, the hydrogen radicals are formed in the RPS and supplied to the processing area. While not bound by theory, exposing the doped diamond-like carbon film to hydrogen radicals is sp 2 This leads to selective etching of hybrid carbon atoms, resulting in the sp of the film. 3 This is thought to increase the fractionation of hybrid carbon atoms, thereby improving etching selectivity.

[0082]

[0087] In step 350, after the doped diamond-like carbon film 412 is formed on the substrate, the substrate is released from the chuck. During step 350, the chucking voltage is turned off. The reactive gas is also turned off and optionally purged from the processing chamber. In one or more embodiments, the RF power is reduced during step 350 (e.g., about 200 watts). Optionally, the controller 110 monitors the impedance change to determine whether the electrostatic charge has dissipated to ground through the RF path. Once the substrate is released from the electrostatic chuck, the residual gas is purged from the processing chamber. The processing chamber is pumped down, and the substrate is lifted by lift pins and transported out of the chamber.

[0083]

[0088] Figure 5 shows a flow chart of method 500 using a doped diamond-like carbon film according to one or more embodiments described herein. The doped diamond-like carbon film 412, after being formed on a substrate, can be used as a patterning mask to form a three-dimensional structure (such as a stepped structure) in an etching process. The doped 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 doped diamond-like carbon film 412. In step 520, the doped diamond-like carbon film 412 may be etched in a pattern corresponding to the patterned photoresist layer, and then this pattern is etched onto the substrate 530. In step 540, material can be deposited in the etched portion of the substrate 402. In step 550, the doped diamond-like carbon film 412 can be removed using a solution containing hydrogen peroxide and sulfuric acid. One exemplary solution containing hydrogen peroxide and sulfuric acid is known as piranha solution or piranha etching solution. The doped diamond-like carbon film 412 can also be removed using etching chemicals containing oxygen and halogens (e.g., fluorine or chlorine) (e.g., Cl2 / O2, CF4 / O2, Cl2 / O2 / CF4). The doped diamond-like carbon film 412 can also be removed by chemical mechanical polishing (CMP).

[0084] Logical implementation example:

[0089] The following non-limiting embodiments are provided to further illustrate the implementations described herein. However, these embodiments are not intended to cover all embodiments described herein, nor to limit their scope. Some actual and predicted results are shown in Table II.

[0085]

[0090] In one or more embodiments, the low-stress, high-density boron-doped diamond-like carbon film of the present disclosure is deposited using approximately 150 sccm of acetylene, approximately 100 sccm of helium, and 100 sccm of diborane (diluted with 90 vol% H2) as the deposition gas. The substrate is at a temperature of approximately 10°C, the chamber pressure is maintained at approximately 5 mTorr, during which approximately 2,500 watts of RF (13.56 MHz) power and approximately 1,000 watts (2 MHz) through the substrate pedestal (electrostatic chuck) are applied to the CVD reactor having Ar and / or He as the diluent gas.

[0086]

[0091] The resulting boron-doped diamond-like carbon film has a density greater than 2 g / cc, for example, 2.5 g / cc to about 3 g / cc, or about 5 g / cc, a stress of 500 MPa or less, for example, 550 MPa or 600 MPa, and a K < 0.15 at 633 nm. The boron-doped diamond-like carbon film has higher etching selectivity than currently available amorphous carbon films or other conventional undoped diamond-like carbon films.

[0087]

[0092] In other embodiments, the high-density tungsten-doped diamond-like carbon films of the present disclosure were manufactured by flowing approximately 150 sccm of acetylene, approximately 100 sccm of helium, and 20 sccm of tungsten hexafluoride as deposition gases. The substrate was at a temperature of approximately 10°C, the chamber pressure was maintained at approximately 5 mTorr, and during this time, approximately 2,500 watts of RF (13.56 MHz) power and approximately 1,000 watts (2 MHz) through the substrate pedestal (electrostatic chuck) were applied to a CVD reactor having Ar and / or He as diluent gases.

[0088]

[0093] The resulting tungsten-doped diamond-like carbon film has a density greater than 3 g / cc, for example, 3.5 g / cc to about 10 g / cc, or about 12 g / cc, a stress of 550 MPa or less, for example, 600 MPa or 650 MPa, and a K < 0.15 at 633 nm. The tungsten-doped diamond-like carbon film has higher etching selectivity than currently available amorphous carbon films or other conventional undoped diamond-like carbon films. TIFF2023533711000003.tif94170

[0089] Extreme ultraviolet (EUV) patterning method

[0094] When using metal-containing photoresists in extreme ultraviolet (EUV) patterning, the selection of the underlying layer is crucial to prevent nanofailures (e.g., bridge formation defects and spacing defects) in semiconductor devices. Conventional underlying layers for EUV patterning (lithography) are spin-on carbon (SOC) materials. However, during patterning, metals such as tin can diffuse through the SOC material, leading to nanofailures in semiconductor devices. Such nanofailures can degrade, degrade, and interfere with semiconductor performance.

[0090]

[0095] On the other hand, the high-density carbon films described herein have superior film quality (e.g., improved hardness and density). Such hardness and density enable the high-density carbon films to act as a significantly stronger barrier against metal intrusion and prevent (or at least reduce) minute defects than conventional SOC films. In one or more embodiments, doped diamond-like carbon films are provided for use as underlayers for extreme ultraviolet (EUV) lithography.

[0091]

[0096] In one or more embodiments, the doped diamond-like carbon film used as an underlayer for EUV lithography may be any film described herein. The doped diamond-like carbon film has a total amount of carbon atoms in it of about 40% to about 90% sp 3 It may have a hybrid carbon atom content, a density exceeding 2 g / cc, for example, a density of about 2.5 g / cc to about 12 g / cc or about 3 g / cc to about 10 g / cc, and an elastic modulus of about 150 GPa to about 400 GPa.

[0092]

[0097] In some embodiments, the doped diamond-like carbon film used as an underlayer for EUV lithography has a density of 2.5 g / cc to 12 g / cc and an elastic modulus of about 180 GPa to about 200 GPa. The doped diamond-like carbon film has a density of about 3 g / cc and an elastic modulus of about 195 GPa. In other embodiments, the doped diamond-like carbon film has a stress of about 600 MPa, a refractive index of about 2.0 to about 3.0, and an extinction coefficient of about 0.2 and about 0.3.

[0093]

[0098] Thus, a method and apparatus are provided for forming a doped diamond-like carbon film or a hard mask layer containing the same, which can be used to form a stepped structure for manufacturing three-dimensional stacking of semiconductor devices. By utilizing a doped diamond-like carbon film as a hard mask layer having desired robust film properties and etching selectivity, improved control of the dimensions and profiles of the resulting film stacks can be obtained, potentially enhancing the electrical performance of chip devices in applications for three-dimensional stacking of semiconductor devices.

[0094]

[0099] In other words, some of the advantages of this disclosure provide a process for depositing or forming a doped diamond-like carbon film on a substrate. A typical PE-CVD hard mask film is a hybrid sp 3The proportion of atoms is very low, and therefore the elastic modulus and etching selectivity are also low. In some embodiments described herein, low process pressure (less than 1 Torr) and bottom-driven plasma result in more than 60% hybrid sp². 3 This enables the fabrication of doped films containing atoms, resulting in improved etching selectivity compared to conventionally available hard mask films. In addition, some of the embodiments described herein are carried out at low substrate temperatures, allowing for the deposition of other dielectric films at temperatures much lower than currently possible, opening up the possibility of applications with low thermal balances that have not been addressed by CVD until now. Furthermore, some of the embodiments described herein can be used as underlayers for EUV lithography.

[0095]

[0100] While the foregoing applies to embodiments of the present disclosure, other embodiments and further embodiments of the present disclosure may be devised without departing from the fundamental scope of the present disclosure, and the scope of the present disclosure is determined by the following claims. All documents described herein, including any prior documents and / or test procedures, are incorporated herein by reference, insofar as they do not conflict with this text. As is obvious from the above summary and specific embodiments, the forms of the present disclosure are illustrated and described, but various modifications can be made without departing from the essence and scope of the present disclosure. Therefore, the present disclosure is not intended to be limited by the forms of the present disclosure illustrated and described. Similarly, the word “comprising” is considered synonymous with the word “including” in the interpretation of U.S. 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 is also assumed to be preceded by the transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is,” and vice versa.

[0096]

[0101] Certain embodiments and features are described using sets of upper and lower numerical limits. Unless otherwise indicated, it should be recognized that ranges are assumed to include any combination of any two values ​​(e.g., any lower value and any upper value, any two lower values, and / or any two upper values). Some of the following claims describe certain lower limits, upper limits, and ranges.

Claims

1. 1. A method for processing a substrate, comprising: flowing a deposition gas including a hydrocarbon compound and a dopant 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 at the substrate by applying a first RF bias to the electrostatic chuck and depositing a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density greater than 2.6 g / cc and a stress less than -500 MPa, the doped diamond-like carbon film comprising 45 atomic % to 95 atomic % sp 3 hybridized carbon atoms; The method includes:

2. The method of claim 1, wherein the doped diamond-like carbon film has a density between 2.7 g / cc and 12 g / cc.

3. 10. The method of claim 1, wherein the dopant compound comprises a metal dopant comprising tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof.

4. 2. The method of claim 1, wherein the dopant compound comprises tungsten hexafluoride, tungsten hexacarbonyl, molybdenum pentachloride, cyclopentadienyl dicarbonyl cobalt, dicobalt hexacarbonyl butyl acetylene (CCTBA), bis(cyclopentadienyl) cobalt, bis(methylcyclopentadienyl) nickel, vanadium pentachloride, zirconium tetrachloride, or any combination thereof.

5. The method of claim 1 , wherein the dopant compound comprises a non-metallic dopant comprising boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof.

6. 10. The method of claim 1, wherein the dopant compound comprises disilane, diborane, triethylborane, silane, disilane, trisilane, germane, ammonia, hydrazine, phosphine, adducts thereof, or any combination thereof.

7. The method of claim 1, wherein the doped diamond-like carbon film comprises between 0.1 atomic % and 20 atomic % of the dopant.

8. The doped diamond-like carbon film is 50 atomic % to 90 atomic % sp ３ The method of claim 1 , comprising hybrid carbon atoms.

9. 2. 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.

10. The deposition gas may be helium, argon, xenon, neon, nitrogen (N ２ ), hydrogen (H ２ ), or any combination thereof.

11. 10. 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.degree. C. and 50.degree.

12. The method of claim 1 , wherein the doped diamond-like carbon film has an elastic modulus greater than 150 GPa.

13. The method of claim 1 , wherein generating the plasma at the substrate further comprises applying a second RF bias to the electrostatic chuck.

14. 14. The method of claim 13, wherein the electrostatic chuck comprises a chucking electrode and an RF electrode separate from the chucking electrode, the first RF bias is applied to the RF electrode and the second RF bias is applied to the chucking electrode.

15. 14. The method of claim 13, wherein the first RF bias is 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 is supplied at a frequency between 350 KHz and 100 MHz and at a power between 10 Watts and 3,000 Watts.

16. 1. A method for processing a substrate, comprising: flowing a deposition gas including a hydrocarbon compound and a dopant compound into a process space of a process chamber having a substrate disposed on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode, the process space being maintained at a pressure between 0.5 mTorr and 10 Torr; generating a plasma at the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density of greater than 2.6 g / cc to 12 g / cc and a stress of -600 MPa to -300 MPa, the doped diamond-like carbon film having 50 atomic % to 90 atomic % sp ３ generating a plasma comprising hybrid carbon atoms; The method includes:

17. The method of claim 16, wherein the doped diamond-like carbon film has a density between 3 g / cc and 10 g / cc.

18. 17. The method of claim 16, wherein the dopant compound comprises a metal dopant comprising tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof.

19. 17. The method of claim 16, wherein the dopant compound comprises a non-metal dopant comprising boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof.

20. 1. A method for processing a substrate, comprising: flowing a deposition gas including a hydrocarbon compound and a dopant compound into a process space of a process chamber having a substrate disposed on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode, the process space being maintained at a pressure between 0.5 mTorr and 10 Torr; generating a plasma at the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a doped diamond-like carbon film on the substrate, the doped diamond-like carbon film having a density of greater than 2.6 g / cc to 12 g / cc and a stress of -600 MPa to -300 MPa; forming a patterned photoresist layer over the doped diamond-like carbon film; Etching the doped 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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