KR20230029911A - Methods for Creating High Density Doped Carbon Films for Hardmask and Other Patterning Applications - Google Patents

Abstract

Embodiments of the present disclosure relate generally to the fabrication of integrated circuits. More specifically, the embodiments described herein provide techniques for depositing high-density films for patterning applications. In one or more embodiments, flowing a deposition gas containing a hydrocarbon compound and a dopant compound into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck - the processing volume at a pressure between about 0.5 mTorr and about 10 Torr. A method of processing a substrate comprising a retained - is provided. The method also includes generating a plasma on the substrate by applying a first RF bias to an electrostatic chuck to deposit a doped diamond-like carbon film on the substrate, wherein the doped diamond-like carbon film has a density greater than 2 g/cc and - Has a stress of less than 500 MPa.

Description

Methods for Creating High Density Doped Carbon Films for Hardmask and Other Patterning Applications

[0001] Embodiments of the present disclosure relate generally to the fabrication of integrated circuits. More specifically, embodiments described herein provide techniques for deposition of high-density films for patterning applications.

[0002] Integrated circuits have evolved into complex devices that may include millions of transistors, capacitors, and resistors on a single chip. Advances in chip designs continue to require faster circuitry and greater circuit density. Demands for faster circuitry with greater circuit densities place corresponding demands on the materials used to fabricate such integrated circuits. In particular, as the dimensions of integrated circuit components decrease on the sub-micron scale, it is now possible to use low resistivity conductive materials as well as low dielectric constant materials to obtain suitable electrical performance from such components. It is necessary to use insulating materials.

[0003] Demands for greater integrated circuit densities also place demands on the process sequences used in the fabrication of integrated circuit components. For example, in process sequences using conventional photolithographic techniques, an energy sensitive resist layer is formed over a stack of material layers disposed on a substrate. A layer of energy sensitive resist is exposed to an image of the pattern to form a photoresist mask. A mask pattern is then transferred to one or more of the material layers of the stack using an etch process. The chemical etchant used in the etch process is selected to have a greater etch selectivity to the material layers of the stack than the mask of energy sensitive resist. That is, the chemical etchant etches one or more layers of the material stack at a much faster rate than the energy sensitive resist. The etch selectivity for one or more material layers of the stack, over the resist, prevents the energy sensitive resist from being consumed prior to completion of pattern transfer.

[0004] As the pattern dimensions are reduced, the thickness of the energy sensitive resist is correspondingly reduced to control the pattern resolution. Such thin resist layers may be insufficient to mask the underlying material layers during the pattern transfer step due to attack by the chemical etchant. An intermediate layer (e.g., silicon oxynitride, silicon carbide, or carbon film), called a hardmask, due to its greater resistance to chemical etchants, forms an energy-sensitive resist layer and an underlying layer to facilitate pattern transfer. It is often used between layers of material. Hardmask materials that have both high etch selectivity and high deposition rates are desirable. As critical dimensions (CD) decrease, current hardmask materials lack the desired etch selectivity to underlying materials (eg, oxides and nitrides) and are often difficult to deposit.

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

[0006] Embodiments of the present disclosure relate generally to the fabrication of integrated circuits. More specifically, the embodiments described herein provide techniques for deposition of high-density films for patterning applications. In one or more embodiments, a method of processing a substrate includes flowing a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck. where the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating a plasma in the substrate by applying a first RF bias to an electrostatic chuck to deposit a doped diamondoid carbon film on the substrate, wherein the doped diamondoid carbon film has a density greater than 2 g/cc. density and a stress of less than -500 MPa.

[0007] In some embodiments, a method of processing a substrate includes flowing a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck. wherein the electrostatic chuck has a chucking electrode and an RF electrode separate from the chucking electrode, wherein the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating a plasma in 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 diamondoid carbon film on the substrate. The doped diamondoid carbon film has a density of greater than 2 g/cc to about 12 g/cc and a stress of about -600 MPa to about -300 MPa. The doped diamondoid carbon film contains from about 50 atomic percent (atomic percent) to about 90 atomic percent sp ³ hybridized carbon atoms.

[0008] In other embodiments, a method of processing a substrate includes flowing a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck. Include steps. The electrostatic chuck has a chucking electrode and an RF electrode separate from the chucking electrode, and the processing volume is 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 RF electrode and a second RF bias to the chucking electrode to deposit a doped diamond-like carbon film on the substrate, wherein the doping The diamond-like carbon film having a density of greater than 2 g/cc to about 12 g/cc and a stress of about -600 MPa to about -300 MPa. The method further includes 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, and etching the pattern into the substrate. to include

[0009] In one or more embodiments, a film for use as an underlayer for an extreme ultraviolet ("EUV") lithography process is provided, the film comprising about 40% to about 90%, based on the total amount of carbon atoms in the film. an sp ³ hybridized carbon atom content of about 0.1 atomic % to about 20 atomic % of one or more dopants, a density of greater than 2.5 g/cc to about 12 g/cc, and an elastic modulus of greater than or equal to about 150 GPa to about 400 GPa. includes

[0010] In such a way that the above-listed features of the present disclosure may be understood in detail, a more detailed description of the foregoing briefly summarized implementations may be made with reference to implementations, some of which are illustrated in the accompanying drawings exemplified in the However, it should be noted that the accompanying drawings depict only typical implementations of the present disclosure and are therefore not to be regarded as limiting the scope of the present disclosure, as it allows for other equally effective implementations. Because you can.
[0011] FIG. 1A shows a schematic cross-sectional view of a deposition system that can be used in the practice of embodiments described herein.
[0012] FIG. 1B shows a schematic cross-sectional view of another deposition system that may be used in the practice of embodiments described herein.
[0013] FIG. 2 shows a schematic cross-sectional view of an electrostatic chuck that can be used in the apparatus of FIGS. 1A and 1B, for practice of embodiments described herein.
[0014] FIG. 3 shows a flow diagram of a method for forming a doped diamondoid carbon film on a film stack disposed on a substrate in accordance with one or more embodiments of the present disclosure.
4A and 4B show a sequence for forming a doped diamondoid carbon film on a film stack formed on a substrate, in accordance with one or more embodiments of the present disclosure.
[0016] FIG. 5 shows a flow diagram of a method using a doped diamondoid carbon film, in accordance with one or more embodiments of the present disclosure.
[0017] For ease of understanding, the same reference numbers have been used where possible to indicate like elements that are common to the drawings. It is contemplated that elements and features of one embodiment may be advantageously incorporated into other embodiments without further recitation.

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

[0019] The many details, dimensions, angles and other features shown in the drawings merely illustrate particular embodiments. Accordingly, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the present disclosure. Moreover, additional embodiments of the present disclosure may be practiced without some of the details set forth below.

[0020] Embodiments described herein will be described below with reference to a plasma-enhanced chemical vapor deposition (PE-CVD) process that can be performed using any suitable thin film deposition system. Examples of suitable systems are CENTURA® systems capable of using a DXZ® processing chamber, PRECISION 5000® systems, PRODUCER® systems, PRODUCER® GT™ systems, PRODUCER® XP Precision™ systems, PRODUCER® SE™ systems , the Sym3® processing chamber, and the Mesa™ processing chamber, all commercially available from Applied Materials, Inc. of Santa Clara, CA. 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 PE-CVD processes described herein may be advantageously used. Device descriptions set forth herein are illustrative and should not be understood or construed as limiting the scope of the embodiments described herein.

[0021] Current hardmask applications for memory and other devices generally use thick carbon films (e.g., about 300 nm to about 1.5 microns) that are essentially amorphous, but their etch selectivity is increasingly It is no longer sufficient to meet stringent requirements and subsequent high-aspect ratio etching of nodes. To achieve a higher etching selectivity, the density and Young's modulus of the film need to be improved. One of the major challenges in achieving greater etch selectivity and improved Young's modulus is that the high compressive stress of such films due to the resulting high wafer/substrate warpage makes such films unsuitable for applications. Thus, for carbon (diamond-shaped) films with high density and modulus (eg higher sp ³ content, more diamondoid) with high etch selectivity with low stress (eg <-500 MPa) there is a need for

[0022] Embodiments described herein provide high density (eg, >2 g/cc), high modulus (eg, >150 GPa), and low stress (eg, <-500 MPa). and improved methods of fabricating doped diamond-like carbon films having Doped diamondoid carbon films prepared in accordance with the embodiments described herein are inherently amorphous and can be etched with much higher modulus (e.g., >150 GPa) with lower stress than current patterning films. have selectivity. Doped diamondoid carbon films prepared according to the embodiments described herein have low stress as well as high sp ³ carbon content. In general, the deposition process described herein is also fully compatible with current integration schemes for hardmask applications.

[0023] In one or more embodiments, the doped diamondoid carbon films described herein are subjected to chemical vapor deposition (CVD) using a deposition gas containing one or more hydrocarbon compounds and one or more dopant compounds, such as plasma enhanced It may be formed by CVD and/or thermal CVD processes. Exemplary hydrocarbon compounds include ethyne or acetylene (C ₂ H ₂ ), propene (C ₃ H ₆ ), methane (CH ₄ ), butene (C ₄ H ₈ ), 1,3-dimethyladamantane, bicyclo[ 2.2.1]hepta-2,5-diene (2,5-norbornadiene), adamantine (C ₁₀ H ₁₆ ), norbornene (C ₇ H ₁₀ ), their derivatives, their isomers , or any combination thereof.

[0024] The dopant compound may be or include one or more metal dopants, one or more non-metal dopants, or combinations thereof. A dopant compound can be one or more chemical precursors used in a vapor deposition process such as CVD or ALD. The metal dopant can be or include one or more of tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof. Thus, the metal dopant may be or may be one or more of tungsten precursors, molybdenum precursors, cobalt precursors, nickel precursors, vanadium precursors, hafnium precursors, zirconium precursors, tantalum precursors, or any combination thereof. can include Exemplary metal dopants include tungsten hexafluoride, tungsten hexacarbonyl, molybdenum pentachloride, cyclopentadienyl dicarbonyl cobalt, dicobalt hexacarbonyl butylacetylene (CCTBA), bis(cyclopentadienyl) cobalt, bis( methylcyclopentadienyl) nickel, vanadium pentachloride, hafnium tetrachloride, tetrakis(dimethylamino) hafnium, tetrakis(diethylamino) hafnium, zirconium tetrachloride, bis(cyclopentadienyl) zirconium dihydride, tetra Kiss(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. The non-metal dopant may be or include one or more of boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof. Thus, the non-metal dopant may be or include one or more of boron precursors, silicon precursors, germanium precursors, nitrogen precursors, phosphorus precursors, or any combination thereof. Exemplary non-metal dopants may be or include disilane, diborane, triethylborane, silane, disilane, trisilane, germane, ammonia, hydrazine, phosphine, adducts thereof, or any combination thereof. there is.

[0025] The substrate and/or processing volume may be heated and maintained at independent temperatures during the deposition process. The substrate and/or processing volume is about -50°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. °C, about 30 °C, about 50 °C, about 100 °C, about 150 °C, about 200 °C, about 300 °C, about 400 °C, about 500 °C, or about 600 °C. For example, the substrate and/or processing volume may be about -50°C to about 600°C, about -50°C to about 450°C, about -50°C to about 350°C, about -50°C to about 200°C, about -50°C °C to about 100 °C, about -50 °C to about 50 °C, about -50 °C to about 0 °C, about 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 It may be heated to a temperature of 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 10°C to about 50°C. .

[0026] The processing volume of the processing chamber is maintained at sub-atmospheric pressures during the deposition process. The processing volume of the processing chamber is 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 volume of the processing chamber may be about 0.1 mTorr to about 10 Torr, about 0.1 mTorr to about 5 Torr, about 0.1 mTorr to about 1 Torr, about 0.1 mTorr to about 500 mTorr, about 0.1 mTorr to about 100 mTorr, about 0.1 mTorr to about 10 mTorr, about 1 mTorr to about 10 Torr, about 1 mTorr to about 5 Torr, about 1 mTorr to about 1 Torr, about 1 mTorr to about 500 mTorr, about 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 is maintained at a pressure of

[0027] The deposition gas may include, for example, one or more diluent gases _, carrier gases, and _/ or Alternatively, purge gases may be further included. The deposition gas may further include etchant gases such as chlorine (Cl ₂ ), carbon tetrafluoride (CF ₄ ), and/or nitrogen trifluoride (NF ₃ ) to improve film quality. . A plasma (eg, capacitively coupled plasma) may be formed from the top and bottom electrodes or side electrodes. The electrodes may be formed of single power electrodes, dual power electrodes, or more electrodes, and may operate at about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, and about 100 MHz. Depositing a thin film of diamondoid carbon for use as a hardmask and/or etch stop or any other application requiring smooth carbon films with multiple frequencies such as, but not limited to, MHz. alternatively or concurrently in a CVD system with any or all of the reactant gases listed herein for The high etch selectivity of doped diamondoid carbon films is achieved by having a higher density and modulus than current generation films. Without being bound by theory, it is believed that the higher density and modulus is a result of the high content of sp ³ hybridized carbon atoms in the doped diamondoid carbon film, which in turn can be achieved by a combination of low pressure and plasma power.

[0028] In one or more embodiments, using a plasma generated at the substrate level by applying a bias of about 2,500 watts (about 13.56 MHz) to the electrostatic chuck, maintained at about 10° C. and a pressure of about 2 mTorr. A doped diamond-like carbon film is deposited in a chamber having a substrate pedestal. In other embodiments, about 1,000 Watts of additional RF at about 2 MHz was also delivered to the electrostatic chuck, thereby creating a dual-bias plasma at the substrate level.

[0029] In one or more embodiments, hydrogen radicals are supplied through the RPS, which results in selective etching of the sp ² hybridized carbon atoms, thus further increasing the sp ³ hybridized carbon atom fraction of the film, and thus , which further increases the etching selectivity. The doped diamondoid carbon film comprises at least 40 atomic percent (atomic %), about 45 atomic %, about 50 atomic %, about 55 atomic %, or about 58 atomic %, based on the total amount of carbon atoms in the doped diamond-like carbon film. to about 60 atomic %, about 65 atomic %, about 70 atomic %, about 75 atomic %, about 80 atomic %, about 85 atomic %, about 88 atomic %, about 90 atomic %, about 95 atomic % sp ³ hybridized carbon. It may have a concentration or ratio of atoms (eg, sp ³ hybridized carbon atom content). For example, the doped diamondoid carbon film may contain, based on the total amount of carbon atoms in the doped diamondoid carbon film, at least 40 atomic % to about 95 atomic %, about 45 atomic % to about 95 atomic %, about 50 atomic % to about 95 atomic %, about 50 atomic % to about 90 atomic %, about 50 atomic % to about 85 atomic %, about 50 atomic % to about 80 atomic %, about 50 atomic % to about 75 atomic %, about 50 atomic % to about 70 atomic %, about 50 atomic % to about 65 atomic %, about 65 atomic % to about 95 atomic %, about 65 atomic % to about 90 atomic %, about 65 atomic % to about 85 atomic %, about 65 atomic % to about 80 atomic %, about 65 atomic % to about 75 atomic %, about 65 atomic % to about 70 atomic %, about 65 atomic % to about 68 atomic %, about 75 atomic % to about 95 atomic %, about 75 atomic % to about 90 atomic %, about 75 atomic % to about 85 atomic %, about 75 atomic % to about 80 atomic % or about 75 atomic % to ⁷⁸ atomic %.

[0030] The doped diamondoid carbon film contains about 0.01 atomic %, about 0.05 atomic %, about 0.1 atomic %, about 0.3 atomic %, about 0.5 atomic %, about 0.8 atomic %, based on the total amount of atoms in the doped diamond-like carbon film. atomic %, about 1 atomic %, about 1.2 atomic %, about 1.5 atomic %, about 1.8 atomic %, about 2 atomic %, about 2.5 atomic %, or from about 2.8 atomic % to about 3 atomic %, about 3.5 atomic %, about 4 atomic%, about 5 atomic%, about 6 atomic%, about 7 atomic%, about 8 atomic%, about 9 atomic%, about 10 atomic%, about 12 atomic%, about 15 atomic%, about 18 atomic%, about 20 atomic %, about 25 atomic %, about 30 atomic %, or a concentration or percentage of the dopant. For example, the doped diamondoid carbon film may contain from about 0.01 atomic % to about 25 atomic %, from about 0.1 atomic % to about 25 atomic %, from about 0.5 atomic % to about 0.5 atomic % based on the total amount of atoms in the doped diamond-like carbon film. 25 atomic %, about 1 atomic % to about 25 atomic %, about 2 atomic % to about 25 atomic %, about 3 atomic % to about 25 atomic %, about 5 atomic % to about 25 atomic %, about 7 atomic % to about 25 atomic %, about 10 atomic % to about 25 atomic %, about 12 atomic % to about 25 atomic %, about 15 atomic % to about 25 atomic %, about 18 atomic % to about 25 atomic %, about 20 atomic % to about 25 atomic %, about 0.1 atomic % to about 20 atomic %, about 0.5 atomic % to about 20 atomic %, about 1 atomic % to about 20 atomic %, about 2 atomic % to about 20 atomic %, about 3 atomic % to about 20 atomic %, about 5 atomic % to about 20 atomic %, about 7 atomic % to about 20 atomic %, about 10 atomic % to about 20 atomic %, about 12 atomic % to about 20 atomic %, about 15 atomic % to about 20 atomic %, about 18 atomic % to about 20 atomic %, about 0.1 atomic % to about 18 atomic %, about 0.5 atomic % to about 18 atomic %, about 1 atomic % to about 18 atomic %, about 2 atomic % to about 18 atomic %, about 3 atomic % to about 18 atomic %, about 5 atomic % to about 18 atomic %, about 7 atomic % to about 18 atomic %, about 10 atomic % to about 18 atomic %, about 12 atomic % to about 18 atomic %, about 15 atomic % to about 18 atomic %, about 0.1 atomic % to about 15 atomic %, about 0.5 atomic % to about 15 atomic %, about 1 atomic % to about 15 atomic %, about 2 atomic % to about 15 atomic %, about 3 atomic % to about 15 atomic %, about 5 atomic % to about 15 atomic %, about 7 atomic % to about 15 atomic %, about 10 atomic % to about 15 atomic %, about 12 atomic % to about 15 atomic %, about 0.01 atomic % to about 10 atomic %, about 0.1 atomic % to about 10 atomic %, about 0.5 atomic % to about 10 atomic %, about 1 atomic % to about 10 atomic %, about 2 atomic % to about 10 atomic %, about 3 atomic % to about 10 atomic %, about 4 atomic % to about 10 atomic %, about 5 atomic % to about 10 atomic %, about 7 atomic % to about 10 atomic %, about 0.01 atomic % to about 5 atomic %, about 0.1 Atomic % to about 5 atomic %, about 0.5 atomic % to about 5 atomic %, about 1 atomic % to about 5 atomic %, about 2 atomic % to about 5 atomic %, or about 3 atomic % to about 5 atomic % dopant. may have a concentration or percentage of

[0031] The doped diamondoid carbon film contains greater than 2 g/cc, such as 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, and 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 greater. For example, the doped diamondoid carbon film may have a density greater than 2 g/cc to about 12 g/cc, greater than 2 g/cc to about 10 g/cc, greater than 2 g/cc to about 8 g/cc, 2 g/cc Greater than about 7 g/cc, greater than 2 g/cc to about 5 g/cc, greater than 2 g/cc to about 4 g/cc, greater than 2 g/cc to about 3 g/cc, greater than or equal to about 2.5 g/cc to about 12 g/cc, greater than about 2.5 g/cc to about 10 g/cc, greater than about 2.5 g/cc to about 8 g/cc, greater than about 2.5 g/cc to about 7 g/cc, about 2.5 g/cc cc or more to about 5 g/cc, about 2.5 g/cc or more to about 4 g/cc, about 2.5 g/cc or more to about 3 g/cc, about 3 g/cc or more to about 12 g/cc, about 3 g/cc or greater to about 10 g/cc, greater than or equal to about 3 g/cc to about 8 g/cc, greater than or equal to about 3 g/cc to about 7 g/cc, greater than or equal to about 3 g/cc to about 5 g/cc, and a density of greater than about 3 g/cc to about 4 g/cc, or greater than about 3 g/cc to about 3.5 g/cc.

[0032] The doped diamondoid carbon film may have a density 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 800 Å, about 1,000 Å, about 2,000 Å, about 3,000 Å Å, about 5,000 Å, about 8,000 Å, about 10,000 Å, about 15,000 Å, about 20,000 Å, or greater. For example, a doped diamondoid carbon film may have a voltage range 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, or about 5 Å to about 1,000 Å. Å, from about 5 Å to about 500 Å, from about 5 Å to about 200 Å, from about 5 Å to about 100 Å, from about 5 Å to about 50 Å, from about 300 Å to about 20,000 Å, from about 300 Å to about 10,000 Å, from about 00 Å to about 5,000 Å, from about 300 Å About 3,000 Å, from about 300 Å to about 2,000 Å, from about 300 Å to about 1,000 Å, from about 300 Å to about 500 Å, from about 300 Å to about 200 Å, from about 300 Å to about 100 Å, from about 300 Å to about 50 Å, from about 1,000 Å to about 20,000 Å, A thickness of from about 1,000 Å to about 10,000 Å, from about 1,000 Å to about 5,000 Å, from about 1,000 Å to about 3,000 Å, from about 1,000 Å to about 2,000 Å, from about 2,000 Å to about 20,000 Å, or from about 2,000 Å to about 3,000 Å can have

[0033] The doped diamondoid carbon film has a refractive index greater than 2, such as about 2.1, about 2.2, about 2.3, about 2,4 or about 2.5 to about 2.6, about 2.7, about 2.8, about 2,9, or about 3, or It can have an n-value (n (at 633 nm)). For example, a doped diamondoid carbon film may have a range of 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, or 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, or a refractive index or n-value (n (at 633 nm)).

[0034] The doped diamondoid carbon film may have an extinction coefficient or k-value (K (at 633 nm)) greater than 0.1, such as about 0.15, about 0.2, about 0.25, or about 0.3. For example, the doped diamondoid carbon film has an extinction coefficient of greater than 0.1 to about 0.3, greater than 0.1 to about 0.25, greater than 0.1 to about 0.2, greater than 0.1 to about 0.15, about 0.2 to about 0.3, or about 0.2 to about 0.25; or It can have a k-value (K (at 633 nm)).

[0035] The doped diamondoid carbon film is less than -250 MPa, less than -275 MPa, less than about -300 MPa, less than about -350 MPa, less than about -400 MPa, less than about -450 MPa, less than about -500 MPa, less than about may have a stress of -550 MPa or less, about -600 MPa, or less. For example, a doped diamondoid carbon film about -600 MPa to about -300 MPa, about -600 MPa to about -350 MPa, about -600 MPa to about -400 MPa, about -600 MPa to about -450 MPa, About -600 MPa to about -500 MPa, about -600 MPa to about -550 MPa, about -550 MPa to about -300 MPa, about -550 MPa to about -350 MPa, about -550 MPa to about -400 MPa, About -550 MPa to about -450 MPa, about -550 MPa to about -500 MPa, about -500 MPa to about -300 MPa, about -500 MPa to about -350 MPa, about -500 MPa to about -400 MPa, or about -500 MPa to about -450 MPa.

[0036] The doped diamondoid carbon film may have a density greater than 150 GPa, such as 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. It may have an elastic modulus of GPa. For example, the doped diamondoid carbon film may have a density greater than 150 GPa to about 400 GPa, greater than 150 GPa to about 375 GPa, greater than 150 GPa to about 350 GPa, greater than 150 GPa to about 300 GPa, greater than 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.

[0037] In some embodiments, the doped diamondoid carbon film is the underlying layer for an extreme ultraviolet ("EUV") lithography process. In some examples, the nitrogen-doped diamondoid carbon film is an underlayer for an EUV lithography process and has an sp ³ hybridized carbon atom content of about 40% to about 90%, based on the total amount of carbon atoms in the film, greater than 2 g/cc to It has a density of about 12 g/cc, and an elastic modulus of greater than or equal to about 150 GPa to about 400 GPa.

[0038] FIG. 1A shows a schematic diagram of a substrate processing system 132 that can be used to perform doped diamondoid carbon film deposition according to embodiments described herein. The substrate processing system 132 includes a process chamber 100 coupled to a gas panel 130 and a controller 110 . The process chamber 100 includes an upper wall 124 , a side wall 101 , and a lower wall 122 , which generally define a processing volume 126 . The processing volume 126 of the process chamber 100 is provided with a substrate support assembly 146 . The substrate support assembly 146 generally includes an electrostatic chuck 150 supported by a stem 160 . Electrostatic chuck 150 may typically be made of aluminum, ceramics, and other suitable materials. The electrostatic chuck 150 may be vertically moved inside the process chamber 100 using a displacement mechanism (not shown).

[0039] A vacuum pump 102 is coupled to a port formed at the bottom of the process chamber 100. A vacuum pump 102 is used to maintain a desired gas pressure in the process chamber 100 . The vacuum pump 102 also evacuates the post-processing gases and by-products of the process from the process chamber 100 .

[0040] The substrate processing system 132 may include additional equipment for controlling the chamber pressure, such as valves (eg, valves positioned between the process chamber 100 and the vacuum pump 102 to control the chamber pressure). throttle valves and shut-off valves) may additionally be included.

[0041] On top of the process chamber 100 above the electrostatic chuck 150, a gas distribution assembly 120 having a plurality of openings 128 is disposed. The openings 128 of the gas distribution assembly 120 are used to introduce process gases (eg, deposition gas, dilution gas, carrier gas, purge gas) into the process chamber 100 . Apertures 128 may have different sizes, numbers, distributions, shapes, designs and diameters to facilitate the flow of various processing gases for different process requirements. The gas distribution assembly 120 is connected to a gas panel 130 that allows various gases to be supplied to the processing volume 126 during processing. A plasma is formed from the processing gas mixture exiting the gas distribution assembly 120 to enhance thermal decomposition of the processing gases resulting in the deposition of material on the surface 191 of the substrate 190 .

[0042] The gas distribution assembly 120 and electrostatic chuck 150 may form a pair of spaced apart electrodes in the processing volume 126. One or more RF power sources 140 provide a bias potential to the gas distribution assembly 120 through an optional matching network 138 to create a plasma between the gas distribution assembly 120 and the electrostatic chuck 150. facilitates Alternatively, RF power source 140 and matching network 138 are coupled to gas distribution assembly 120 or electrostatic chuck 150, or to both gas distribution assembly 120 and electrostatic chuck 150, or It may be coupled to an antenna (not shown) disposed outside of the process chamber 100 . In one or more embodiments, RF power supply 140 may generate power at a frequency of about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz. . In some examples, RF power supply 140 may provide between about 100 Watts and about 3,000 Watts of power at a frequency between about 50 kHz and about 13.6 MHz. In other examples, the RF power supply 140 may provide between about 500 Watts and about 1,800 Watts of power at a frequency between about 50 kHz and about 13.6 MHz.

[0043] The controller 110 includes a central processing unit (CPU) 112, memory 116 and support circuitry 114 used to control the process sequence and regulate the gas flows from the gas panel 130. do. CPU 112 may be any type of general purpose computer processor that may be used in an industrial setting. Software routines may be stored in memory (such as random access memory, read only memory, floppy or hard disk drive, or other form of digital storage). 116) can be stored. Support circuitry 114 is typically coupled to CPU 112 and may include cache, clock circuits, input/output systems, power supplies, and the like. Bi-directional communications between the controller 110 and the various components of the substrate processing system 132 are handled via a number of signal cables, collectively referred to as signal buses 118, of which A portion is shown in Figure 1A.

[0044] FIG. 1B shows a schematic cross-sectional view of another substrate processing system 180 that may be used in the practice of embodiments described herein. The substrate processing system 180 is configured to flow processing gases from the gas panel 130 through the sidewall 101 and across the surface 191 of the substrate 190 . and is similar to the substrate processing system 132 of FIG. 1A. Also, the gas distribution assembly 120 shown in FIG. 1A is replaced with an electrode 182. Electrodes 182 may be configured to generate secondary electrons. In one or more embodiments, electrode 182 is a silicon-containing electrode.

[0045] FIG. 2 shows a schematic cross-sectional view of a substrate support assembly 146 used in the processing systems of FIGS. 1A and 1B, which may be used in the practice of embodiments described herein. Referring to FIG. 2 , the electrostatic chuck 150 may include a heater element 170 suitable for controlling the temperature of a substrate 190 supported on an upper surface 192 of the electrostatic chuck 150 . can The heater element 170 may be embedded within the electrostatic chuck 150 . The electrostatic chuck 150 may be resistively heated by applying current to the heater element 170 from the heater power source 106 . The heater power source 106 may be coupled through an RF filter 216. An RF filter 216 may be used to protect the heater power source 106 from RF energy. Heater element 170 may be made of nickel-chromium wire encapsulated with a nickel-iron-chromium alloy (eg, ^INCOLOY® alloy) sheath tube. The current supplied from the heater power source 106 is regulated by the controller 110 to control the heat generated by the heater element 170, thereby substantially dissipating the substrate 190 and the electrostatic chuck 150 during film deposition. Keep at a constant temperature. The supplied current may be adjusted to selectively control the temperature of the electrostatic chuck 150 between about -50°C and about 600°C.

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

[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 coupled to a chucking power source 212 and, when energized, electrostatically clamps the substrate 190 to the upper surface 192 of the electrostatic chuck 150.

[0048] The chucking electrode 210 may consist of a monopolar or bipolar electrode, or may have other suitable arrangements. The chucking electrode 210 may be coupled via an RF filter 214 to a chucking power source 212, which electrostatically holds the substrate 190 on the top surface 192 of the electrostatic chuck 150. Provides direct current (DC) power for fixing. The RF filter 214 prevents RF power used to form plasma within the process chamber 100 from damaging electrical equipment or causing electrical hazards outside the chamber. The electrostatic chuck 150 may be made of a ceramic material such as aluminum nitride or aluminum oxide (eg, alumina). Alternatively, the electrostatic chuck 150 may be made of a polymer such as polyimide, polyetheretherketone (PEEK), polyaryletherketone (PAEK), or the like.

[0049] The power application system 220 is coupled to the substrate support assembly 146. The power application system 220 may include a heater power source 106 , a chucking power source 212 , a first radio frequency (RF) power source 230 and a second RF power source 240 . The power application system 220 further includes a controller 110 and a sensor device 250 in communication with both the controller 110 and the first RF power supply 230 and the second RF power supply 240. can include The controller 110 can also be used to control a plasma from a processing gas by applying RF power from the first RF power source 230 and the second RF power source 240 to deposit a material layer on the substrate 190. there is.

[0050] As described above, the electrostatic chuck 150 includes a chucking electrode 210 that can function to chuck the substrate 190 in one aspect while also functioning as a first RF electrode. The electrostatic chuck 150 may also include a second RF electrode 260 , and together with the chucking electrode 210 , RF power may be applied to tune the plasma. The first RF power source 230 can be coupled to the second RF electrode 260 while the second RF power source 240 can be coupled to the chucking electrode 210 . A first matching network and a second matching network may be provided to 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 conductive material as shown. Alternatively, the second RF electrode 260 may be a mesh of conductive material.

[0051] The first RF power source 230 and the second RF power source 240 may generate power at the same frequency or different frequencies. In one or more embodiments, one or both of the first RF power supply 230 and the second RF power supply 240 may be configured to operate 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 supply 230 can generate power at a frequency of 13.56 MHz and the second RF power supply 240 can generate power at a frequency of 2 MHz, or vice versa. possible. The RF power from one or both of the first RF power supply 230 and the second RF power supply 240 can be varied to tune the plasma. For example, sensor device 250 can be used to monitor RF energy from one or both of first RF power source 230 and second RF power source 240 . Data from the sensor device 250 may be passed to the controller 110, which may be used to change the power applied by the first RF power source 230 and the second RF power source 240. can

[0052] In one or more embodiments, the electrostatic chuck 150 may have the chucking electrode 210 and the RF electrode separated from each other, a first RF bias may be applied to the RF electrode 260, and a second RF bias may be applied to the RF electrode 260. may be applied to the chucking electrode 210 . In one or more examples, the first RF bias is provided with a power of about 10 Watts to about 3,000 Watts at a frequency of about 350 KHz to about 100 MHz, and the second RF bias is provided with a power of about 10 Watts at a frequency of about 350 KHz to about 100 MHz. Watts to about 3,000 Watts of power. In other examples, a first RF bias is provided with a power of about 2,500 Watts to about 3,000 Watts at a frequency of about 13.56 MHz and a second RF bias is provided with a power of about 800 Watts to about 1,200 Watts at a frequency of about 2 MHz. do.

[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 otherwise introduced into the processing volume of a process chamber, such as a PE-CVD chamber. The hydrocarbon compound and dopant compound may be independently flowed or introduced into the processing volume. In some examples, one or more substrates are positioned on an electrostatic chuck in a process chamber. In the electrostatic chuck, the chucking electrode and the RF electrode may be separated from each other. A plasma may be ignited or otherwise generated at or near the substrate (eg, at substrate level) by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode. A doped diamondoid carbon film is deposited or otherwise formed on the substrate. In some embodiments, a patterned photoresist layer may be deposited or otherwise formed over the doped diamond-like carbon film, the doped diamond-like carbon film etched or otherwise formed in a pattern corresponding to the patterned photoresist layer; A pattern is etched or otherwise formed into the substrate.

[0054] In general, the following exemplary deposition process parameters may be used to form a doped diamondoid carbon film. The substrate temperature may range from about 50°C to about 350°C (eg, from about 10°C to about 100°C; or from about 10°C to about 50°C). The chamber pressure may range from a pressure of about 0.5 mTorr to about 10 Torr (eg, about 2 mTorr to about 50 mTorr; or about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may be about 10 sccm to about 1,000 sccm (eg, about 100 sccm to about 200 sccm or about 150 sccm to about 200 sccm). The flow rate of the dopant may be between about 1 sccm and about 500 sccm (eg, between about 10 sccm and about 150 sccm or between about 20 sccm and about 100 sccm). The flow rate of the dilution gas or purge gas may be between about 50 sccm and about 50,000 sccm (eg, between about 50 sccm and about 500 sccm; or between about 50 sccm and about 100 sccm).

[0055] The doped diamondoid carbon film may be deposited to a thickness of about 5 Å to about 20,000 Å (eg, about 300 Å to about 5,000 Å; about 2,000 Å to about 3,000 Å, or about 5 Å to about 200 Å). The process parameters shown in Table 1 provide examples of process parameters for a 300 mm substrate in a deposition chamber commercially available from Applied Materials, Inc. of Santa Clara, Calif.

[0056] The doped diamondoid carbon film may have a refractive index or n-value (n (at 633 nm)) greater than 2.0, for example from about 2.1 to about 3.0, such as 2.3. The doped diamondoid carbon film may have an extinction coefficient or k-value (K (at 633 nm)) greater than 0.1, for example from about 0.2 to about 0.3, such as 0.25. The doped diamondoid carbon film is less than -100 MPa, such as about -1,000 MPa to about -100 MPa, about -600 MPa to about -300 MPa, about -600 MPa to about -500 MPa, such as about -550 MPa. It may have a stress (MPa). The doped diamondoid carbon film has a density greater than 2 g/cc, for example greater than about 2.5 g/cc, greater than about 2.8 g/cc, such as from about 3 g/cc to about 3 g/cc to about 12 g/cc ( g/cc). The doped diamondoid carbon film can have a modulus of elasticity (GPa) greater than 150 GPa, such as from about 200 GPa to about 400 GPa.

[0057] Figure 3 shows a flow diagram of a method 300 for forming a doped diamondoid carbon film on a film stack disposed on a substrate in accordance with one embodiment of the present disclosure. A doped diamondoid carbon film formed on the film stack can be used as a hardmask for forming, for example, stair-like structures in the film stack. 4A and 4B are schematic cross-sectional views illustrating a sequence for forming a doped diamond-like carbon film on a film stack disposed on a substrate according to method 300. Although method 300 is described below with reference to a hardmask layer that can be formed on a film stack that is used to fabricate stepped structures for three-dimensional semiconductor devices in the film stack, method 300 can also be used in other ways. It can be advantageously used in device manufacturing applications. It should also be understood that the operations shown in FIG. 3 may be performed in a different order and/or concurrently than the order shown in FIG. 3 .

[0058] Method 300, at operation 310, positions a substrate, such as substrate 402 shown in FIG. 4A, within a processing volume of a process chamber, such as process chamber 100 shown in FIG. 1A or 1B. It starts by doing The substrate 402 may be the substrate 190 shown in FIGS. 1A, 1B and 2 . Substrate 402 may be positioned on top surface 192 of an electrostatic chuck, such as electrostatic chuck 150 . Substrate 402 may be a silicon-based material, or any suitable insulating or conductive material as desired, which may be used to form structure 400, such as stepped structures, in film stack 404. 402 has a film stack 404 disposed on it.

[0059] As shown in the embodiment shown in FIG. 4A, the substrate 402 may have a substantially planar surface, an uneven surface, or a substantially planar surface on which structures are formed. . A film stack 404 is formed on a substrate 402 . In one or more embodiments, film stack 404 may be used to form a gate structure, contact structure or interconnect structure in a front end or back end process. Method 300 may be performed on film stack 404 to form stepped structures in film stack 404 used in memory structures, such as NAND structures. In one or more embodiments, the substrate 402 is crystalline silicon (eg, Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, Doped and undoped silicon substrates and patterned and unpatterned substrates silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire and It can be the same material. The substrate 402 can have rectangular or square panels as well as substrates of various dimensions, such as 200 mm, 300 mm, 450 mm, or other diameters. Unless otherwise stated, the embodiments and examples described herein are practiced on substrates having a 200 mm diameter, 300 mm diameter or 450 mm diameter. In embodiments where an SOI structure is used for substrate 402, substrate 402 may include a buried dielectric layer disposed on a silicon crystalline substrate. In one or more embodiments presented herein, substrate 402 may be a crystalline silicon substrate.

[0060] In one or more embodiments, the film stack 404 disposed on the substrate 402 may have multiple vertically stacked layers. The film stack 404 includes a first layer (shown as 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n ) and a second layer 408b ₁ , 408b ₂ , 408b ₃ that are iteratively formed on the film stack 404 . , ..., shown as 408b _n ). Pairs are formed repeatedly until the desired number of pairs of first and second layers is reached, the first layer (shown as 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n ) and the second layer ( 408b ₁ , 408b ₂ , 408b ₃ , …, shown as 408b _n ) alternately.

[0061] The film stack 404 may be part of a semiconductor chip such as a three-dimensional memory chip. Three repeating layers of first layers (shown as 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n ) and second layers (shown as 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n ) 4A and 4B, it is noted that any desired number of repeating pairs of first and second layers may be used as desired.

[0062] In one or more embodiments, the film stack 404 may be used to form multiple gate structures for a three-dimensional memory chip. The first layers 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n formed in the film stack 404 may be a first dielectric layer, and the second layers 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n ) may be the second dielectric layer. A suitable dielectric layer that may be used to form the first layers 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n and the second layers 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n These include, among others, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, titanium nitride, composites of oxides and nitrides, at least one oxide layer interspersed with a nitride layer, and combinations thereof. In one or more embodiments, the dielectric layers may be a high-k material with a dielectric constant greater than 4. Suitable examples of high-k materials are 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, among others. , aluminum doped hafnium dioxide, bismuth strontium titanium (BST) and platinum zirconium titanium (PZT), dopants thereof, or any combination thereof.

[0063] In one or more examples, the first layers 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n are silicon oxide layers, and the second layers 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n ) are silicon nitride layers or polysilicon layers disposed on the first layers 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n . In one or more embodiments, the thickness of the first layers 408a ₁ , 408a ₂ , 408a ₃ , ..., 408a _n may be controlled between about 50 Å and about 1000 Å, such as about 500 Å, and each The thickness of the two layers 408b ₁ , 408b ₂ , 408b ₃ , ..., 408b _n may be controlled to be about 50 Å to about 1,000 Å, such as about 500 Å. The film stack 404 may have a total thickness of about 100 Å to about 2,000 Å. In one or more embodiments, the total thickness of the film stack 404 is between about 3 microns and about 10 microns, and may vary as technology advances.

[0064] It is noted that the doped diamondoid carbon film may be formed on any surfaces or any portion of the substrate 402 with or without the film stack 404 present on the substrate 402.

[0065] In operation 320, a chucking voltage is applied to the electrostatic chuck and the substrate 402 is clamped or otherwise placed in the electrostatic chuck. In one or more embodiments, when the substrate 402 is positioned on the top surface 192 of the electrostatic chuck 150, the top surface 192 provides support for the substrate 402 during processing and the substrate 402 ) to clamp. The electrostatic chuck 150 closely plans the substrate 402 to the top surface 192, preventing backside deposition. An electrical bias is provided to the substrate 402 through the chucking electrode 210 . The chucking electrode 210 may be in electronic communication with a chucking power supply 212 that supplies a biasing voltage to the chucking electrode 210 . In one or more embodiments, the chucking voltage is between about 10 volts and about 3,000 volts, between about 100 volts and about 2,000 volts, or between about 200 volts and about 1,000 volts.

[0066] During operation 320, several process parameters may be adjusted according to the process. In one embodiment suitable for processing 300 mm substrates, the process pressure in the processing volume will be maintained between about 0.1 mTorr and about 10 Torr (eg, between about 2 mTorr and about 50 mTorr; or between about 5 mTorr and about 20 mTorr). can In some embodiments suitable for processing a 300 mm substrate, the processing temperature and/or substrate temperature is between about -50°C and about 350°C (eg, between about 0°C and about 50°C; or between about 10°C and about 20°C). ) can be maintained.

[0067] In one or more embodiments, a constant chucking voltage is applied to the substrate 402. In some embodiments, a chucking voltage may be pulsed to the electrostatic chuck 150 . In other embodiments, a backside gas may be applied to the substrate 402 while applying a chucking voltage to control the temperature of the substrate. Backside gases may include, but are not limited to, helium, argon, neon, nitrogen (N ₂ ), hydrogen (H ₂ ), or any combination thereof.

[0068] In operation 330, a plasma is created at the substrate, eg, adjacent to the substrate or near the substrate level, by applying a first RF bias to the electrostatic chuck. Plasma generated at the substrate may be generated in a plasma region between the substrate and the electrostatic chuck. The first RF bias is between about 10 Watts and about 10 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). It may be about 3,000 watts. In one or more embodiments, the first RF bias is provided with a power of about 2,500 Watts to about 3,000 Watts at a frequency of about 13.56 MHz. In one or more embodiments, the first RF bias is provided to the electrostatic chuck 150 through the second RF electrode 260 . The second RF electrode 260 may be in electronic communication with the first RF power supply 230 that supplies a biasing voltage to the second RF electrode 260 . In one or more embodiments, the bias power is between about 10 Watts and about 3,000 Watts, between about 2,000 Watts and about 3,000 Watts, or between about 2,500 Watts and about 3,000 Watts. The first RF power source 230 provides 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). can create

[0069] In one or more embodiments, operation 330 further includes applying a second RF bias to the electrostatic chuck. The second RF bias is about 10 Watts to about 100 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). It may be about 3,000 watts. In some examples, the second RF bias is provided with a power of about 800 Watts to about 1,200 Watts at a frequency of about 2 MHz. In other examples, the second RF bias is provided to the substrate 402 via the chucking electrode 210 . The chucking electrode 210 may be in electronic communication with the second RF power source 240 that supplies a biasing voltage to the chucking electrode 210 . In one or more examples, 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 provides 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). can create In one or more embodiments, the chucking voltage supplied in operation 320 is maintained during operation 330 .

[0070] In some embodiments, during operation 330, a first RF bias is provided to the substrate 402 via the chucking electrode 210 and a second RF bias is provided to the substrate via the second RF electrode 260. (402). In one or more examples, the first RF bias is about 2,500 Watts (about 13.56 MHz) and the second RF bias is about 1,000 Watts (about 2 MHz).

[0071] During operation 340, a deposition gas is flowed into the processing volume 126 to form a doped diamondoid carbon film on the film stack. A deposition gas may flow into the processing volume 126 from the gas panel 130 through the gas distribution assembly 120 or through the sidewall 101 . The deposition gas contains one or more hydrocarbon compounds and one or more dopant compounds. The hydrocarbon compound may be or include one, two, or more than one hydrocarbon compounds in any state of matter. Similarly, the dopant compound may be or include one, two, or more than one dopant compounds in any state of matter. The hydrocarbon and/or dopant compounds can be any liquid or gas, however, to simplify the hardware required for material metering, control, and delivery to the processing volume, some advantages arise when any of the precursors are vapor at room temperature. can be realized

[0072] The deposition gas may further include an inert gas, a diluent gas, a nitrogen-containing gas, an etchant gas, or any combination thereof. In one or more embodiments, the chucking voltage supplied during operation 320 is maintained during operation 340 . In some embodiments, the process conditions established during operation 320 and the plasma formed during operation 330 are maintained during operation 340 .

[0073] 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 examples, the hydrocarbon compound has the general formula C _x H _y , where x ranges from 1 to about 20 and y ranges from 1 to about 20. Suitable hydrocarbon compounds are, for example, C ₂ H ₂ , C ₃ H ₆ , CH ₄ , C ₄ H ₈ , 1,3-dimethyladamantane, bicyclo[2.2.1]hepta 2,5-diene (2, 5-norbornadiene), adamantine (C ₁₀ H ₁₆ ), norbornene (C ₇ H ₁₀ ), or any combination thereof. In one or more examples, ethyne is utilized due to the formation of a more stable intermediate species, which allows for more surface mobility.

[0074] The hydrocarbon compound can be or include one or more alkanes (eg, C _n H _2n+2 , where n is 1 to 20). Suitable hydrocarbon compounds include, for example, alkanes such as methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), and their isomers isobutane, 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-dimethyl butane, or any combination thereof.

[0075] The hydrocarbon compound can be or include one or more alkenes (eg, 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, and the like, dienes such as butadiene, isoprene, pentadiene, hexadiene, or any combination thereof. Additional suitable hydrocarbons include, for example, halogenated alkenes, such as monofluoroethylene, difluoroethylenes, trifluoroethylene, tetrafluoroethylene, monochloroethylene, dichloroethylenes, trichloroethylene, tetrachlorethylene. , or any combination thereof.

[0076] The hydrocarbon compound can be or include one or more alkynes (eg, C _n H _2n-2 , where n is 1 to 20). Suitable hydrocarbon compounds include, for example, alkynes such as ethyne or acetylene (C ₂ H ₂ ), propyne (C ₃ H ₄ ), butylene (C ₄ H ₈ ), vinylacetylene, or any combination thereof. include

[0077] The hydrocarbon compound is one or more aromatic hydrocarbon compounds such as benzene, styrene, toluene, xylene, ethylbenzene, acetophenone, methyl benzoate, phenyl acetate, phenol, cresol, furan, etc., alpha-terpinene, cymene, or 1,1,3,3-tetramethylbutylbenzene, t-butylether, t-butylethylene, methyl-methacrylate, and t-butylfurfurylether, formulas C ₃ H ₂ and C ₅ H ₄ may be or include compounds having, halogenated aromatic compounds including monofluorobenzene, difluorobenzenes, tetrafluorobenzenes, hexafluorobenzene, or any combination thereof.

[0078] Exemplary tungsten precursors are tungsten hexafluoride, tungsten hexachloride, tungsten hexacarbonyl, bis(cyclopentadienyl) tungsten dihydride, bis(tertbutylimino) bis(dimethylamino)tungsten, or these may be or include any combination of Exemplary molybdenum precursors may be or include molybdenum pentachloride, molybdenum hexacarbonyl, bis(cyclopentadienyl)molybdenum dichloride, or any combination thereof. Exemplary cobalt precursors may be or include one or more of cobalt carbonyl compounds, cobalt amidinate compounds, cobaltocene compounds, cobalt dienyl compounds, complexes thereof, or any combination thereof. there is. Exemplary cobalt precursors include cyclopentadienyl dicarbonyl cobalt (CpCo(CO) ₂ ), dicobalt hexacarbonyl butylacetylene (CCTBA), (cyclopentadienyl) (cyclohexadienyl) cobalt, (cyclobutadienyl) Nyl) (cyclopentadienyl) cobalt, bis(cyclopentadienyl) cobalt, bis(methylcyclopentadienyl) cobalt, bis(ethylcyclopentadienyl) cobalt, cyclopentadienyl (1,3-hexadie may be or include one or more of (nyl) cobalt, (cyclopentadienyl)(5-methylcyclopentadienyl) cobalt and bis(ethylene)(pentamethylcyclopentadienyl) cobalt, or any combination thereof. .

[0079] Exemplary nickel precursors are bis(cyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel, allyl(cyclopentadienyl)nickel, or any of these It may be a combination of or may include them. Exemplary vanadium precursors may be or include vanadium pentachloride, bis(cyclopentadienyl) vanadium, or any combination thereof. Exemplary zirconium precursors may be or include zirconium tetrachloride, bis(cyclopentadienyl)zirconium dihydride, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, or any combination thereof. there is.

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

[0081] Exemplary tantalum-containing compounds include pentakis(ethylmethylamino) tantalum (PEMAT), pentakis(diethylamino)tantalum (PDEAT), pentakis(dimethylamino)tantalum (PDMAT), and PEMAT, PDEAT , and any derivatives of PDMAT. Exemplary tantalum-containing compounds also include tert-butylimino tris(diethylamino)tantalum (TBTDET), tert-butylimino tris(dimethylamino)tantalum (TBTDMT), bis(cyclopentadienyl) tantalum trihydride fluoride, bis(methylcyclopentadienyl) tantalum trihydride, and tantalum hydride, TaX ₅ , where X is fluorine (F), bromine (Br), or chlorine (Cl), and/or derivatives thereof may or may include it. Exemplary nitrogen-containing compounds include nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and derivatives thereof.

[0082] Exemplary silicon precursors include silane, disilane, trisilane, tetrasilane, pentasilane, hexasilane, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorosilane, substituted silanes, may be or include plasma derivatives thereof, or any combination thereof. Exemplary boron precursors may be or include diborane, triborane, tetraborane, triethylborane (Et ₃ B), dimethylamino borane, or any combination thereof.

[0083] The nitrogen-containing compound may be or include one or more of pyridine compounds, aliphatic amines, amines, nitriles, and similar compounds. Exemplary nitrogen-containing compounds may be or include nitrogen gas, atomic nitrogen, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, pyridine, and derivatives thereof. can do. Exemplary phosphorus precursors may be or include phosphine, triphenylphosphine, trimethylphosphine, triethylphosphine, or any combination thereof. Exemplary germanium precursors may be or include germane, tetramethyl germanium, triethyl germanium hydride, triphenyl germanium hydride, or any combination thereof.

[0084] In one or more embodiments, the deposition gas further contains one or more diluent 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 (H ₂ ), nitrogen (N ₂ ), ammonia (NH ₃ ) , nitric oxide (NO), or any combination thereof, may be co-flowed or otherwise supplied into the processing volume 126 along with, inter alia, the deposition gas. Argon, helium, and/or nitrogen may be used to control the density and deposition rate of the doped diamondoid carbon film. In some cases, the addition of N ₂ and/or NH ₃ can be used to control the hydrogen ratio of the doped diamondoid carbon film, as discussed below. Alternatively, diluent gases may not be used during deposition.

[0085] In some embodiments, the deposition gas further contains an etchant gas. Suitable etchant gases may be or may be chlorine (Cl ₂ ), fluorine (F ₂ ), hydrogen fluoride (HF), carbon tetrafluoride (CF ₄ ), nitrogen trifluoride (NF ₃ ), or any combination thereof. can include Without being bound by theory, it is believed that the etchant gases selectively etch sp ² hybridized carbon atoms from the film, thereby increasing the fraction of sp ³ hybridized carbon atoms in the film, which increases the etch selectivity of the film.

[0086] In one or more embodiments, after the doped diamondoid carbon film 412 is formed on the substrate during operation 340, the doped diamondoid carbon film 412 is exposed to hydrogen radicals. In some embodiments, the doped diamondoid carbon film is exposed to hydrogen radicals during the deposition process of operation 340 . In other embodiments, hydrogen radicals are formed in the RPS and delivered to the processing region. Without being bound by theory, exposing a doped diamondoid carbon film to hydrogen radicals results in selective etching of the sp ² hybridized carbon atoms, thereby increasing the sp ³ hybridized carbon atom fraction of the film, and thus selective etching. It is believed to increase rain.

[0087] In operation 350, after the doped diamondoid carbon film 412 is formed on the substrate, the substrate is de-chucking. During operation 350, the chucking voltage is turned off. Reactive gases are turned off and optionally purged from the processing chamber. In one or more embodiments, during operation 350, the RF power is reduced (eg, about 200 Watts). Optionally, controller 110 monitors the impedance change to determine if static charges are dissipated through the RF path to ground. When the substrate is unchucked from the electrostatic chuck, residual gases are purged from the processing chamber. The processing chamber is pumped down and the substrate is moved over the lift pins and transported out of the chamber.

[0088] Figure 5 shows a flow diagram of a method 500 of using a doped diamondoid carbon film, in accordance with one or more embodiments described and discussed herein. After the doped diamond-like carbon film 412 is formed on the substrate, the doped diamond-like carbon film 412 is used as a patterning mask to form a three-dimensional structure, such as a staircase. As such, it can be utilized in the etching process. Doped diamondoid carbon film 412 may be patterned using standard photoresist patterning techniques. In operation 510, a patterned photoresist (not shown) may be formed over the doped diamondoid carbon film 412. In operation 520, the doped diamondoid carbon film 412 may be etched with a pattern corresponding to the patterned photoresist layer, and then the pattern may be etched into the substrate 402 in operation 530. At operation 540 , material may be deposited within the etched portions of substrate 402 . In operation 550, the doped diamondoid carbon film 412 may 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 etch. The doped diamond-like carbon film 412 may also contain etching chemicals containing oxygen and halogens (eg, fluorine or chlorine), such as Cl ₂ /O ₂ , CF ₄ /O ₂ , Cl ₂ /O ₂ /CF ₄ can be used to remove it. The doped diamondoid carbon film 412 may be removed by a chemical mechanical polishing (CMP) process.

Prophetic examples:

[0089] The following non-limiting prophetic examples are provided to further illustrate those described herein. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the embodiments described herein. Some of the actual and predicted results are outlined in Table 2.

[0090] In one or more examples, a low stress, high density boron-doped diamondoid carbon film of the present disclosure contains about 150 sccm of acetylene, about 100 sccm of helium, and 100 sccm of diborane (90 vol% H diluted in ₂ ). The substrate is at a temperature of about 10° C., the chamber pressure is about 2,500 Watts RF (13.56 MHz) power and about 1,000 Watts (2 MHz) on the substrate pedestal (electrostatic chuck) in a CVD reactor with Ar and/or He as diluent gases. ) and maintained at about 5 mTorr.

[0091] The obtained boron-doped diamondoid carbon film has a density greater than 2 g/cc, such as 2.5 g/cc to about 3 g/cc or about 5 g/cc, and a density of -500 MPa or less, such as -550 MPa or -600 MPa. stress of MPa, and K@633 nm < 0.15. A boron-doped diamondoid carbon film has a greater etch selectivity than currently available amorphous carbon films or other conventional undoped diamondoid carbon films.

[0092] In other examples, a low-stress, high-density tungsten-doped diamond-like carbon film of the present disclosure is prepared by flowing about 150 sccm of acetylene, about 100 sccm of helium, and 20 sccm of tungsten hexafluoride as deposition gases. It became. The substrate is at a temperature of about 10° C. and the chamber pressure is about 2,500 Watts RF (13.56 MHz) power and about 1,000 Watts (2 MHz) was maintained at about 5 mTorr.

[0093] The obtained tungsten-doped diamondoid carbon film has a density greater than 3 g/cc, such as 3.5 g/cc to about 10 g/cc or about 12 g/cc, and a density of -550 MPa or less, such as -600 MPa or -650 stress of MPa, and K@633 nm < 0.15. A tungsten-doped diamondoid carbon film has a greater etch selectivity than currently available amorphous carbon films or other conventional undoped diamondoid carbon films.

Extreme Ultraviolet (“EUV”) Patterning Methods

[0094] The bottom layer's selection is to avoid nanofailures (e.g., bridging defects) in semiconductor devices when using metal-containing photoresists in extreme ultraviolet ("EUV") patterning schemes. and spacing defects). Conventional lower layers for EUV patterning (lithography) schemes are spin on carbon (SOC) materials. However, during patterning, metals, such as tin, diffuse through SOC materials, for example, causing nanodefects in the semiconductor device. Such nanodefects act to reduce, degrade, and inhibit semiconductor performance.

[0095] On the other hand, the high-density carbon films described herein have excellent film qualities such as improved hardness and density. Such hardness and density allow the high-density carbon film to act as a stronger barrier to metal infiltration and to prevent or at least reduce nanodefects to a greater extent than conventional SOC films. In one or more embodiments, a doped diamond-like carbon film for use as an underlayer for an extreme ultraviolet ("EUV") lithography process is provided.

[0096] In one or more embodiments, a doped diamondoid carbon film for use as an underlayer for an EUV lithography process may be any film described herein. The doped diamondoid carbon film has an sp3 hybridized carbon atom content of from about 40% to about 90%, based on the total amount of carbon atoms in the doped diamondoid carbon film, greater than 2 g/cc, such as from about 2.5 g/cc to about It may have a density of 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.

[0097] In some embodiments, a doped diamond-like carbon film for use as an underlayer for an EUV lithography process has a density of about 2.5 g/cc to about 12 g/cc; and an elastic modulus of about 180 GPa to about 200 GPa. The doped diamondoid carbon film may have a density of about 3 g/cc and an elastic modulus of about 195 GPa. In other embodiments, the doped diamondoid 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 to about 0.3.

[0098] Accordingly, methods and apparatuses are provided for forming a hardmask layer that is or contains a doped diamond-like carbon film that can be used to form stepped structures for fabricating three-dimensional stacks of semiconductor devices. do. By using a doped diamond-like carbon film with the desired robust film properties and etch selectivity as a hardmask layer, improved dimensional and profile control of the resulting structures formed in the film stack can be obtained, and the electrical performance of chip devices can be improved. It can be improved in applications for three-dimensional stacking of semiconductor devices.

[0099] In summary, some of the benefits of the present disclosure are to provide a process for depositing or otherwise forming doped diamond-like carbon films on a substrate. Conventional PE-CVD hardmask films have a very low percentage of hybridized sp ³ atoms and thus low modulus and etch selectivity. In some embodiments described herein, low process pressures (less than 1 Torr) and a bottom driven plasma enable the fabrication of doped films with about 60% or more hybridized sp ³ atoms, such that the previous to improve the etch selectivity compared to hardmask films available for Additionally, some of the embodiments described herein are performed at low substrate temperatures, which allows the deposition of other dielectric films at much lower temperatures than is currently possible, thereby reducing thermal degradation currently unaddressable by CVD. Enables applications with a thermal budget. Additionally, some of the embodiments described herein can be used as an underlying layer for an EUV lithography process.

[00100] While the foregoing relates to embodiments of the present disclosure, other and additional embodiments may be devised without departing from the basic scope of the present disclosure, which scope is covered by the following claims. It is decided. All documents described herein, including any priority documents and/or test procedures, are incorporated herein by reference unless otherwise contradicted by this specification. As is apparent from the foregoing general description and specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications may be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of US law. Similarly, whenever a composition, element, or group of elements is preceded by the transition phrase "comprising," the composition, element, or recitation of elements is preceded by "consisting essentially of." It is understood that the same composition or group of elements as the transition phrases “consisting of,” “selected from the group consisting of,” or “is” and vice versa are contemplated.

[00101] Certain embodiments and features have been described using a series of upper numerical limits and lower series of numerical limits. Including combinations of any two values, e.g., a combination of any lower value and any upper value, a combination of any two lower values, and/or a combination of any two upper values, unless otherwise indicated. It should be appreciated that ranges of Certain lower limits, upper limits and ranges appear in one or more claims below.

Claims (20)

As a method of processing a substrate,
flowing a deposition gas comprising a hydrocarbon compound and a dopant compound into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck, wherein the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr; and
generating a plasma in 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 - having a stress of less than 500 MPa. The method of claim 1 , wherein the doped diamondoid carbon film has a density of about 2.5 g/cc to about 12 g/cc. 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. The method of claim 3, wherein the dopant compound is tungsten hexafluoride, tungsten hexacarbonyl, molybdenum pentachloride, cyclopentadienyl dicarbonyl cobalt, dicobalt hexacarbonyl butylacetylene (CCTBA), bis(cyclopentadienyl) cobalt, bis(methylcyclopentadienyl) nickel, vanadium pentachloride, zirconium tetrachloride, or any combination thereof. The method of claim 1 , wherein the dopant compound comprises a non-metal dopant comprising boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof. 6. The method of claim 5, wherein the dopant compound comprises disilane, diborane, triethylborane, silane, disilane, trisilane, germane, ammonia, hydrazine, phosphine, adducts thereof, or any combination thereof. How to. The method of claim 1 , wherein the doped diamondoid carbon film comprises from about 0.1 atomic percent to about 20 atomic percent of the dopant. The method of claim 1 , wherein the doped diamondoid carbon film comprises from about 50 atomic percent to about 90 atomic percent sp ³ hybridized carbon atoms. The method of claim 1, wherein the hydrocarbon compound is ethyne, 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, nitrogen (N ₂ ), hydrogen (H ₂ ), or any combination thereof. The method of claim 1 , wherein the processing volume is maintained at a pressure of about 5 mTorr to about 100 mTorr and the substrate is maintained at a temperature of about 0° C. to about 50° C. The method of claim 1 , wherein the doped diamondoid carbon film has an elastic modulus greater than 150 GPa. The method of claim 1 , wherein generating the plasma at the substrate further comprises applying a second RF bias to the electrostatic chuck. 14. The method of claim 13, wherein the electrostatic chuck has a chucking electrode and an RF electrode separate from the chucking electrode, wherein the first RF bias is applied to the RF electrode and the second RF bias is applied to the chucking electrode. , method. 14. The method of claim 13, wherein the first RF bias is provided with a power of about 10 Watts to about 3,000 Watts at a frequency of about 350 KHz to about 100 MHz, and the second RF bias is provided at a frequency of about 350 KHz to about 100 MHz. at a power of about 10 Watts to about 3,000 Watts. As a method of processing a substrate,
flowing a deposition gas comprising a hydrocarbon compound and a dopant compound into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separate from the chucking electrode, the processing the volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr; and
generating a plasma in 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 The film has a density of greater than 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 comprising about 50 atomic percent to about 90 atomic percent sp ³ hybridized comprising carbon atoms. 17. The method of claim 16, wherein the doped diamondoid carbon film has a density of about 3 g/cc to about 10 g/cc. 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. 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. As a method of processing a substrate,
flowing a deposition gas comprising a hydrocarbon compound and a dopant compound into a processing volume of a process chamber having a substrate positioned on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separate from the chucking electrode, the processing volume is maintained at a pressure of about 0.5 mTorr to about 10 Torr;
generating a plasma in 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 the membrane has a density of greater than 2 g/cc to about 12 g/cc and a stress of about -600 MPa to about -300 MPa;
forming a patterned photoresist layer over 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 into the substrate.

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