Method for manufacturing a high-density doped carbon film for hard mask 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 the present disclosure generally relate to the manufacture of integrated circuits. More particularly, the embodiments described herein provide techniques for the deposition of high density films for patterning applications.

Background Art

[0002] Description of Related Art

[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 densities. The demand for faster circuits with higher circuit densities also places corresponding demands on the materials used in the manufacture of such integrated circuits. Specifically, as the dimensions of integrated circuit components shrink to the sub-micron range, it is currently necessary to use not only conductive materials with low resistivity but also insulating materials with low dielectric constant in order to obtain appropriate electrical performance from such components.

[0003]

[0003] The demand for greater integrated circuit density also places demands on the processing sequences used in the manufacture of integrated circuit components. For example, in a processing sequence using conventional photolithography techniques, a layer of energy-sensitive resist is formed on a material layer of a laminate disposed on a substrate. This energy-sensitive resist layer is exposed to an image of a pattern to form a photoresist mask. Thereafter, an etching process is used to transfer the mask pattern to one or more material layers of the laminate. The chemical etchant used in this etching process is selected to have a higher etching selectivity for the material layer of the laminate than for the mask of the energy-sensitive resist. That is, this 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 over the resist prevents the consumption of the energy-sensitive resist before the pattern transfer is completed.

[0004]

[0004] As the pattern dimensions shrink, in order to control the pattern resolution, the thickness of the energy-sensitive resist also becomes correspondingly smaller. Such a thin resist layer may be insufficient to mask the underlying material layer during the pattern transfer process due to the 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 since it has higher resistance to chemical etchants, it facilitates pattern transfer. A hard mask material having both high etching selectivity and a high deposition rate is required. Since the critical dimension (CD) is becoming smaller, existing hard mask materials lack the desired etching selectivity compared to the underlying materials (e.g., oxides and nitrides), and in many cases, deposition is difficult.

[0005]

[0005] Therefore, in the art, there is a need for an improved hard mask layer and a method for depositing an improved hard mask layer.

SUMMARY OF THE INVENTION

[0006]

[0006] Embodiments of the present disclosure generally relate to the manufacture of integrated circuits. More particularly, the embodiments described herein provide techniques for the 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 space of a processing chamber having a substrate disposed on an electrostatic chuck, the processing space being maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating a plasma on 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 of less than 500 MPa.

[0007]

[0007] In some embodiments, a method of processing a substrate includes flowing a deposition gas comprising one or more hydrocarbon compounds and one or more dopant compounds into a processing space of a processing chamber having a substrate disposed 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 a plasma on the substrate by applying a first RF bias to the RF electrode and a second RF bias to the electrostatic chuck to deposit a doped diamond-like carbon film on the substrate. The doped diamond-like carbon film has a density greater than 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 contains about 50 atomic percent (at%) to about 90 at% of sp 3 hybrid carbon atoms.

[0008]

[0008] In other embodiments, a method of processing a substrate includes flowing a deposition gas comprising one or more hydrocarbon compounds and one or more dopant compounds into a processing space of a processing chamber having a substrate disposed 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 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, and the doped diamond-like carbon film has a density greater than 2 g / cc to about 12 g / cc and a stress of about - 500 MPa to about -It has a stress of 300 MPa. This method further includes forming a patterned photoresist layer on a 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.

[0009]

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

[0010]

[0010] To enable a more detailed understanding of the features of the present disclosure described above, a more specific description of the present disclosure, briefly summarized above, can be obtained by referring to the implementations, some of which are illustrated in the accompanying drawings. However, it should be noted that since the present disclosure may admit other equally effective embodiments, the accompanying drawings show only typical embodiments of the present disclosure and are therefore not considered to limit the scope of the present invention.

Brief Description of the Drawings

[0011]

Figure 1A

Figure 1B

Figure 2

Figure 3

Figure 4A

Figure 4B

Figure 5

[0012]

[0017] For ease of understanding, the same reference numbers are used whenever possible to refer to the same elements common to the figures. It is contemplated that the elements and features of one embodiment can be beneficially incorporated into other embodiments without further recitation.

[0013]

[0018] The embodiments provided herein relate to a doped diamond-like carbon film and a method for depositing or forming a doped diamond-like carbon film on a substrate. Specific details are presented in the following description and FIGS. 1A-5 to provide a complete understanding of the various embodiments of the present disclosure. To avoid unnecessarily obscuring the description of the various embodiments, other details regarding well-known structures and systems often associated with plasma processing and deposition of doped diamond-like carbon films are not set forth in the following disclosure.

[0014]

[0019] Many of the detailed examples, dimensions, angles, and other features shown in the drawings are merely illustrative of particular implementations. Accordingly, other implementations may have other detailed examples, components, dimensions, angles, and features without departing from the spirit or scope of the present disclosure. Additionally, further embodiments of the present disclosure are possible without some of the detailed examples described below.

[0015]

[0020] The embodiments described herein are explained below with reference to plasma enhanced chemical vapor deposition (PE-CVD) processes that can be carried out using any suitable thin film deposition system. Examples of suitable systems include DXZ® processing chambers, PRECISION5000® systems, PRODUCER® systems, PRODUCER® GT™ systems, PRODUCER® XP Precision™ systems, PRODUCER® SE™ systems, Sym3® processing chambers, and CENTURA® systems that can use Mesa™ processing chambers, all of which are available from Applied Materials Inc. located in Santa Clara, California. Other tools capable of performing PE-CVD processes can also be adapted to benefit from the embodiments described herein. Additionally, any system that enables the CVD processes described herein can be advantageously used. The description of any apparatus herein is exemplary 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 mainly utilize thick carbon films that are essentially amorphous (e.g., about 300 nm to about 1.5 microns), but their etch selectivities are no longer sufficient to meet the increasingly stringent requirements and high aspect ratio etching of future nodes. To achieve higher etch selectivities, the density and Young's modulus of the film need to be improved. One of the main challenges in achieving higher etch selectivities and improved Young's modulus is that the high compressive stress of such films results in a large wafer / substrate warpage, making them unsuitable for applications. Therefore, there is a need for carbon films having high etch selectivity and low stress (e.g., < - 500 MPa) and high density and modulus of elasticity (diamond-like) with a higher (e.g., sp 3 content and more diamond-like).

[0017]

[0022] The embodiments described herein include improvements to a method for manufacturing a doped diamond-like carbon film having high density (e.g., >2 g / cc), high elastic modulus (e.g., >150 GPa), and low stress (e.g., < - 500 MPa). The doped diamond-like carbon film produced according to the embodiments described herein is inherently amorphous and has a higher etching selectivity with a lower stress and a higher elastic modulus (e.g., >150 GPa) than current patterning films. The doped diamond-like carbon film produced according to the embodiments described herein not only has low stress but also has a high sp 3 carbon content. Generally, the deposition processes described herein are also fully compatible with current integration schemes for hard mask applications.

[0018]

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

[0019]

[0024] The dopant compound is, or can include, one or more metal dopants, one or more non-metal dopants, or a combination thereof. The dopant compound can be one or more chemical precursors used in a vapor deposition process such as CVD or ALD. The metal dopant is, or can include, one or more of tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof. Thus, the metal dopant is, or can include, one or more of a tungsten precursor, a molybdenum precursor, a cobalt precursor, a nickel precursor, a vanadium precursor, a hafnium precursor, a zirconium precursor, a tantalum precursor, or any combination thereof. Exemplary metal dopants are tungsten hexafluoride, tungsten hexacarbonyl, molybdenum pentachloride, cyclopentadienyldicarbonylcobalt, dicobalt hexacarbonylbutylacetylene (CCTBA), bis(cyclopentadienyl)cobalt, bis(methylcyclopentadienyl)nickel, vanadium pentachloride, hafnium tetrachloride, tetrakis(dimethylamino)hafnium, tetrakis(diethylamino)hafnium, zirconium tetrachloride, bis(cyclopentadienyl)zirconium dihydride, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, tantalum pentachloride, tantalum pentafluoride, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, their adducts, their derivatives, or any combination thereof. The non-metal dopant is, or can include, one or more of boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof. Thus, the non-metal dopant is, or can include, one or more of a boron precursor, a silicon precursor, a germanium precursor, a nitrogen precursor, a phosphorus precursor, or any combination thereof.Exemplary non-metallic dopants are disilane, diborane, triethylborane, silane, disilane, trisilane, germanium, ammonia, hydrazine, phosphine, addition compounds thereof, or any combination thereof, or may include these.

[0020]

[0025] The substrate and / or the processing space can be heated and maintained at an individual temperature during the deposition process. The substrate and / or the processing space can be heated to a temperature of 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, 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 the processing space can be heated to a temperature of about 50°C to about 600°C, about 50°C to about 450°C, about 50°C to about 350°C, about 50°C to about 200°C, about 50°C to about 100°C, about 50°C to about 50°C, about 50°C to about 0°C, about 0°C to about 600°C, about 0°C to about 450°C, about 0°C to about 350°C, about 0°C to about 200°C, about 0°C to about 120°C, about 0°C to about 100°C, about 0°C to about 80°C, about 0°C to about 50°C, about 0°C to about 25°C, about 10°C to about 600°C, about 10°C to about 450°C, about 10°C to about 350°C, about 10°C to about 200°C, about 10°C to about 100°C, or about 10°C to about 50°C.

[0021]

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

[0022]

[0027] The deposition gas may further include one or more dilution gases, carrier gases, and / or purge gases, such as, for example, helium, argon, xenon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof. The deposition gas may further include etchant gases such as chlorine (Cl2), carbon tetrafluoride (CF4), and / or nitrogen trifluoride (NF3) to improve the quality of the film. Plasma (e.g., capacitively coupled plasma) can be formed from either the top and bottom electrodes or the side electrodes. These electrodes may be formed from a single power supply electrode, a dual power supply electrode, or more electrodes with multiple frequencies (such as about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, and about 100 MHz, but not limited thereto), and are used in a CVD system alternatively or simultaneously with any or all of the reaction gases listed herein to deposit a thin film of diamond-like carbon used as a hard mask and / or an etch stop, or a smooth carbon film required for any other application. The high etching selectivity of the doped diamond-like carbon film is achieved by having a higher density and modulus of elasticity than the existing deposited films. Without being bound by theory, it is believed that the improvement in density and modulus of elasticity is brought about by an increase in the content of sp 3 hybrid carbon atoms in the doped diamond-like carbon film, and this increase in content can be achieved by combining low pressure and plasma power output.

[0023]

[0028] In one or more embodiments, the doped diamond-like carbon film is deposited in a processing chamber having a substrate pedestal maintained at about 10° C., with the pressure maintained at about 2 mTorr and a 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 provided through the RPS, which are 2 This leads to selective etching of the hybrid carbon atoms, thus reducing the sp 3 The fraction of hybrid carbon atoms is further increased, thereby further increasing the etch selectivity. The doped diamond-like carbon film has at least about 40 atomic % (at%), about 45 at%, about 50 at%, about 55 at%, or about 58 at% to about 60 at%, about 65 at%, about 70 at%, about 75 at%, about 80 at%, about 85 at%, about 88 at%, about 90 at%, about 92 at%, or about 95 at%, based on the total amount of carbon atoms in the doped diamond-like carbon film. 3 The concentration or proportion of hybrid carbon atoms (e.g., sp 3 For example, the doped diamond-like carbon film may have a hybrid carbon atom content of at least 40 at% to about 95 at%, about 45 at% to about 95 at%, about 50 at% to about 95 at%, about 50 at% to about 90 at%, about 50 at% to about 85 at%, about 50 at% to about 80 at%, about 50 at% to about 75 at%, about 50 at% to about 70 at%, about 50 at% to about 60 at%, about 50 at% to about 75 at%, about 50 at% to about 70 at%, about 50 at% to about 60 at%, about 50 at% to about 8 ... 5 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%. 3 The hybrid carbon atom concentration or proportion may be any number of carbon atoms.

[0025]

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

[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 more. For example, the doped diamond-like carbon film has 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, greater than 2 g / cc to 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, about 2.5 g / cc or more to about 12 g / cc, about 2.5 g / cc or more to about 10 g / cc, about 2.5 g / cc or more to about 8 g / cc, about 2.5 g / cc or more to about 7 g / cc, about 2.5 g / 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 more to about 10 g / cc, 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 a thickness of about 5 Å, about 10 Å, about 50 Å, about 100 Å, about 150 Å, about 200 Å, or about 300 Å to about 400 Å, about 500 Å, about 800 Å, about 1,000 Å, about 2,000 Å, about 3,000 Å, about 5,000 Å, about 8,000 Å, about 10,000 Å, about 15,000 Å, about 20,000 Å, or more than this. For example, the doped diamond-like carbon film may have a thickness of about 5 Å to about 20,000 Å, about 5 Å to about 10,000 Å, about 5 Å to about 5,000 Å, about 5 Å to about 3,000 Å, about 5 Å to about 2,000 Å, about 5 Å to about 1,000 Å, about 5 Å to about 500 Å, about 5 Å to about 200 Å, about 5 Å to about 100 Å, about 5 Å to about 50 Å, about 300 Å to about 20,000 Å, about 300 Å to about 10,000 Å, about 300 Å to about 5,000 Å, about 300 Å to about 3,000 Å, about 300 Å to about 2,000 Å, about 300 Å to about 1,000 Å, about 300 Å to about 500 Å, about 300 Å to about 200 Å, about 300 Å to about 100 Å, about 300 Å to about 50 Å, about 1,000 Å to about 20,000 Å, about 1,000 Å to about 10,000 Å, about 1,000 Å to about 5,000 Å, about 1,000 Å to about 3,000 Å, about 1,000 Å to about 2,000 Å, about 2,000 Å to about 20,000 Å, or about 2,000 Å to about 3,000 Å.

[0028]

[0033] The 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, the 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] The doped diamond-like carbon film may individually have an absorption coefficient or k value (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, the doped diamond-like carbon film may have an absorption coefficient or k value (k at 633 nm) greater than 0.1 to about 0.3, greater than 0.1 to about 0.25, greater than 0.1 to about 0.2, greater than 0.1 to about 0.15, about 0.2 to about 0.3, or about 0.2 to about 0.25.

[0030]

[0035] The doped diamond-like carbon film - may have a stress of less than 250 MPa, less than -275 MPa, about -300 MPa or less, about -350 MPa or less, about -400 MPa or less, about -450 MPa or less, about -500 MPa or less, about -550 MPa or less, or about -600 MPa or less. For example, the doped diamond-like carbon film may have a stress of 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 3 - 50 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 - It can have a stress of 450 MPa.

[0031]

[0036] The doped diamond-like carbon film can have a modulus of elasticity 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, the doped diamond-like carbon film can have a modulus of elasticity of 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.

[0032]

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

[0033]

[0038] Figure 1A shows a schematic diagram of a substrate processing system 132 that can be used to deposit a doped diamond-like carbon film according to the embodiments described herein. The substrate processing system 132 includes a processing chamber 100 coupled to a gas panel 130 and a controller 110. The processing chamber 100 generally includes an upper wall 124, side walls 101, and a bottom wall 122, which define a processing space 126. A substrate support assembly 146 is provided within the processing space 126 of the processing chamber 100. The substrate support assembly 146 generally includes an electrostatic chuck 150 supported by a stem 160. The electrostatic chuck 150 can typically be fabricated from aluminum, ceramic, and other suitable materials. The electrostatic chuck 150 can be moved vertically within the processing chamber 100 using a displacement mechanism (not shown).

[0034]

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

[0035]

[0040] The substrate processing system 132 may further include additional devices for controlling the chamber pressure, such as valves (e.g., throttle valves, isolation valves, etc.), positioned between the processing chamber 100 and the vacuum pump 102.

[0036]

[0041] A gas distribution assembly 120 having a plurality of apertures 128 is disposed above the electrostatic chuck 150 and at the top of the processing chamber 100. The apertures 128 of the gas distribution assembly 120 are utilized to introduce a processing gas (e.g., deposition gas, dilution gas, carrier gas, purge gas) into the processing chamber 100. The apertures 128 can have various sizes, quantities, distribution patterns, shapes, designs, and diameters to facilitate the flow of various processing gases for various processing requirements. The gas distribution assembly 120 is connected to a gas panel 130, and the gas panel 130 enables the supply of various gases to the processing space 126 during processing. Plasma is formed from the processing gas mixture exiting the gas distribution assembly 120 to enhance the thermal decomposition of the processing gas that results in the deposition of material on the surface 191 of the substrate 190.

[0037]

[0042] The gas distribution assembly 120 and the electrostatic chuck 150 can 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 supply 140 and the matching network 138 can 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 can be connected to an antenna (not shown) disposed outside the processing chamber 100. In one or more embodiments, the RF power supply 140 can generate power at a frequency of about 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz. In some embodiments, the RF power supply 140 can supply power of about 100 watts to about 3,000 watts at a frequency of about 50 kHz to about 13.6 MHz. In other embodiments, the RF power supply 140 can supply power of about 500 watts to about 1,800 watts at a frequency of about 50 kHz to about 13.6 MHz.

[0038]

[0043] The controller 110 includes a central processing unit (CPU) 112, a memory 116, and support circuitry 114, which are utilized to control processing sequences and regulate the gas flow from the gas panel 130. The CPU 112 may be any form of general-purpose computer processor that can be used in an industrial setting. Software routines may be stored in the memory 116, for example, in random access memory, read-only memory, floppy, or hard disk drives, or other forms of digital storage. The support circuitry 114 is conventionally connected to the CPU 112 and may include a cache, clock circuits, input / output systems, power supplies, and the like. Bidirectional communication between the controller 110 and the various components of the substrate processing system 132 is processed through a number of signal cables (collectively referred to as the signal bus 118, a portion of which is shown in FIG. 1A).

[0039]

[0044] FIG. 1B shows a schematic cross-sectional view of another substrate processing integration system 180 that can be used to practice the embodiments described herein. The substrate processing system 180 is similar to the substrate processing system 132 of FIG. 1A, except that it is configured to flow a processing gas from the gas panel 130, through the sidewall 101, from end to end across the surface 191 of the substrate 190. In addition, the gas distribution assembly 120 shown in FIG. 1A is replaced by an electrode 182. The electrode 182 may be configured as a secondary charge generation device. 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 FIGS. 1A and 1B that can be used in practicing the embodiments described herein. Referring to FIG. 2, the electrostatic chuck 150 can 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 can be embedded in the electrostatic chuck 150. The electrostatic chuck 150 can be resistively heated by applying a current from a heater power supply 106 to the heater element 170. The heater power supply 106 can be connected through an RF filter 216. The RF filter 216 can be used to protect the heater power supply 106 from RF energy. The heater element 170 can be made of nickel - chromium wire encapsulated within a sheath tube of nickel - iron - chromium alloy (e.g., INCOLOY (registered trademark)). The current supplied from the heater power supply 106 is adjusted by a controller 110 so as to control the heat generated by the heater element 170 and thus maintain the substrate 190 and the electrostatic chuck 150 at a substantially constant temperature during film deposition. The supplied current can be adjusted to selectively control the temperature of the electrostatic chuck 150 from about 50°C to about 600°C.

[0041]

[0046] Referring to FIG. 1, in a conventional manner, a temperature sensor 172 (such as a thermocouple) can be embedded in the electrostatic chuck 150 to monitor the temperature of the electrostatic chuck 150. The measured temperature is used by a 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 can be a mesh of a conductive material. The chucking electrode 210 can be embedded in the electrostatic chuck 150. The chucking electrode 210 is connected to a chucking power supply 212 and, 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 monopolar or bipolar electrode, or may have another suitable configuration. The chucking electrode 210 may be connected to the chucking power supply 212 through the RF filter 214, and the chucking power supply 212 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 an electrical malfunction. 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, polyether ether ketone (PEEK), or polyaryl ether ketone (PAEK).

[0044]

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

[0045]

[0050] As described above, in one aspect, the electrostatic chuck 150 includes a chucking electrode 210 that functions to chuck the substrate 190 and can also function as a first RF electrode. The electrostatic chuck 150 may also include a second RF electrode 260, which, together with the chucking electrode 210, can apply RF power to adjust 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. For each of the first RF power supply 230 and the second RF power supply 240, a first matching network and a second matching network may be provided. The second RF electrode 260 may be a solid metal plate of a conductive material as shown in the figure. 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 can 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 can individually generate power at a frequency of 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 can generate power at a frequency of 13.56 MHz, the second RF power supply 240 can generate power at a frequency of 2 MHz, or vice versa. The RF power from one or both of the first RF power supply 230 and the second RF power supply 240 can be changed to adjust the plasma. For example, the sensor device 250 can 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. The data from the sensor device 250 may be transmitted to the controller 110, and the controller 110 can be utilized to change the power applied 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 examples, the first RF bias is supplied at a frequency of about 350 KHz to about 100 MHz and 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 and a power of about 10 watts to about 3,000 watts. In other examples, the first RF bias is supplied at a frequency of about 13.56 MHz and 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 and 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 examples, one or more substrates are disposed on an electrostatic chuck within the processing chamber. The electrostatic chuck can 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 at or near the substrate (e.g., at the substrate level). A 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, and the doped diamond-like carbon film is etched or formed in a pattern corresponding to the patterned photoresist layer, and the pattern is etched or formed on the substrate.

[0049]

[0054] Generally, the following exemplary deposition process parameters may be used to form a doped diamond-like carbon film. The substrate temperature may range from about 50°C to about 350°C (e.g., from about 10°C to about 100°C, or from about 10°C to about 50°C). The chamber pressure may range from about 0.5 mTorr to about 10 Torr (e.g., from about 2 mTorr to about 50 mTorr, or from about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may be from about 10 sccm to about 1,000 sccm (e.g., from about 100 sccm to about 200 sccm, or from about 150 sccm to about 200 sccm). The flow rate of the dopant compound may be from about 1 sccm to about 1,000 sccm (e.g., from about 10 sccm to about 150 sccm, or from about 20 sccm to about 100 sccm). The flow rate of the dilution gas or purge gas may be from about 50 sccm to about 50,000 sccm (e.g., from about 50 sccm to about 500 sccm, or from about 50 sccm to about 100 sccm). TIFF0007704828000001.tif73170

[0050]

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

[0051]

[0056] The doped diamond-like carbon film may have a refractive index or n value (n at 633 nm) greater than 2.0, e.g., about 2.1 to about 3.0, 2.3, etc. The doped diamond-like carbon film may have an absorption coefficient or k value (K at 633 nm) greater than 0.1, e.g., about 0.2 to about 0.3, 0.25, etc. The doped diamond-like carbon film has a stress of less than about - 100 MPa (e.g., about - 1,000 MPa to about - 100 MPa, about- 600 MPa to approximately - 300 MPa, approximately - 600 MPa to approximately - 500 MPa, approximately - It may have (such as 550 MPa, etc.). The doped diamond-like carbon film may have a density exceeding 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.). The doped diamond-like carbon film may have an elastic modulus exceeding 150 GPa (for example, about 200 GPa to about 400 GPa).

[0052]

[0057] FIG. 3 shows a flowchart of a method 300 for forming a doped diamond-like carbon film on a film laminate disposed on a substrate according to an embodiment of the present disclosure. The doped diamond-like carbon film formed on the film laminate can be used, for example, as a hard mask for forming a stepped structure in the film laminate. FIGS. 4A and 4B are schematic cross-sectional views showing a sequence for forming a doped diamond-like carbon film on a film laminate disposed on a substrate by the method 300. The method 300 will be described later in relation to a hard mask layer that can be formed on a film laminate used for manufacturing a stepped structure in the film laminate for a three-dimensional semiconductor device, but the method 300 can also be advantageously used in other device manufacturing applications. Further, it should be understood that the steps shown in FIG. 3 can be implemented simultaneously and / or in an order different from the order shown in FIG. 3.

[0053]

[0058] Method 300 begins in step 310 by positioning a substrate (such as substrate 402 shown in FIG. 4A) within a processing chamber (such as processing chamber 100 shown in FIG. 1A or FIG. 1B). Substrate 402 can be the substrate 190 shown in FIGS. 1A, 1B, and 2. Substrate 402 can be positioned on top of an electrostatic chuck (e.g., top surface 192 of electrostatic chuck 150). Substrate 402 can be a silicon-based material, or any suitable insulating or conductive material as needed, with a film stack 404 disposed on top, and these materials can be utilized to form a structure 400 (e.g., a stepped structure) in the film stack 404.

[0054]

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

[0055]

[0060] In one or more embodiments, the film stack 404 disposed on the substrate 402 can have a number of vertically stacked layers. The film stack 404 includes a first layer (408a1, 408a2, 408a3,..., 408a n shown as), and a second layer (408b1, 408b2, 408b3,..., 408b nmay include pairs including (shown as). These pairs include a first layer (408a1, 408a2, 408a3,..., 408a n shown as) and a second layer (408b1, 408b2, 408b3,..., 408b n shown as), and the pairs of the first layer and the second layer are repeatedly formed until the target number is reached.

[0056]

[0061] The film laminate 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 shown as) are shown in three in FIGS. 4A and 4B. It should be noted that, if necessary, any target number of repeating pairs of the first layer and the second layer may be used.

[0057]

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

[0058]

[0063] In one or more embodiments, the first layers 408a1, 408a2, 408a3,..., 408a n are silicon oxide layers, and the second layers 408b1, 408b2, 408b3,..., 408b n are silicon nitride layers or polysilicon layers disposed on the first layers 408a1, 408a2, 408a3,..., 408a n In one or more embodiments, the thickness of the first layers 408a1, 408a2, 408a3,..., 408a n may be controlled to be about 50 Å to about 1,000 Å (e.g., about 500 Å), and the thickness of each of the second layers 408b1, 408b2, 408b3,..., 408b n may be controlled to be about 50 Å to about 1,000 Å (e.g., 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 about 3 microns to about 10 microns and will change as technology progresses.

[0059]

[0064] Note that a diamond-like carbon film doped on any surface or any part of the substrate 402 can be formed regardless of the presence of the film stack 404 on the substrate 402.

[0060]

[0065] In step 320, a chucking voltage is applied to the electrostatic chuck to clamp or place the substrate 402 on the electrostatic chuck. In one or more embodiments where the substrate 402 is positioned on the upper surface 192 of the electrostatic chuck 150, during processing, the upper surface 192 supports and clamps the substrate 402. The electrostatic chuck 150 brings the substrate 402 into close contact with the upper surface 192 to prevent backside deposition. An electrical bias is provided to the substrate 402 via the chucking electrode 210. The chucking electrode 210 can be in electrical communication 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 from about 10 volts to about 3,000 volts, from about 100 volts to about 2,000 volts, or from about 200 volts to about 1,000 volts.

[0061]

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

[0062]

[0067] In one or more embodiments, a constant chucking voltage is applied to the substrate 402. In some embodiments, the chucking voltage can be pulsed to the electrostatic chuck 150. In other embodiments, a backside gas can be applied to the substrate 402 while the chucking voltage is being applied to control the temperature of the substrate. The backside gas can include, but is not limited to, helium, argon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof.

[0063]

[0068] In step 330, by applying a first RF bias to the electrostatic chuck, plasma is generated on the substrate, for example, adjacent to the substrate or in the vicinity of the substrate level. The plasma generated on the substrate can be generated within the plasma region between the substrate and the electrostatic chuck. The first RF bias can have a frequency of about 350 KHz to about 100 MHz (for example, 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz) and a power of about 10 watts to about 3,000 watts. In one or more embodiments, the first RF bias is supplied to the electrostatic chuck 150 via the second RF electrode 260. The second RF electrode 260 can be electrically communicable with a first RF power supply 230 that 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 can generate power at a frequency of about 350 KHz to about 100 MHz (for example, 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 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) and can be from about 10 watts to about 3,000 watts. 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 examples, the second RF bias is supplied to the substrate 402 via the chucking electrode 210. The chucking electrode 210 can be in electrical communication with a second RF power source 240 that supplies a bias voltage to the chucking electrode 210. In one or more embodiments, the bias power is from about 10 watts to about 3,000 watts, from about 500 watts to about 1,500 watts, or from about 800 watts to about 1,200 watts. The second RF power source 240 can generate power 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 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, the first RF bias can be supplied to the substrate 402 via the chucking electrode 210, and the second RF bias can be supplied to the substrate 402 via the second RF electrode 260. In one or more embodiments, the first RF bias is about 2,500 watts (about 13.56 MHz) and the second RF bias is about 1,000 watts (about 2 MHz).

[0066]

[0071] In process 340, deposition gas is flowed into the processing space 126 to form a diamond-like carbon film doped on the film laminate. The deposition gas can be flowed 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 includes one or more hydrocarbon compounds and one or more dopant compounds. The hydrocarbon compound can be one, two, or more hydrocarbon compounds in any state of matter, or can include these. Similarly, the dopant compound can be one, two, or more hydrocarbon compounds in any state of matter, or can include these. The hydrocarbon and / or dopant compound can be either liquid or gas, but if any of the precursors are vapor at room temperature, some advantages may be realized to simplify the hardware required for material metering, control, and supply to the processing space.

[0067]

[0072] The deposition gas can further include an inert gas, a dilution gas, an etchant gas, or a combination thereof. In one or more embodiments, the chucking voltage supplied during process 320 is also maintained during process 340. In some embodiments, the processing conditions established during process 320 and the plasma formed during process 330 are also maintained during process 340.

[0068]

[0073] In one or more embodiments, the hydrocarbon compound is a gaseous hydrocarbon or a liquid hydrocarbon. The hydrocarbon can be one or more alkanes, one or more alkenes, one or more alkynes, one or more aromatics, or any combination thereof, or can include these. In some embodiments, the hydrocarbon compound has the general formula C x H y where x has a range of 1 to 20 and y has a 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), adamantane (C 10 H 16 ), norbornene (C7H10 ) or any combination thereof is included. In one or more embodiments, ethyne is utilized to form more stable intermediates that enable improved surface mobility.

[0069]

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

[0070]

[0075] The hydrocarbon compound is one or more alkenes (e.g., C n H 2n , where n is from 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] The hydrocarbon compound is one or more alkynes (e.g., C n H 2n2, n is from 1 to 20), or may include these. Suitable hydrocarbons include, for example, alkynes (e.g., acetylene (C2H4), propyne (C3H4), butylene (C4H8), vinyl acetylene, or combinations thereof).

[0072]

[0077] The hydrocarbon compound is 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 - butylfurfuryl ether, a compound having chemical formulas C3H2 and C5H4, a halogenated aromatic compound (including monofluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene, or any combination thereof), or may include these.

[0073]

[0078] Exemplary tungsten precursors can be, or can include, tungsten hexafluoride, tungsten hexachloride, tungsten hexacarbonyl, bis(cyclopentadienyl)dihydrogen tungsten, bis(tert-butylimino)bis(dimethylamino)tungsten, or any combination thereof. Exemplary molybdenum precursors can be, or can include, molybdenum pentachloride, molybdenum hexacarbonyl, bis(cyclopentadienyl)molybdenum dichloride, or any combination thereof. Exemplary cobalt precursors can be, or can include, one or more of cobalt carbonyl compounds, cobalt amidinate compounds, cobaltocene compounds, cobalt diene compounds, complexes thereof, or any combination thereof. Exemplary cobalt precursors can be, or can include, cyclopentadienyldicarbonylcobalt (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.

[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 dihydride, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, or any combination thereof, or may include these.

[0075]

[0080] Hafnium precursors are one or more hafnium cyclopentadiene compounds, one or more hafnium amino compounds, one or more hafnium alkyl compounds, one or more hafnium alkoxy compounds, their substitutes, their complexes, their addition compounds, their salts, or any combination thereof, or may include these. Exemplary hafnium precursors are bis(methylcyclopentadienyl)dimethylhafnium ((MeCp)2HfMe2), bis(methylcyclopentadienyl)methylmethoxyhafnium ((MeCp)2Hf(OMe)(Me)), bis(cyclopentadienyl)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 addition compounds, their salts, or any combination thereof, or may include these.

[0076]

[0081] Exemplary tantalum-containing compounds can be, or can include, pentakis(ethylmethylamino)tantalum (PEMAT), pentakis(diethylamino)tantalum (PDEAT), pentakis(dimethylamino)tantalum (PDMAT), and any derivatives of PEMAT, PDEAT, and PDMAT. Exemplary tantalum-containing compounds can also be 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 can include nitrogen gas, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, and derivatives thereof.

[0077]

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

[0078]

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

[0079]

[0084] In one or more embodiments, the deposition gas further includes one or more dilution gases, one or more carrier gases, and / or one or more purge gases. In particular, suitable dilution gases, carrier gases, and / or purge gases such as helium (He), argon (Ar), xenon (Xe), hydrogen (H2), nitrogen (N2), ammonia (NH3), nitric oxide (NO), or any combination thereof may be co-flowed or supplied into the processing space 126 together with the deposition gas. 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 below. Alternatively, no dilution gas may be used during deposition.

[0080]

[0085] In some embodiments, the deposition gas further includes an etchant gas. Suitable etchant gases are chlorine (Cl2), fluorine (F2), hydrogen fluoride (HF), carbon tetrafluoride (CF4), nitrogen trifluoride (NF3), or combinations thereof, or include these. Without being bound by theory, the etchant gas is sp from the film 2Selectively etch hybrid carbon atoms, and thus the sp in the film 3 It is thought that increasing the fraction of hybrid carbon atoms increases the etching selectivity of the film.

[0081]

[0086] In one or more embodiments, in step 340, after the doped diamond-like carbon film 412 is formed on the substrate, 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, hydrogen radicals are formed within the RPS and supplied to the processing region. Without being bound by theory, exposing the doped diamond-like carbon film to hydrogen radicals leads to selective etching of sp 2 hybrid carbon atoms, resulting in an increase in the fraction of sp 3 hybrid carbon atoms in the film, which is thought to enhance the etching selectivity.

[0082]

[0087] In step 350, after the doped diamond-like carbon film 412 is formed on the substrate, the substrate is unchucked. 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 (e.g., to about 200 watts) during step 350. Optionally, the controller 110 monitors the change in impedance to determine whether the static charge has dissipated to ground through the RF path. When the substrate is unchucked 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 transferred out of the chamber.

[0083]

[0088] FIG. 5 shows a flow diagram of a method 500 of using a doped diamond-like carbon film according to one or more embodiments described and explained herein. The doped diamond-like carbon film 412 can be utilized as a patterning mask for forming a three-dimensional structure (such as a stepped structure) in an etching process after being formed on a substrate. 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 into the substrate 530. In step 540, a material can be deposited into 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 a piranha solution or piranha etchant. The doped diamond-like carbon film 412 can also be removed using an etching chemical containing oxygen and a halogen (such as fluorine or chlorine) (such as Cl2 / O2, CF4 / O2, Cl2 / O2 / CF4). The doped diamond-like carbon film 412 can also be removed by a chemical mechanical polishing (CMP) process.

[0084] Logical Example:

[0089] The following non-limiting examples are provided to further illustrate the implementations described herein. However, these examples are not intended to cover all of the embodiments described herein, nor are they intended to limit the scope thereof. Some of the 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 uses about 150 sccm of acetylene, about 100 sccm of helium, and 100 sccm of diborane (diluted with 90 vol% H2) as deposition gases. The substrate is at a temperature of about 10 °C, the chamber pressure is maintained at about 5 mTorr, during which about 2,500 watts of RF (13.56 MHz) power and about 1,000 watts (2 MHz) through the substrate pedestal (electrostatic chuck) are applied to a CVD reactor having Ar and / or He as dilution gases.

[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, and - 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 a 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 film of the present disclosure was produced by flowing about 150 sccm of acetylene, about 100 sccm of helium, and 20 sccm of tungsten hexafluoride as deposition gases. The substrate is at a temperature of about 10 °C, the chamber pressure is maintained at about 5 mTorr, during which about 2,500 watts of RF (13.56 MHz) power and about 1,000 watts (2 MHz) through the substrate pedestal (electrostatic chuck) are applied to a CVD reactor having Ar and / or He as dilution 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, and - a stress of 550 MPa or less, for example, - 600 MPa or -It has a stress of 650 MPa and a K < 0.15 at 633 nm. The tungsten-doped diamond-like carbon film has a higher etching selectivity than currently available amorphous carbon films or other conventional undoped diamond-like carbon films. TIFF0007704828000002.tif94170

[0089] Extreme ultraviolet (EUV) patterning method

[0094] When using a metal-containing photoresist in an extreme ultraviolet (EUV) patterning method, the selection of the underlying layer is important to prevent nanofailures (e.g., bridge formation defects and spacing formation defects) in semiconductor devices. Conventional underlying layers for EUV patterning (lithography) methods are spin-on carbon (SOC) materials. However, during patterning, metals such as tin diffuse through, for example, SOC materials, leading to nanofailures in semiconductor devices. Such nanofailures act to lower, deteriorate, and interfere with semiconductor performance.

[0090]

[0095] On the other hand, the high-density carbon films described herein have excellent film quality (e.g., improved hardness and density). Due to such hardness and density, the high-density carbon films can act as a much stronger barrier against metal intrusion and prevent (or at least reduce) nanofailures compared to conventional SOC films. In one or more embodiments, a doped diamond-like carbon film is provided for use as an underlying layer for extreme ultraviolet (EUV) lithography processing.

[0091]

[0096] In one or more embodiments, the doped diamond-like carbon film used as an underlying layer for EUV lithography processing can be any of the films described herein. The doped diamond-like carbon film has about 40% to about 90% sp based on the total amount of carbon atoms in the doped diamond-like carbon film. 3It 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 the lower layer for EUV lithography processing 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 absorption coefficients of about 0.2 and about 0.3.

[0093]

[0098] Thus, provided are a method and an apparatus for forming a doped diamond-like carbon film that can be used for forming a stepped structure for manufacturing a three-dimensional stack of semiconductor devices or for forming a hard mask layer including the same. By using a doped diamond-like carbon film as a hard mask layer having desired strong film properties and etching selectivity, an improvement in the dimensional and profile control of the structure formed of the film stack can be obtained as a result, and the electrical performance of the chip device can be enhanced in applications for three-dimensional stacks of semiconductor devices.

[0094]

[0099] That is, due to some of the advantages of the present disclosure, a process for depositing or forming a doped diamond-like carbon film on a substrate is provided. A typical PE-CVD hard mask film has a very low proportion of hybrid sp 3 atoms and thus has low elastic modulus and etching selectivity. In some embodiments described herein, with a low process pressure (less than 1 Torr) and bottom driven plasma, more than about 60% of the hybrid sp 3It becomes possible to manufacture a doped film having atoms, which brings about an improvement in etching selectivity as compared with conventionally available hard mask films. In addition, some of the embodiments described herein are implemented at a low substrate temperature, which enables the deposition of other dielectric films at a temperature much lower than the currently possible temperature, opening up the possibility of applications with a low heat budget that could not be addressed by CVD heretofore. In addition, some of the embodiments described herein can be used as an underlying layer for EUV lithography processing.

[0095]

[0100] The above is directed to embodiments of the present disclosure, but other and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the following claims. All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, to the extent they do not conflict with the text hereof. As will be apparent from the above summary and the specific embodiments, the forms of the present disclosure have been illustrated and described, but various modifications can be made without departing from the essence and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure by the forms of the present disclosure illustrated and described. Similarly, the term "comprising" is considered synonymous with the term "including" as construed in U.S. law. Similarly, when a transitional phrase "comprising" precedes a composition, element, or group of elements, it is always assumed that the same composition or group of elements also has a transitional phrase such as "consisting essentially of", "consisting of", "selected from the group of consisting of", or "is" prior to the listing of the composition and one or more elements, and vice versa.

[0096]

[0101] Certain embodiments and features are described using a set of upper numerical limits and a set of lower numerical limits. It should be recognized that, unless otherwise indicated, ranges are contemplated that include any combination of two values (e.g., any combination of any lower value and any upper value, any combination of any two lower values, and / or any combination of any two upper values). One or more of the following claims recite certain lower limits, upper limits, and ranges.

Claims

1. A method for processing a substrate, comprising: flowing a deposition gas containing a hydrocarbon compound and a dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, wherein the processing space is maintained at a pressure of 0.5 mTorr to 10 Torr; generating plasma on the substrate by applying a first RF bias to the electrostatic chuck, and depositing a doped diamond-like carbon film on the substrate, wherein the doped diamond-like carbon film has a density greater than 2.6 g / cc and a stress less than -500 MPa, and the doped diamond-like carbon film contains 45 atomic % to 95 atomic % of sp3 hybridized carbon atoms; A method comprising the above steps.

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

3. The method according to claim 1, wherein the dopant compound contains a metal dopant including tungsten, molybdenum, cobalt, nickel, vanadium, hafnium, zirconium, tantalum, or any combination thereof.

4. The method according to claim 1, wherein the dopant compound contains tungsten hexafluoride, tungsten hexacarbonyl, molybdenum pentachloride, cyclopentadienyldicarbonylcobalt, dicobalt hexacarbonyl butylacetylene (CCTBA), bis(cyclopentadienyl)cobalt, bis(methylcyclopentadienyl)nickel, vanadium pentachloride, zirconium tetrachloride, or any combination thereof.

5. The method according to claim 1, wherein the dopant compound contains a non-metal dopant including boron, silicon, germanium, nitrogen, phosphorus, or any combination thereof.

6. The method according to claim 1, wherein the dopant compound contains disilane, diborane, triethylborane, silane, disilane, trisilane, german, ammonia, hydrazine, phosphine, addition compounds thereof, or any combination thereof.

7. The method according to claim 1, wherein the doped diamond-like carbon film contains 0.1 atomic % to 20 atomic % of dopants.

8. The method according to claim 1, wherein the doped diamond-like carbon film contains 50 atomic% to 90 atomic% of sp ３ hybrid carbon atoms.

9. The method according to claim 1, wherein the hydrocarbon compound comprises ethylene, propylene, methane, butene, 1,3-dimethyladamantane, bicyclo[2.2.1]hepta-2,5-diene, adamantane, norbornene, or any combination thereof.

10. The deposition gas further includes helium, argon, xenon, neon, nitrogen (N ２ ), hydrogen (H ２ ), or any combination thereof, the method according to claim 1.

11. The method according to claim 1, wherein the processing space is maintained at a pressure of 5 mTorr to 100 mTorr, and the substrate is maintained at a temperature of 0 °C to 50 °C.

12. The method according to claim 1, wherein the doped diamond-like carbon film has an elastic modulus exceeding 150 GPa.

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

14. The electrostatic chuck has a chucking electrode and an RF electrode separated 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. The method according to claim 13.

15. The method according to claim 13, wherein the first RF bias is supplied at a frequency of 350 kHz to 100 MHz and a power of 10 watts to 3,000 watts, and the second RF bias is supplied at a frequency of 350 kHz to 100 MHz and a power of 10 watts to 3,000 watts.

16. A method for processing a substrate, comprising: Flowing a deposition gas containing a hydrocarbon compound and a dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, wherein 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 0.5 mTorr to 10 Torr; In order to deposit a doped diamond-like carbon film on the substrate, plasma is generated on the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode, wherein the doped diamond-like carbon film has a density of more than 2.6 g / cc to 12 g / cc and a stress of -600 MPa to -300 MPa, and the doped diamond-like carbon film contains 50 atomic % to 90 atomic % of sp ３ generating plasma, including hybrid carbon atoms, A method comprising.

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

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

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

20. A method for processing a substrate, comprising: flowing a deposition gas containing a hydrocarbon compound and a dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, wherein 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 0.5 mTorr to 10 Torr; 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, wherein the doped diamond-like carbon film has a density of more than 2.6 g / cc to 12 g / cc and a stress of -600 MPa to -300 MPa; forming a patterned photoresist layer on 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; and a method comprising the steps of:

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