Method for producing a high density nitrogen doped carbon film for hard mask and other patterning applications

Abstract

FIELD OF THE DISCLOSURE Embodiments of the present disclosure generally relate to integrated circuit manufacturing. More specifically, embodiments described herein provide techniques for depositing nitrogen-doped diamond-like carbon films for patterning applications. In one or more embodiments, a method for processing a substrate includes flowing a deposition gas containing a hydrocarbon compound and a nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, and applying a first RF bias to the electrostatic chuck to generate a plasma on or above the substrate, thereby depositing a nitrogen-doped diamond-like carbon film on the substrate. The nitrogen-doped diamond-like carbon film has a density greater than 1.5 g / cc and a compressive stress of about 20 MPa to less than 600 MPa.

Description

Technical Field

[0001]

[0001] Embodiments of the present disclosure generally relate to the manufacture of integrated circuits. More specifically, the embodiments described and explained 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 density. The demand for faster circuits with higher circuit density also places corresponding requirements 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 over a material layer of a stack 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 stack. The chemical etchant used in this etching process is selected to have a higher etching selectivity for the material layers of the stack than for the energy-sensitive resist mask. That is, this chemical etchant etches one or more layers of the material stack at a much faster rate than the energy-sensitive resist. The etching selectivity for one or more material layers of the stack over the resist prevents depletion of the energy-sensitive resist before pattern transfer is complete.

[0004]

[0004] As pattern dimensions shrink, the thickness of the energy-sensitive resist also correspondingly decreases in order to control pattern resolution. Such thin resist layers can sometimes be insufficient to mask the underlying material layers during the pattern transfer process due to erosion by chemical etchants. An intermediate layer called a hard mask (e.g., silicon oxynitride, silicon carbide, or a carbon film) is often used between the energy-sensitive resist layer and the underlying material layer and facilitates pattern transfer because it has higher resistance to chemical etchants. A hard mask material having both high etching selectivity and a fast deposition rate is desired. Due to the decreasing critical dimension (CD), existing hard mask materials lack the desired etching selectivity compared to underlying materials (e.g., oxides and nitrides) and are often difficult to deposit.

[0005]

[0005] Accordingly, there is a need in the art 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 specifically, the embodiments described and explained herein provide techniques for the deposition of high density films such as nitrogen doped diamond-like carbon films for patterning applications. In one or more embodiments, a method of processing a substrate includes flowing a deposition gas containing a hydrocarbon compound and a nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, and applying a first RF bias to the electrostatic chuck to generate a plasma on or above the substrate to deposit a nitrogen doped diamond-like carbon film on the substrate. The nitrogen doped diamond-like carbon film has a density greater than 1.5 g / cc and a compressive stress of about - 20 MPa to - less than 600 MPa. In some examples, the nitrogen doped diamond-like carbon film has a density greater than 1.5 g / cc to about 2.1 g / cc and a compressive stress of about - 200 MPa to - less than 600 MPa.

[0007]

[0007] In some embodiments, a method of processing a substrate includes flowing a deposition gas containing a hydrocarbon compound and a nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode, and the processing space being maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method further includes generating a plasma above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a nitrogen doped diamond-like carbon film on the substrate. The nitrogen doped diamond-like carbon film contains about 0.1 atomic % to about 20 atomic % nitrogen and about 50 atomic % to about 90 atomic % sp 3 hybrid carbon atoms, has a density greater than 1.5 g / cc and about - 20 MPa to - less than 600 MPa compressive stress.

[0008]

[0008] In another embodiment, a method of processing a substrate includes flowing a deposition gas including a hydrocarbon compound and a nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, the electrostatic chuck having a chucking electrode and an RF electrode separated from the chucking electrode, the processing space being maintained at a pressure of about 0.5 mTorr to about 10 Torr. The method also includes generating a plasma above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a nitrogen-doped diamond-like carbon film on the substrate. The nitrogen-doped diamond-like carbon film contains about 0.1 atomic % to about 20 atomic % nitrogen and has a density greater than 1.5 g / cc and a compressive stress of about - 20 MPa to - less than 600 MPa. The method further includes forming a patterned photoresist layer on the nitrogen-doped diamond-like carbon film, etching the nitrogen-doped diamond-like carbon film in a pattern corresponding to the patterned photoresist layer, and etching the pattern into the substrate.

[0009]

[0009] In one or more embodiments, a nitrogen-doped diamond-like carbon film is provided for use as an underlayer in extreme ultraviolet (EUV) lithography processes, containing about 0.1 atomic % to about 20 atomic % nitrogen and about 50 atomic % to about 90 atomic % or about 60 atomic % to about 70 atomic % of sp 3 hybrid carbon atoms. The nitrogen-doped diamond-like carbon film has a density of greater than 1.5 g / cc to about 2.1 g / cc, about 1.55 g / cc to less than 2 g / cc, or about 1.6 g / cc to about 1.8 g / cc and a compressive stress of about - 20 MPa to - less than 600 MPa, about - 200 MPa to about - 500 MPa, or about - 250 MPa to - 400 MPa.

[0010]

[0010] To enable a detailed understanding of the features of the present disclosure described above, a more specific description of the present disclosure briefly summarized above is obtained by reference to the implementation, and some implementations are illustrated in the accompanying drawings. However, since the present disclosure may also admit other equally effective embodiments, it should be noted that 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

Embodiments for Carrying Out the Invention

[0012]

[0017] For ease of understanding, the same reference numbers are used, where possible, to denote the same elements common to the figures. The elements and features of one embodiment are considered to be beneficially incorporated into other embodiments without further recitation.

[0013]

[0018] Embodiments provided herein relate to a nitrogen-doped diamond-like carbon film and a method for depositing or forming a nitrogen-doped diamond-like carbon film on a substrate. To provide a complete understanding of the various embodiments of the present disclosure, specific details are presented in the following description and FIGS. 1A-5. 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 diamond-like carbon films are not set forth in the following disclosure.

[0014]

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

[0015]

[0020] Embodiments described herein include improvements to a method for manufacturing a nitrogen-doped diamond-like carbon film having a high density (e.g., >1.5 g / cc), a high elastic modulus (e.g., >60 GPa), and a low compressive stress (e.g., < - 500 MPa). The nitrogen-doped diamond-like carbon film produced according to the embodiments described herein is amorphous and has a higher etching selectivity with lower stress than current patterning films. The nitrogen-doped diamond-like carbon film produced according to the embodiments described herein not only has a low compressive stress but also sp 3The carbon content is high. Generally, the deposition processes described herein are also fully compatible with current integration schemes for hard mask applications.

[0016]

[0021] In one or more embodiments, the nitrogen-doped diamond-like carbon films 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 nitrogen dopant compounds. In one or more examples, a deposition gas that includes one or more hydrocarbon compounds, one or more nitrogen dopant compounds, and optionally one or more dilution gases can be flowed or introduced into the processing space of the processing chamber. The substrate is positioned on or disposed on an electrostatic chuck within the processing space, and the electrostatic chuck has a chucking electrode and an RF electrode separated from the chucking electrode. The method further includes generating a plasma on and / or above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode to deposit a nitrogen-doped diamond-like carbon film on the substrate.

[0017]

[0022] The embodiments described and explained herein are described 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 enabling 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.

[0018]

[0023] 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), adamantene (C 10 H 16 ), norbornene (C7H 10) It may be or include these derivatives, these isomers, or any combination thereof. Exemplary nitrogen dopant compounds may be or include dinitrogen (N2), atomic nitrogen, ammonia, hydrazine, methyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, azoisobutane, ethyl azide, pyridine, their derivatives, their addition compounds (abducts), or any combination thereof. The deposition gas may further include one, two, 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. In some embodiments, the deposition gas may further include an etchant gas such as chlorine (Cl2), carbon tetrafluoride (CF4), and / or nitrogen trifluoride (NF3) to improve the quality of the film.

[0019]

[0024] The substrate and / or the processing space can be heated and maintained at an independent temperature during the deposition process. The substrate and / or the processing space can be heated to a temperature of about 50°C, about 40°C, about 25°C, about 10°C, about 5°C, about 0°C, about -5°C, or about -10°C to about 15°C, about 20°C, about 23°C, about 30°C, about 50°C, about 100°C, about 150°C, about 200°C, about 300°C, about 400°C, about 500°C or about 600°C. For example, the substrate and / or 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 40°C to about 200°C, about 40°C to about 100°C, about 40°C to about 80°C, about 40°C to about 50°C, about 40°C to 25°C, about 40°C to about 10°C, about 40°C to about 0°C, about 0°C to about 600°C, about 0°C to about 450°C, about 0°C to about 350°C, about 0°C to about 200°C, about 0°C to about 120°C, about 0°C to about 100°C, about 0°C to about 80°C, about 0°C to about 50°C, about 0°C to about 25°C, about 10°C to 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.

[0020]

[0025] 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. In one or more embodiments, when generating plasma and depositing a nitrogen-doped diamond-like carbon film on a substrate maintained at a temperature of about 0 °C to about 50 °C, the processing space is held at a pressure of about 0.5 mTorr to about 10 Torr, about 1 mTorr to about 500 mTorr, or about 5 mTorr to about 100 mTorr.

[0021]

[0026] Plasma (e.g., capacitively coupled plasma) can be formed from either top and bottom electrodes or side electrodes. These electrodes can be formed from a single power supply electrode, from dual power supply electrodes, or from 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 alternatively or simultaneously used in a CVD system 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 nitrogen-doped diamond-like carbon film is achieved by having a higher density and elastic modulus than existing deposited films. Without being bound by theory, the improvement in density and elastic modulus is thought to be brought about by an increase in the content of sp 3 hybrid carbon atoms in the film, and this increase in content can be achieved by combining low pressure and plasma power.

[0022]

[0027] In one or more embodiments, the nitrogen-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 bias of about 2,500 watts (about 13.56 MHz) applied to an electrostatic chuck to generate plasma at or above the substrate level. 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.

[0023]

[0028] In one or more embodiments, hydrogen radicals are supplied through RPS, which leads to the selective etching of sp 2 hybrid carbon atoms, and thus the sp 3Increase the fraction of hybrid carbon atoms further, thereby further enhancing the etching selectivity. The nitrogen-doped diamond-like carbon film has at least 40 atomic percent (at%), about 45 at%, about 50 at%, about 55 at%, or about 58 at% to about 60 at%, about 65 at%, about 70 at%, about 75 at%, about 80 at%, about 85 at%, about 88 at%, about 90 at%, about 92 at%, or about 95 at% of sp, based on the total amount of carbon atoms in the nitrogen-doped diamond-like carbon film. 3 The concentration or ratio of hybrid carbon atoms (e.g., sp 3 hybrid carbon atom content). For example, the nitrogen-doped diamond-like carbon film has at least 40 at% to about 95 at%, about 45 at% to about 95 at%, about 50 at% to about 95 at%, about 50 at% to about 90 at%, about 50 at% to about 85 at%, about 50 at% to about 80 at%, about 50 at% to about 75 at%, about 50 at% to about 70 at%, about 50 at% to about 65 at%, about 55 at% to about 75 at%, about 55 at% to about 70 at%, about 55 at% to about 65 at%, about 55 at% to about 60 at%, about 60 at% to about 80 at%, about 60 at% to about 75 at%, about 60 at% to about 70 at%, about 60 at% to about 65 at%, about 65 at% to about 95 at%, about 65 at% to about 90 at%, about 65 at% to about 85 at%, about 65 at% to about 80 at%, about 65 at% to about 75 at%, about 65 at% to about 70 at%, about 65 at% to about 68 at%, about 75 at% to about 95 at%, about 75 at% to about 90 at%, about 75 at% to about 85 at%, about 75 at% to about 80 at%, or about 75 at% to about 78 at% of sp 3 The concentration or ratio of hybrid carbon atoms can be.

[0024]

[0029] In some embodiments, the nitrogen-doped diamond-like carbon film has less than 60 at%, for example, less than 55 at% or less than 50 at% of sp 2 The concentration or ratio of hybrid carbon atoms (e.g., sp 2It may have a (hybrid carbon atom content). The nitrogen-doped diamond-like carbon film has, based on the total amount of carbon atoms in the nitrogen-doped diamond-like carbon film, about 5 at%, about 10 at%, about 15 at%, about 20 at%, about 25 at%, about 28 at%, about 30 at%, about 32 at%, about 35 at%, about 36 at%, about 38 at%, about 40 at%, about 45 at%, about 50 at%, about 55 at%, or about 60 at% of sp 2 It may have a concentration or ratio of hybrid carbon atoms. For example, the nitrogen-doped diamond-like carbon film has, based on the total amount of carbon atoms in the nitrogen-doped diamond-like carbon film, about 5 at% to about 60 at%, about 5 at% to about 50 at%, about 5 at% to about 45 at%, about 5 at% to about 40 at%, about 5 at% to about 38 at%, about 5 at% to about 36 at%, about 5 at% to about 35 at%, about 5 at% to about 32 at%, about 5 at% to about 30 at%, about 5 at% to about 25 at%, about 5 at% to about 20 at%, about 5 at% to about 15 at%, about 5 at% to about 10 at%, about 20 at% to about 60 at%, about 20 at% to about 50 at%, about 20 at% to about 45 at%, about 20 at% to about 40 at%, about 20 at% to about 38 at%, about 20 at% to about 36 at%, about 20 at% to about 35 at%, about 20 at% to about 32 at%, about 20 at% to about 30 at%, about 20 at% to about 25 at%, about 20 at% to about 22 at%, about 30 at% to about 60 at%, about 30 at% to about 50 at%, about 30 at% to about 45 at%, about 30 at% to about 40 at%, about 30 at% to about 38 at%, about 30 at% to about 36 at%, about 30 at% to about 35 at%, about 30 at% to about 32 at%, about 32 at% to about 38 at%, about 32 at% to about 36 at%, about 32 at% to about 34 at%, about 34 at% to about 38 at%, about 34 at% to about 36 at% of sp 2 It may have a concentration or ratio of hybrid carbon atoms.

[0025]

[0030] The concentration or ratio of nitrogen in the nitrogen-doped diamond-like carbon film is 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 nitrogen-doped diamond-like carbon film.For example, the concentration or ratio of nitrogen in the nitrogen-doped diamond-like carbon film is 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%, 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 nitrogen-doped diamond-like carbon film.

[0026]

[0031] The nitrogen-doped diamond-like carbon film has a density of 1.5 g / cc (grams per cubic centimeter (cm 3)) having a density exceeding, for example, about 1.55 g / cc, about 1.6 g / cc, about 1.65 g / cc, or from about 1.68 g / cc to about 1.7 g / cc, about 1.72 g / cc, about 1.75 g / cc, about 1.78 g / cc, about 1.8 g / cc, about 1.85 g / cc, about 1.9 g / cc, about 1.95 g / cc, about 1.98 g / cc, about 2 g / cc, about 2.05 g / cc, about 2.1 g / cc, or a density exceeding this.For example, the nitrogen-doped diamond-like carbon film has a density greater than 1.5 g / cc to about 2.1 g / cc, greater than 1.5 g / cc to about 2.05 g / cc, greater than 1.5 g / cc to about 2 g / cc, greater than 1.5 g / cc to about 1.9 g / cc, greater than 1.5 g / cc to about 1.85 g / cc, greater than 1.5 g / cc to about 1.8 g / cc, greater than 1.5 g / cc to about 1.78 g / cc, greater than 1.5 g / cc to about 1.75 g / cc, greater than 1.5 g / cc to about 1.72 g / cc, greater than 1.5 g / cc to about 1.7 g / cc, greater than 1.5 g / cc to about 1.68 g / cc, greater than 1.5 g / cc to about 1.65 g / cc, greater than 1.5 g / cc to about 1.6 g / cc, about 1.6 g / cc to about 2.1 g / cc, about 1.6 g / cc to about 2.05 g / cc, about 1.6 g / cc to about 2 g / cc, about 1.6 g / cc to about 1.9 g / cc, about 1.6 g / cc to about 1.85 g / cc, about 1.6 g / cc to about 1.8 g / cc, about 1.6 g / cc to about 1.78 g / cc, about 1.6 g / cc to about 1.75 g / cc, about 1.6 g / cc to about 1.72 g / cc, about 1.6 g / cc to about 1.7 g / cc, about 1.6 g / cc to about 1.68 g / cc, about 1.6 g / cc to about 1.65 g / cc, about 1.68 g / cc to about 2.1 g / cc, about 1.68 g / cc to about 2.05 g / cc, about 1.68 g / cc to about 2 g / cc, about 1.68 g / cc to about 1.9 g / cc, about 1.68 g / cc to about 1.85 g / cc, about 1.68 g / cc to about 1.8 g / cc, about 1.68 g / cc to about 1.78 g / cc, about 1.68 g / cc to about 1.75 g / cc, about 1.68 g / cc to about 1.72 g / cc, about 1.68 g / cc to about 1.7 g / cc, about 1.7 g / cc to about 1.75 g / cc, about 1.7 g / cc to about 1.72 g / cc, less than 2 g / cc and greater than 1.55 g / cc, less than 2 g / cc and greater than 1.6 g / cc, less than 2 g / cc and greater than 1.65 g / cc, less than 2 g / cc and greater than 1.68 g / cc, less than 2 g / cc and greater than 1.7 g / cc, less than 2 g / cc and greater than 1.72 g / cc, less than 2 g / cc and greater than 1.75 g / cc, or less than 2 g / cc and greater than 1.8 g / cc.

[0027]

[0032] The nitrogen-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 600 Å, about 700 Å, about 800 Å, about 1,000 Å, about 2,000 Å, about 3,000 Å, about 5,000 Å, about 6,000 Å, about 8,000 Å, about 10,000 Å, about 15,000 Å, about 20,000 Å, or more than this. For example, the nitrogen-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 200 Å to about 20,000 Å, about 200 Å to about 10,000 Å, about 200 Å to about 6,000 Å, about 200 Å to about 5,000 Å, about 200 Å to about 3,000 Å, about 200 Å to about 2,000 Å, about 200 Å to about 1,000 Å, about 200 Å to about 500 Å, about 600 Å to about 3,000 Å, about 600 Å to about 2,000 Å, about 600 Å to about 1,500 Å, about 600 Å to about 1,000 Å, about 600 Å to about 800 Å, about 1,000 Å to about 20,000 Å, about 1,000 Å to about 10,000 Å, about 1,000 Å to about 5,000 Å, about 1,000 Å to about 3,000 Å, about 1,000 Å to about 2,000 Å, about 2,000 Å to about 20,000 Å, or about 2,000 Å to about 3,000 Å.

[0028]

[0033] The nitrogen-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 nitrogen-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 nitrogen-doped diamond-like carbon film may 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 nitrogen-doped diamond-like carbon film may have an absorption coefficient or k value (k at 633 nm) 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.

[0030]

[0035] The nitrogen-doped diamond-like carbon film - has a compressive stress of less than 600 MPa, for example, about - 10 MPa, about - 20 MPa, about - 50 MPa, about - 80 MPa, about - 100 MPa, about - 150 MPa, about - 200 MPa, about - 250 MPa, about - 275 MPa, or about - 300 MPa to about - 325 MPa, about - 350 MPa, about - 375 MPa, about - 400 MPa, about - 425 MPa, about - 450 MPa, about - 475 MPa, about - 500 MPa, about - 550 MPa, about - 580 MPa, or about - 590 MPa. For example, the nitrogen-doped diamond-like carbon film may have a compressive stress of about - 20 MPa to - less than 600 MPa, about - 50 MPa to - less than 600 MPa, about - 100 MPa to - less than 600 MPa, about - 200 MPa to - less than 600 MPa, about - 250 MPa to - less than 600 MPa, about - 300 MPa to -Less than 600 MPa, approximately - 350 MPa to - Less than 600 MPa, approximately - 400 MPa to - Less than 600 MPa, approximately - 450 MPa to - Less than 600 MPa, approximately - 500 MPa to - Less than 600 MPa, approximately - 20 MPa to approximately - 500 MPa, approximately - 100 MPa to approximately - 500 MPa, approximately - 200 MPa to approximately - 500 MPa, approximately - 250 MPa to approximately - 500 MPa, approximately - 300 MPa to approximately - 500 MPa, approximately - 350 MPa to approximately - 500 MPa, approximately - 400 MPa to approximately - 500 MPa, approximately - 450 MPa to approximately - 500 MPa, approximately - 20 MPa to approximately - 400 MPa, approximately - 100 MPa to approximately - 400 MPa, approximately - 200 MPa to approximately - 400 MPa, approximately - 250 MPa to approximately - 400 MPa, approximately - 300 MPa to approximately - 400 MPa, or approximately - 350 MPa to approximately - It may have a compressive stress of 400 MPa.

[0031]

[0036] The nitrogen-doped diamond-like carbon film may have a modulus of elasticity exceeding 50 GPa or exceeding 60 GPa, for example, about 65 GPa, about 70 GPa, about 75 GPa, about 90 GPa, about 100 GPa, about 125 GPa, or about 150 GPa to about 175 GPa, about 200 GPa, about 250 GPa, about 275 GPa, about 300 GPa, about 350 GPa, or about 400 GPa. For example, the nitrogen-doped diamond-like carbon film may have a modulus of elasticity of exceeding 60 GPa to about 400 GPa, exceeding 60 GPa to about 350 GPa, exceeding 60 GPa to about 300 GPa, exceeding 60 GPa to about 250 GPa, exceeding 60 GPa to about 200 GPa, exceeding 60 GPa to about 150 GPa, exceeding 60 GPa to about 125 GPa, exceeding 60 GPa to about 100 GPa, exceeding 60 GPa to about 80 GPa, about 65 GPa to about 400 GPa, about 65 GPa to about 350 GPa, about 65 GPa to about 300 GPa, about 65 GPa to about 250 GPa, about 65 GPa to about 200 GPa, about 65 GPa to about 150 GPa, about 65 GPa to about 125 GPa, about 65 GPa to about 100 GPa, about 65 GPa to about 80 GPa, about 80 GPa to about 400 GPa, about 80 GPa to about 350 GPa, about 80 GPa to about 300 GPa, about 80 GPa to about 250 GPa, about 80 GPa to about 200 GPa, about 80 GPa to about 150 GPa, about 80 GPa to about 125 GPa, or about 80 GPa to about 100 GPa. In one or more embodiments, the nitrogen-doped diamond-like carbon film has the aforementioned modulus of elasticity and may have a thickness of about 600 Å.

[0032]

[0037] In some embodiments, the nitrogen-doped diamond-like carbon film is a bottom layer for extreme ultraviolet ( "EUV") lithography processing. In some embodiments, the film used as the bottom layer for EUV lithography processing is sp 3 The content of the sp hybrid carbon atoms is about 40% to about 90% based on the total amount of carbon atoms in the film, the density is more than 1.5 g / cc to about 1.9 g / cc, and the modulus of elasticity is about 60 GPa to about 150 GPa, or about 200 GPa.

[0033]

[0038] Figure 1A shows a schematic diagram of a substrate processing system 132 that can be used to deposit a nitrogen-doped diamond-like carbon film according to the embodiments described herein. The substrate processing system 132 includes a processing chamber 100 connected to a gas panel 130 and a controller 110. The processing chamber 100 generally includes an upper wall 124, side walls 101, and a bottom wall 122, and these walls 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 manufactured from aluminum, ceramic, and other suitable materials. The electrostatic chuck 150 can be moved vertically inside the processing chamber 100 using a displacement mechanism (not shown).

[0034]

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

[0035]

[0040] The substrate processing system 132 may further include an additional device for controlling the chamber pressure, such as a valve (e.g., a throttle valve or an isolation valve), 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 an electrostatic chuck 150 and at the top of a 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, which 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 in the range 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 in the range 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 the processing sequence and regulate the gas flow from the gas panel 130. The CPU 112 may be any form of general-purpose computer processor 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 circuitry, 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 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. Additionally, 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] FIG. 2 shows a schematic cross-sectional view of a substrate support assembly 146 used in the processing systems of FIGS. 1A and 1B that may be used in practicing the 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 the upper surface 192 of the electrostatic chuck 150. The heater element 170 may be embedded in the electrostatic chuck 150. The electrostatic chuck 150 may be resistively heated by applying a current from a heater power supply 106 to the heater element 170. The heater power supply 106 may be connected through an RF filter 216. The RF filter 216 may be used to protect the heater power supply 106 from RF energy. The heater element 170 may be made of nickel-chromium wire encapsulated within a sheath tube of a nickel-iron-chromium alloy (e.g., INCOLOY®). 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 thereby maintain the substrate 190 and the electrostatic chuck 150 at a substantially constant temperature during film deposition. The supplied current may 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) may be embedded in the electrostatic chuck 150 to monitor the temperature of the electrostatic chuck 150. The measured temperature is used by the controller 110 to control the power supplied to the heater element 170 to maintain the substrate at a desired temperature.

[0042]

[0047] The electrostatic chuck 150 includes a chucking electrode 210, which may be a mesh of a conductive material. The chucking electrode 210 may be embedded in the electrostatic chuck 150. The chucking electrode 210 is connected to a chucking power supply 212 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 a chucking power supply 212 through an 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 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] A 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 both the controller 110 and both the first RF power supply 230 and the second RF power supply 240. The controller 110 may further be utilized to control the plasma from the processing 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, the electrostatic chuck 150 is In one aspect, it 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, and 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 with a power of about 10 watts to about 3,000 watts, and the second RF bias is supplied at a frequency of about 350 KHz to about 100 MHz and with 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 with a power of about 2,500 watts to about 3,000 watts, and the second RF bias is supplied at a frequency of about 2 MHz and with a power of about 800 watts to about 1,200 watts.

[0048]

[0053] In one or more embodiments, a deposition gas containing one or more hydrocarbon compounds and one or more nitrogen dopant compounds may be flowed or introduced into the processing space of a processing chamber such as a PE-CVD chamber. The hydrocarbon compound and the nitrogen dopant compound may be independently flowed or introduced into the processing space. 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 nitrogen-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 nitrogen-doped diamond-like carbon film, and the nitrogen-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 nitrogen-doped diamond-like carbon film. The substrate temperature may be in the range of about 50°C to about 350°C (e.g., about 40°C to about 100°C, about 10°C to about 100°C, or about 10°C to about 50°C). The chamber pressure may be in the range of chamber pressure of about 0.5 mTorr to about 10 Torr (e.g., about 2 mTorr to about 50 mTorr, or about 2 mTorr to about 10 mTorr). The flow rate of the hydrocarbon compound may be about 20 sccm to about 5,000 sccm (e.g., about 50 sccm to about 1,000 sccm, about 100 sccm to about 200 sccm, or about 150 sccm to about 200 sccm). The flow rate of the nitrogen dopant compound (e.g., N2) may be about 1 sccm to about 3,000 sccm (e.g., about 5 sccm to about 500 sccm, about 10 sccm to about 150 sccm, or about 20 sccm to about 100 sccm). The flow rate of the dilution gas or purge gas (e.g., He) may be about 1 sccm to about 3,000 sccm (e.g., about 5 sccm to about 500 sccm, about 10 sccm to about 150 sccm, or about 20 sccm to about 100 sccm). The nitrogen-doped diamond-like carbon film may be deposited to a thickness of about 200 Å to about 6,000 Å (e.g., depending on the application, about 300 Å to about 5,000 Å, about 400 Å to about 800 Å, about 2,000 Å to about 3,000 Å, or about 5 Å to about 200 Å). In one or more embodiments, the process parameters present examples of process parameters for 300 mm substrates in a deposition chamber available from Applied Materials, Inc. of Santa Clara, California.

[0050]

[0055] FIG. 3 shows a flowchart of a method 300 for forming a nitrogen-doped diamond-like carbon film on a film stack disposed on a substrate according to an embodiment of the present disclosure. The nitrogen-doped diamond-like carbon film formed on the film stack can be used, for example, as a hard mask for forming a stepped structure in the film stack. FIGS. 4A and 4B are schematic cross-sectional views showing a sequence for forming a nitrogen-doped diamond-like carbon film on a film stack disposed on a substrate by the method 300. The method 300 will be described later in connection with a hard mask layer that can be formed on a film stack used for manufacturing a stepped structure in the film stack 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 performed simultaneously and / or in an order different from the order shown in FIG. 3.

[0051]

[0056] The method 300 begins in step 310 by positioning a substrate (such as substrate 402 shown in FIG. 4A) in a processing chamber (such as processing chamber 100 shown in FIG. 1A or FIG. 1B). The substrate 402 can be the substrate 190 shown in FIGS. 1A, 1B, and 2. The substrate 402 can be positioned on an electrostatic chuck (e.g., the upper surface 192 of the electrostatic chuck 150). The substrate 402 can be a silicon-based material, or any suitable insulating or conductive material as required, with a film stack 404 disposed on top, and these materials can be used to form a structure 400 (e.g., a stepped structure) in the film stack 404.

[0052]

[0057] 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 a structure is 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, 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.

[0053]

[0058] 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 those 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.

[0054]

[0059] The film laminate 404 may be a 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 three times 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.

[0055]

[0060] In one or more embodiments, the film laminate 404 can be used to form a plurality of gate structures for a three-dimensional memory chip. The first layers 408a1, 408a2, 408a3,..., 408a n formed in the film laminate 404 may be a first dielectric layer, and the second layers 408b1, 408b2, 408b3,..., 408b n may be a 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.

[0056]

[0061] 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, which will change as technology progresses.

[0057]

[0062] Note that a nitrogen-doped diamond-like carbon film can be formed on any surface or any part of the substrate 402, regardless of whether the film stack 404 exists on the substrate 402.

[0058]

[0063] 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 keeps the substrate 402 in close contact with the upper surface 192 and prevents 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.

[0059]

[0064] 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 processing 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).

[0060]

[0065] 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 be helium, argon, neon, nitrogen (N2), hydrogen (H2), or any combination thereof or can include them.

[0061]

[0066] 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 be at a frequency of about 350 KHz to about 100 MHz (e.g., 350 KHz, about 2 MHz, about 13.56 MHz, about 27 MHz, about 40 MHz, about 60 MHz, or about 100 MHz) and can be from about 10 watts to about 3,000 watts. In one or more embodiments, the first RF bias is supplied at a frequency of about 13.56 MHz with a power of about 2,500 watts to about 3,000 watts. In one or more embodiments, the first RF bias is supplied to the electrostatic chuck 150 via 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 (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).

[0062]

[0067] 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 electrically communicable 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.

[0063]

[0068] 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).

[0064]

[0069] In process 340, deposition gas is flowed into the processing space 126 to form a nitrogen-doped diamond-like carbon film 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 sidewall 101. The deposition gas includes one or more hydrocarbon compounds and one or more nitrogen dopant compounds. The hydrocarbon compound can be one, two, or more hydrocarbon compounds in any state of matter, or can include these. Similarly, the nitrogen dopant compound can be one, two, or more nitrogen dopant compounds in any state of matter, or can include these. The hydrocarbon and / or nitrogen dopant compound can be either a liquid or a gas, but if any of the precursors are vapor at room temperature, some advantages can be realized in order to simplify the hardware required for metering, controlling, and supplying the material to the processing space.

[0065]

[0070] The deposition gas can further include an inert gas, a dilution gas, a nitrogen-containing 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.

[0066]

[0071] 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 represented by, 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 (C7H 10 )、or any combination thereof is included. In one or more embodiments, ethyne is utilized to form a more stable intermediate species that enables improved surface mobility.

[0067]

[0072] 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).

[0068]

[0073] 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).

[0069]

[0074] 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 (such as acetylene (C2H4), propyne (C3H4), butylene (C4H8), vinylacetylene, or combinations thereof).

[0070]

[0075] 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.), 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.

[0071]

[0076] The deposition gas contains one or more nitrogen dopant compounds. Exemplary nitrogen dopant compounds are dinitrogen (N2), atomic nitrogen, ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, pyridine, derivatives thereof, addition compounds thereof, or any combination thereof, or may include these. 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 into the processing space 126 with the deposition gas or supplied in other ways. Argon, helium, and nitrogen can be used to control the density and deposition rate of the nitrogen-doped diamond-like carbon film. In some cases, the addition of N2 and / or NH3 can be used to control the hydrogen ratio in the nitrogen-doped diamond-like carbon film, as will be described later. Alternatively, no dilution gas may be used during deposition.

[0072]

[0077] 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 selectively etches sp 2 hybrid carbon atoms from the film, and thus increases the fraction of sp 3 hybrid carbon atoms in the film, thereby increasing the etching selectivity of the film.

[0073]

[0078] In one or more embodiments, in step 340, after the nitrogen-doped diamond-like carbon film 412 is formed on the substrate, the nitrogen-doped diamond-like carbon film 412 is exposed to hydrogen radicals. In some implementations, the nitrogen-doped diamond-like carbon film is exposed to hydrogen radicals during the deposition process of step 340. In other embodiments, the hydrogen radicals are formed within the RPS and supplied to the processing region. Without being bound by theory, exposing the nitrogen-doped diamond-like carbon film to hydrogen radicals leads to the selective etching of sp 2 hybrid carbon atoms, resulting in an increase in the fraction of sp 3 hybrid carbon atoms in the film, thereby increasing the etching selectivity.

[0074]

[0079] In step 350, after the nitrogen-doped diamond-like carbon film 412 is formed on the substrate, the substrate is de-chucked. 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 de-chucked 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.

[0075]

[0080] FIG. 5 shows a flow diagram of a method 500 of using a nitrogen-doped diamond-like carbon film according to one or more embodiments described and explained herein. After the nitrogen-doped diamond-like carbon film 412 is formed on a substrate, it can be used as a patterning mask for forming a three-dimensional structure (such as a stepped structure) in an etching process. The nitrogen-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 nitrogen-doped diamond-like carbon film 412. In step 520, the nitrogen-doped diamond-like carbon film 412 may be etched in a pattern corresponding to the patterned photoresist layer, and then, in step 530, this pattern is etched into the substrate 402. In step 540, a material can be deposited into the etched portion of the substrate 402. The nitrogen-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 nitrogen-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 nitrogen-containing diamond-like carbon film 412 can also be removed by a chemical mechanical polishing (CMP) process.

[0076] Extreme ultraviolet (EUV) patterning method

[0081] When using a metal-containing photoresist in an extreme ultraviolet (EUV) patterning method, the selection of the underlying layer is important to prevent nanofailures (such as 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 reduce, deteriorate, and interfere with semiconductor performance.

[0077]

[0082] On the other hand, the high-density carbon film described in this specification has excellent film quality (for example, improved hardness and density). Due to such hardness and density, the high-density carbon film can act as a much stronger barrier against metal intrusion and prevent (at least reduce) extremely small defects compared to conventional SOC films. In one or more embodiments, a film is provided for use as an underlayer for extreme ultraviolet (EUV) lithography processing.

[0078]

[0083] In one or more embodiments, the nitrogen-doped diamond-like carbon film used as an underlayer for EUV lithography processing can be any of the films described in this specification. The nitrogen-doped diamond-like carbon film has an sp 3 hybrid carbon atom content of about 40% to about 90% based on the total amount of carbon atoms in the nitrogen-doped diamond-like carbon film, a compressive stress of about -20 MPa to less than about -600 MPa, about -150 MPa to less than about -600 MPa, or about -200 MPa to less than about -600 MPa (for example, about - 225 MPa to about - 500 MPa, or about - 250 MPa to about - 400 MPa), a modulus of elasticity of greater than 60 GPa to about 200 GPa, or greater than 60 GPa to about 150 GPa, and a density of greater than about 1.5 g / cc to about 2.1 g / cc, less than about 1.55 g / cc to 2 g / cc (for example, about 1.6 g / cc to about 1.8 g / cc, about 1.65 g / cc to about 1.75 g / cc, or about 1.68 g / cc to about 1.72 g / cc).

[0079]

[0084] Thus, a method and an apparatus for forming a stepped structure that can be used for manufacturing a three-dimensional stack of semiconductor devices, or for forming a hard mask layer including the same, are provided. By utilizing a nitrogen-doped diamond-like carbon film as a hard mask layer having desired strong film properties and etching selectivity, an improvement in dimension and profile control of a structure formed of a film laminate, which is obtained as a result, can be achieved, and the electrical performance of a chip device can be enhanced in applications for three-dimensional stacking of semiconductor devices.

[0080]

[0085] That is, according to some advantages of the present disclosure, a process for depositing or forming a nitrogen-doped diamond-like carbon film on a substrate is provided. A typical PE-CVD hard mask film has a very low ratio of hybrid sp 3 atoms, and thus has a low elastic modulus and etching selectivity. In some embodiments described herein, low process pressure (less than 1 Torr) and bottom driven plasma enable the production of a doped film having about 60% or more hybrid sp 3 atoms, which results in 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.

[0081]

[0086] The foregoing 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 thereof, 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 foregoing summary and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended to limit the present disclosure thereby. Similarly, the term "comprising" is considered to be synonymous with the term "including" as construed under United States law. Similarly, whenever 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 "consisting essentially of", "consisting of", "selected from the group of consisting of", or "is" preceding the listing of one or more elements, and vice versa is also understood to be the case.

[0082]

[0087] Certain embodiments and features are described using a set of upper limits of numerical values and a set of lower limits of numerical values. It should be recognized that 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), unless otherwise indicated. 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 nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, wherein the nitrogen dopant compound comprises ammonia, hydrazine, methyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, azoisobutane, ethyl azide, pyridine, derivatives thereof, addition compounds thereof, or any combination thereof; generating a plasma above the substrate by applying a first RF bias to the electrostatic chuck to deposit a nitrogen-doped diamond-like carbon film containing about 0.05 atomic % to 7 atomic % nitrogen and having a density greater than 1.5 g / cc and a compressive stress of about -20 MPa to -600 MPa on the substrate; A method comprising the above steps.

2. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film has a compressive stress of about -250 MPa to about -400 MPa.

3. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film has an elastic modulus of greater than 60 GPa to about 200 GPa.

4. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film has a density of about 1.55 g / cc to less than 2 g / cc.

5. The method according to claim 1, wherein the nitrogen dopant compound is flowed into the processing space at a flow rate of about 10 sccm to about 1,000 sccm.

6. The method according to claim 1, wherein the processing space is maintained at a pressure of about 0.5 mTorr to about 10 Torr when generating the plasma and depositing the nitrogen-doped diamond-like carbon film on the substrate.

7. The method according to claim 6, wherein the processing space 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.

8. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film contains about 0.1 atomic % to about 5 atomic % nitrogen.

9. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film contains about 0.1 atomic % to about 3 atomic % nitrogen.

10. The method according to claim 1, wherein the nitrogen-doped diamond-like carbon film contains about 1 atomic % to about 7 atomic % nitrogen.

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

12. 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.

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

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

15. The method according to claim 14, wherein 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.

16. The method according to claim 14, wherein 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.

17. A method of processing a substrate, flowing a deposition gas containing a hydrocarbon compound and a nitrogen dopant compound into a processing space of a processing chamber having a substrate disposed on an electrostatic chuck, wherein the nitrogen dopant compound comprises ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, pyridine, derivatives thereof, addition compounds thereof, or any combination thereof, and 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, flowing the deposition gas; To deposit a nitrogen-doped diamond-like carbon film on the substrate, a first RF bias is applied to the RF electrode and a second RF bias is applied to the chucking electrode to generate plasma above the substrate, wherein the nitrogen-doped diamond-like carbon film contains nitrogen of about 0.05 atomic % to about 7 atomic % and about 50 atomic % to about 90 atomic % of ３ hybrid carbon atoms, has a density exceeding 1.5 g / cc and a compressive stress of about -20 MPa to -600 MPa, and generating plasma A method comprising.

18. The method according to claim 17, wherein the nitrogen-doped diamond-like carbon film contains sp hybrid carbon atoms in an amount of about 55 atomic % to about 75 atomic %. ３ hybrid carbon atoms.

19. The method according to claim 17, wherein the nitrogen-doped diamond-like carbon film has a density of about 1.55 g / cc to less than 2 g / cc, a compressive stress of about -250 MPa to about -400 MPa, and a modulus of elasticity of greater than 60 GPa to about 200 GPa.

20. A method of processing a substrate, Flowing a deposition gas containing a hydrocarbon compound and a nitrogen 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 about 0.5 mTorr to about 10 Torr, flowing the deposition gas, Generating a plasma above the substrate by applying a first RF bias to the RF electrode and a second RF bias to the chucking electrode in order to deposit a nitrogen-doped diamond-like carbon film on the substrate, wherein the nitrogen-doped diamond-like carbon film contains about 0.05 atomic % to about 7 atomic % of nitrogen and has a density exceeding 1.5 g / cc and a compressive stress of about -20 MPa to -600 MPa, generating the plasma, Forming a patterned photoresist layer on the nitrogen-doped diamond-like carbon film, Etching the nitrogen-doped diamond-like carbon film with a pattern corresponding to the patterned photoresist layer, Etching the pattern into the substrate, A method comprising.

21. The method according to claim 20, wherein the nitrogen-doped diamond-like carbon film contains about 0.1 atomic % to about 5 atomic % of nitrogen.

22. The method according to claim 20, wherein the nitrogen dopant compound contains ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethyl azide, pyridine, derivatives thereof, addition compounds thereof, or any combination thereof.

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