High etching selectivity amorphous carbon film

Abstract

Methods and techniques are provided for depositing an amorphous carbon film on a substrate. In one example, the method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes implanting a dopant or inert species into the amorphous carbon film in a second processing region. A combination of implant species, energy, dose, and temperature can be used to improve the hardness of the hard mask. The method further includes patterning the doped amorphous carbon film. The method further includes etching the underlayer.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION Implementations described herein relate generally to integrated circuit manufacturing. More particularly, implementations described herein provide techniques for depositing amorphous carbon films on substrates. [Background technology]

[0002] Integrated circuits have evolved into complex devices that can contain millions of transistors, capacitors, and resistors on a single chip. Evolution in chip design continues to require faster circuits and greater circuit density. The demand for faster circuits with greater circuit density places corresponding demands on the materials used to fabricate such integrated circuits. In particular, as the dimensions of integrated circuit components shrink to the sub-micron range, low resistivity conductive materials and low dielectric constant insulating materials are used to obtain adequate electrical performance from such components.

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

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

[0005] Therefore, there is a need in the art for improved hardmask layers and methods for depositing improved hardmask layers. Summary of the Invention

[0006] Implementations described herein generally relate to integrated circuit manufacturing. More particularly, implementations described herein provide techniques for depositing amorphous carbon films on a substrate. In one implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes forming a doped amorphous carbon film by implanting a dopant or inert species into the amorphous carbon film in a second processing region. The dopant or inert species is selected from carbon, boron, nitrogen, nitrogen dimer, silicon, phosphorus, argon, helium, neon, krypton, xenon, or a combination thereof. The method further includes patterning the doped amorphous carbon film and etching the underlayer.

[0007] In another implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes forming a doped amorphous carbon film in a second processing region by implanting a dopant into the amorphous carbon film. The dopant or inert species is selected from carbon, boron, nitrogen, nitrogen dimer, silicon, phosphorus, argon, helium, neon, krypton, xenon, or combinations thereof. The method further includes patterning the doped amorphous carbon film. The method further includes etching the underlayer, wherein the doped amorphous carbon film has a refractive index of about 2.1 to about 2.2 at 633 nm.

[0008] In yet another implementation, a hard mask layer is provided that includes an amorphous carbon film formed by a plasma-enhanced chemical vapor deposition process followed by a carbon implantation process, where the dopant or inert species is selected from carbon, boron, nitrogen, nitrogen dimer, silicon, phosphorus, argon, helium, neon, krypton, xenon, or combinations thereof. The amorphous carbon film functions as a hard mask layer in an etching process for use in semiconductor applications.

[0009] In yet another implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes forming a doped amorphous carbon film in a second processing region by implanting a dopant or inert species into the amorphous carbon film. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorus, argon, helium, neon, krypton, xenon, beryllium, germanium, or a combination thereof, and wherein the target temperature during implantation of the dopant or inert species is between about −100° C. and about 550° C. The method further includes patterning the doped amorphous carbon film and etching the underlayer.

[0010] In yet another implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes implanting a dopant or inert species into the amorphous carbon film in a second processing region to form a doped amorphous carbon film. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorus, argon, helium, neon, krypton, xenon, beryllium, germanium, or a combination thereof, and the target temperature during implantation of the dopant or inert species is between about −100° C. and about 550° C. The method includes patterning the doped amorphous carbon film and etching the underlayer, wherein the doped amorphous carbon film has a refractive index of about 2.1 to about 2.2 at 633 nm.

[0011] In yet another implementation, a method of forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes forming a doped amorphous carbon film in a second processing region by implanting a carbon dopant into the amorphous carbon film, where a target temperature during implantation of the dopant is between about −100° C. and about 550° C. The method includes patterning the doped amorphous carbon film and etching the underlayer, where the doped amorphous carbon film has a hardness (GPa) of about 14 GPa to about 22 GPa.

[0012] In yet another implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes patterning the amorphous carbon layer. The method further includes implanting a dopant or inert species into the patterned amorphous carbon film in a second processing region to form a doped, patterned amorphous carbon film. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorus, argon, helium, neon, krypton, xenon, beryllium, germanium, or a combination thereof, where the target temperature during implantation of the dopant or inert species is between about −100° C. and about 550° C. The method further includes etching the underlayer.

[0013] In yet another implementation, a method for forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes patterning the amorphous carbon layer. The method further includes implanting a dopant or inert species into the patterned amorphous carbon film in a second processing region to form a doped, patterned amorphous carbon film. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorus, argon, helium, neon, krypton, xenon, beryllium, germanium, or a combination thereof, and the target temperature during implantation of the dopant or inert species is between about -100°C and about 550°C. The implantation can be performed at a tilt angle of 0 degrees with certain species that allow for increased etch rates of the underlayer, or at a tilt angle between 0.1° and 80° and an associated twist angle between 0° and 360°. The associated tilt angle allows ions to penetrate only the hard mask due to the nature of the species, which may reduce the etch rate of the underlying layer. If the line and space features in the carbon hard mask run in one direction rather than two perpendicular directions, the implant can be split into two implants, each at half the desired dose, e.g., 1.0×10 16 ions / cm 2 The dose is 5.0 x 10 15 ions / cm 2 The substrate is implanted for each 180° rotation, so 1.0×10 16 ions / cm 2 The doped amorphous carbon film is deposited to a desired dose of 0.015 to 0.015 .mu.m, resulting in a uniform implantation of both sides of the carbon hard mask feature. The method can further include doping the patterned undoped amorphous carbon film and etching the underlayer, wherein the doped amorphous carbon film has a refractive index of about 2.1 to about 2.2 at 633 nm.

[0014] In yet another implementation, a method of forming an amorphous carbon film is provided. The method includes depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region. The method further includes patterning the amorphous carbon layer. The method further includes forming a doped, patterned amorphous carbon film in a second processing region by implanting a carbon dopant into the patterned amorphous carbon film, where a target temperature during implantation of the dopant is between about −100° C. and about 550° C. The method further includes etching the underlayer, where the doped, patterned amorphous carbon film has a hardness (GPa) of about 14 GPa to about 22 GPa.

[0015] In yet another implementation, instructions that, when executed by a processor, cause the process to perform the operations of the apparatus and / or method described above are stored on a non-transitory computer-readable medium.

[0016] To better understand the above features of the present disclosure, a more detailed description of the implementations briefly summarized above can be had by reference to the implementations, some of which are illustrated in the accompanying drawings. However, it should be noted that the present disclosure may also admit of other equally effective implementations, and therefore the accompanying drawings illustrate only typical implementations of the present disclosure and should not be considered as limiting the scope of the present disclosure. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows a schematic diagram of an apparatus that can be used to practice implementations described herein. [Figure 2] FIG. 1 illustrates a process flow diagram of a method for forming an amorphous carbon hard mask layer over a film stack disposed on a substrate, in accordance with one or more implementations of the present disclosure. [Figures 3A-3H] 1A-1D show schematic cross-sectional views of a substrate structure illustrating a hard mask formation sequence, in accordance with one or more implementations of the present disclosure. [Figure 4] FIG. 1 illustrates a process flow diagram of a method for forming an amorphous carbon hard mask layer on a film stack disposed on a substrate, in accordance with one or more implementations of the present disclosure. [Figure 5A] 1 shows a plot of in-plane strain versus film stress (MPa) for amorphous carbon films formed in accordance with implementations of the present disclosure compared to amorphous carbon films formed using prior art techniques. [Figure 5B] 5B shows a plot of Young's modulus (GPa) versus film stress (MPa) for the amorphous carbon film of FIG. 5A. [Figure 6] FIG. 1 shows a process flow diagram of another method for forming an amorphous carbon hard mask layer on a film stack disposed on a substrate, in accordance with one or more implementations of the present disclosure. [Figures 7A-7I] 1A-1D show schematic cross-sectional views of a substrate structure illustrating a hard mask formation sequence, in accordance with one or more implementations of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0018] For ease of understanding, wherever possible, identical reference numerals have been used to designate identical elements common to the figures. It is contemplated that elements and features of one implementation may be beneficially incorporated in other implementations without further recitation.

[0019] The following disclosure describes techniques for depositing diamond-like carbon films on substrates. Specific details are provided in the following specification and in Figures 1-7I to provide a thorough understanding of various implementations of the present disclosure. Other details describing well-known structures and systems often associated with plasma processing and ion implantation are not provided in the following disclosure to avoid unnecessarily obscuring the description of the various implementations.

[0020] Many of the details, dimensions, angles, and other features shown in the figures are merely illustrative of particular implementations. Thus, other implementations may have other details, components, dimensions, angles, and features without departing from the spirit and scope of the present disclosure. Furthermore, further implementations of the present disclosure may be practiced without some of the details described below.

[0021] Implementations described herein are described below with reference to PECVD deposition processes and ion implantation processes that may be performed using any suitable thin film deposition and implantation system. Examples of suitable systems are the CENTURA® system, PRECISION 5000® system, PRODUCER® system, and PRODUCER® GT system, which may use a DXZ® processing chamber. TM System, PRODUCER® XP Precision TM System, PRODUCER® SE TM System, Sym3® Processing Chamber, and Mesa TM The ion implantation process may include a processing chamber, all of which are commercially available from Applied Materials, Inc., Santa Clara, California. The ion implantation process may be performed by a beamline or plasma implantation tool. Exemplary systems utilized to perform the implantation process include, for example, the VARIAN VIISta® TRIDENT system, the VARIAN VIISta® Thermion system, the VARIAN VIISta® Medium Current Thermion system, the VIISta® 3000XP system, the VIISta® 900XP system, the VIISta® HCP system, and the VIISta® Trident Crion system, all of which are commercially available from Applied Materials, Inc., Santa Clara, California. TMSystems, and VIISta® PLAD systems. Other tools capable of performing PECVD and / or ion implantation processes may also be adapted to benefit from the implementations described herein. Additionally, any system that enables the PECVD and / or ion implantation processes described herein may be advantageously used. The apparatus descriptions provided herein are exemplary and should not be understood or construed as limiting the scope of the implementations described herein.

[0022] Physical constraints in integrated circuit scaling have led to the orthogonal extension of integrated circuits to planar wafer surfaces, i.e., high aspect ratio (HAR), and the three-dimensional utilization of device space. Nanofabrication strategies to address dynamic etch selectivity and increasingly tight manufacturing tolerances have led to a library of hardmask (HM) materials, including silicon-, titanium-, tungsten-, or boron-doped carbon films and dielectric silicon oxide / silicon nitride (ON / OP) films. Combinations of these materials offer advantages in etch selectivity and patterning up to the 1X node. Innovations in amorphous carbon hardmask materials are needed to achieve the high aspect ratio (HAR) benchmark for next-generation device structures. Unlike metal and dielectric solutions, amorphous carbon is easily ashed, resulting in high selectivity to the underlying ON / OP hardmask films. Another advantage of amorphous carbon hardmasks is their corresponding optical properties. This optical property is tunable, providing transparency for aligned, patterned features, eliminating the need for partial hardmask opening processes. However, current amorphous carbon hardmask integration hardware and processes have relatively poor mechanical properties compared to metal-doped and dielectric hardmasks. Etch selectivity for current-generation pure carbon films (e.g., nanocrystalline diamond, ultrananocrystalline diamond, diamond-like carbon, and physical vapor-deposited carbon) has been found to be highest for films with a high sp3 content, similar to diamond hybridization. A long-standing and valuable issue with diamond-like carbon hardmasks is the compressive film stress of >1 GPa due to sp3 hybridized carbon, which limits patterning performance due to lithography overlay and electrostatic chucking constraints.

[0023] Next-generation 3D NAND products with 64x layer stack applications and 100:1 aspect ratios require thin films that enable patterning while resisting deformation, while simultaneously demonstrating improved lithographic overlay. Diamond-like carbon films combine carbon-species-specific etch selectivity with excellent structural integrity. These diamond-like carbon films will only remain competitive if their mechanical properties (of which Young's modulus is a precursor) can be further improved by reducing stress and in-plane strain ("IPD") values.

[0024] Some implementations of the present disclosure provide a process that uses existing hardware with little impact on throughput or implementation costs. Some implementations of the present disclosure address the issues of high lithography overlay and high stress associated with low Young's modulus (E). Some implementations of the present disclosure provide a unique process that increases the elastic modulus of amorphous carbon by approximately two-fold (e.g., from approximately 64 GPa to approximately 138 GPa) by adjusting the plasma deposition mechanism. Ion implantation further improved the Young's modulus of amorphous carbon films by an additional 30% (approximately 180 GPa) and reduced the compressive stress by 75% (approximately -1200 to approximately -300 MPa), further improving film properties. Furthermore, the combination of PECVD and ion implantation resulted in amorphous carbon films with significantly reduced in-plane distortion (<3 nanometer overlay error) compared to current-generation pure carbon hard mask films.

[0025] In improving the performance of amorphous carbon hard mask films, a first aspect of the present disclosure defines a new process window. This new process window targets improved elastic modulus while minimizing in-plane strain despite high stress (e.g., approximately -1200 GPa). Without being bound by theory, it is believed that these improvements can be achieved by increasing the plasma sheath size through reduced pressure, increasing the process gap, and lowering the plasma temperature. Higher sheath potential and Bohm velocity were confirmed by significantly reduced deposition rates despite reduced synthesis temperatures. This leads to the formation of more carbon-carbon bonds and reduced hydrogen content in the films. In one implementation, the extinction coefficient at 633 nm after deposition was measured at 0.72, indicating higher C=C, graphitic properties. Furthermore, reducing the plasma density increased the mean free path and collision energy, improving the uniformity of the ion energy distribution function across the wafer surface. The in-film properties of the weak plasma, which minimizes collision-induced amorphization, show increased Young's modulus (E), hardness, and density. Without being bound by theory, it is believed that a longer mean free path results in a smaller in-plane distortion (IPD), which is a target for lithographic overlay.

[0026] In-line ion implantation, a second aspect of the present disclosure, helps reduce the stress component of amorphous carbon films by up to about 75% (e.g., from about −1200 to about −300 MPa), further improve Young's modulus (e.g., from about 138 to about 177 GPa), and create a more centripetal in-plane strain profile. Ion implantation can be performed over a range of temperatures (e.g., from about −100°C to about 550°C). Lowering the ion implantation temperature of amorphous carbon films has been shown to minimize rearrangement of implanted dopants, confirming beneficial effects of implantation such as densification, sp3 strengthening, and hydrogen reduction. Without being bound by theory, it is believed that ion implantation helps redistribute local stress and reduce overall wafer stress, for example, to about 25% of the post-film deposition value. To avoid HVP of saturation of film improvement, the correct process regime for implantation is developed based on the incoming wafer modulus to optimally enhance modulus while reducing stress.

[0027] The resulting amorphous carbon films have been shown to improve etch selectivity by 30-50% compared to currently available pure carbon hardmask films, while also meeting previous overlay requirements.

[0028] In some implementations of this disclosure, amorphous carbon films were deposited via plasma-enhanced chemical vapor deposition on bare silicon blanket wafers. In some implementations, the carbon precursor was C3H6, with argon and helium gases maintaining the plasma profile and uniformity. The scope of this work also encompasses the use of C4H8, C2H6, C2H4, C2H2, CO2, and CF4, among others. The high-frequency RF for this application was 13.56 MHz. The single-wafer hardware enabled deposition temperatures up to 650°C and maintained plasma stability from center to edge using a gas box, showerhead combination, and planar heater-edge ring configuration. The plasma profile and coupling to the wafer surface could be further tuned by layering the RF for distribution laterally and perpendicular to the wafer surface.

[0029] In some implementations, ion implantation is performed in a single wafer processing tool. A heat exchanger allows for temperature control down to -100°C and the development of low-temperature implantation techniques. The species that provide the high performance demonstrated in this disclosure are ashable ions, allowing the film to maintain its pure carbon character.

[0030] FIG. 1 is a schematic cross-sectional view of a plasma processing chamber 100 configured according to various implementations of the present disclosure. By way of example, the implementation of the plasma processing chamber 100 of FIG. 1 is described in the context of a PECVD system, although any other plasma processing chamber (including other plasma deposition chambers or plasma etch chambers) may fall within the scope of the implementation. The plasma processing chamber 100 includes a wall 102, a bottom 104, and a chamber lid 124, which together enclose a susceptor 105 and a processing region 146. The plasma processing chamber 100 includes a vacuum pump 114, a first RF generator 151, a second RF generator 152, an RF matcher 153, a gas source 154, a top RF current regulator 155, a bottom RF current regulator 157, and a system controller 158, each of which is coupled to the exterior of the plasma processing chamber 100 as shown.

[0031] The walls 102 and bottom 104 may comprise a conductive material, such as aluminum or stainless steel. A slit valve opening may be present through one or more of the walls 102. The slit valve opening 206 is configured to facilitate inserting the substrate 110 into the plasma processing chamber 100 and removing the substrate 110 from the plasma processing chamber 120. A slit valve configured to seal the slit valve opening may be located either inside or outside the plasma processing chamber 100. For clarity, the slit valve and slit valve opening are not shown in FIG. 1 .

[0032] A vacuum pump 114 is coupled to the plasma processing chamber 100 and configured to adjust the vacuum level therein. As shown, a valve 116 may be coupled between the plasma processing chamber 100 and the vacuum pump 114. The vacuum pump 114 evacuates the plasma processing chamber 100 prior to substrate processing and removes process gases from the processing chamber through the valve 116 during processing. The valve 116 may be adjustable to facilitate adjusting the pumping rate of the plasma processing chamber 100. The pumping rate through the valve 116 and the incoming gas flow rate from the gas source 154 determine the chamber pressure and the residence time of the process gases within the plasma processing chamber 100.

[0033] The gas source 154 is coupled to the plasma processing chamber 100 via a tube 123 that penetrates the chamber lid 124. The tube 123 is fluidly coupled to a plenum 148 between the chamber lid 106 and a gas distribution showerhead 128 included in the chamber lid 124. During operation, process gases introduced into the plasma processing chamber 100 from the gas source 154 fill the plenum 148 and then pass through gas passages 129 formed in the gas distribution showerhead 128 for uniform entry into the processing region 146. In alternative implementations, process gases can be introduced into the processing region 146 through inlets and / or nozzles (not shown) attached to the wall 102 in addition to or instead of the gas distribution showerhead 128.

[0034] The susceptor 105 may include any technically feasible device for supporting a substrate (such as the substrate 110 of FIG. 1 ) while it is being processed by the plasma processing chamber 100. In some implementations, the susceptor 105 is disposed on a shaft 112 configured to raise and lower the susceptor 105. In one implementation, the shaft 112 and the susceptor 105 may be at least partially formed from or contain an electrically conductive material (such as tungsten, copper, molybdenum, aluminum, or stainless steel). Alternatively or additionally, the susceptor 105 may be at least partially formed from or contain a ceramic material, such as aluminum oxide (Al2O3), aluminum nitride (AlN), silicon dioxide (SiO2), or the like. In implementations where the plasma processing chamber 100 is a capacitively coupled plasma chamber, the susceptor 105 may be configured to contain an electrode. In such implementations, the metal rod 115 or other conductor is electrically coupled to the electrode 113 and configured to provide a portion of the ground path for the RF power delivered to the plasma processing chamber 100. That is, the metal rod 115 allows the RF power supplied to the plasma processing chamber 100 to pass through the electrode 113 and to ground from outside the plasma processing chamber 100.

[0035] In some implementations, the electrode 113 is also configured to provide an electrical bias from a DC power supply (not shown) to enable electrostatic clamping of the substrate 110 onto the susceptor 105 during plasma processing. In such implementations, the susceptor 105 generally includes a body including one or more ceramic materials, such as those described above, or any other ceramic material suitable for use in an electrostatic chuck. In such implementations, the electrode 113 may be a mesh, such as an RF mesh, or a perforated sheet of material made of molybdenum (Mo), tungsten (W), or other material having a thermal expansion coefficient substantially similar to that of the ceramic material or material included in the body of the susceptor 105. The electrode 113 and the gas distribution showerhead 128 together define a boundary of a processing region 146 in which a plasma is formed. For example, during processing, the susceptor 105 and substrate 110 are elevated and positioned near (e.g., within 10-30 mm) the underside of the gas distribution showerhead 128 to form an at least partially enclosed processing region 146.

[0036] The first RF generator 151 is a radio frequency (RF) power supply configured to provide radio frequency power at a first RF frequency to the discharge electrode 126 via an RF matcher 153. Similarly, the second RF generator 152 is an RF power supply configured to provide radio frequency power at a second RF frequency to the discharge electrode 126 via an RF matcher 153. In some implementations, the first RF generator 151 includes an RF power supply capable of generating RF current at a high frequency (HF), e.g., about 13.56 MHz. Alternatively or additionally, the first RF generator 151 includes a VHF generator capable of generating VHF power (e.g., VHF power at a frequency between about 20 MHz and 200 MHz or higher). In contrast, the second RF generator 152 includes an RF power supply capable of generating so-called low frequency (LF) RF, e.g., RF current at about 350 kHz. Alternatively or additionally, the second RF generator 152 includes an RF generator capable of generating RF power at a frequency between about 1 kHz and about 1 MHz. The first RF generator 151 and the second RF generator 152 are configured to facilitate generation of a plasma between the discharge electrode 126 and the susceptor 105.

[0037] The discharge electrode 126 may include a process gas distribution element, such as a gas distribution showerhead 128 (as shown in FIG. 1 ), and / or an array of gas injection nozzles through which process gases are introduced into the processing region 146. The discharge electrode 126, i.e., the gas distribution showerhead 128, may be oriented substantially parallel to the surface of the substrate 110 and capacitively couples plasma source power to the processing region 146 disposed between the substrate 110 and the gas distribution showerhead 128.

[0038] The RF matcher 153 can be any technically feasible impedance matching device coupled between the first RF generator 151 and the powered electrode of the plasma processing chamber 100, i.e., the gas distribution showerhead 128. The RF matcher 153 is also coupled between the second RF generator 152 and the powered electrode of the plasma processing chamber 100. The RF matcher 153 is configured to match the load impedance (the plasma processing chamber 100) to the source or internal impedance of the driving sources (the first RF generator 151, the second RF generator 152) to enable maximum transfer of RF power from the first RF generator 151 and the second RF generator 152 to the plasma processing chamber 100.

[0039] Forming part of the wall 102 are an upper isolator 107, a conditioning ring 108, and a lower isolator 109. The upper isolator 107 is configured to electrically isolate the conditioning ring 108, which is formed from a conductive material, from the backing plate 106, which in some implementations is energized with RF power during operation. As such, the upper isolator 107 is positioned between the backing plate 106 and the conditioning ring 108 to prevent RF power from being energized to the conditioning ring 108 through the backing plate 106. In some implementations, the upper isolator 107 is configured as a ceramic ring or annulus positioned concentrically about the processing region 146. Similarly, the lower isolator 109 is configured to electrically isolate the conditioning ring 108 from the wall 102. The wall 102 is typically formed from a conductive material and, therefore, may serve as a ground path for a portion of the RF power delivered to the plasma processing chamber 100 during processing. In this manner, the lower isolator 109 allows the conditioning ring 108 to be part of a different ground path for RF power delivered to the plasma processing chamber 100 than that of the wall 102. In some implementations, the upper isolator 107 is configured as or includes a ceramic ring positioned concentrically about the processing region 146.

[0040] The conditioning ring 108 is disposed between the upper isolator 107 and the lower isolator 109, is formed from a conductive material, and is positioned adjacent to the processing region 146. For example, in some implementations, the conditioning ring 108 is formed from a suitable metal such as aluminum, copper, titanium, or stainless steel. In some implementations, the conditioning ring 108 is a metal ring or annulus that is concentrically positioned around the susceptor 105 and the substrate 110 during processing of the substrate 110. Furthermore, the conditioning ring 108 is electrically coupled to ground via a conductor 156 through a top RF current regulator 155, as shown. Thus, the conditioning ring 108 is not a powered electrode, but is generally positioned outside and around the processing region 146. In one example, the conditioning ring 108 is positioned in a plane substantially parallel to the substrate 110 and is part of the path to ground for the RF energy used to form a plasma in the processing region 146. As a result, an additional RF ground path 141 is established between the gas distribution showerhead 128 and ground via the top RF current adjuster 155. In this manner, varying the impedance of the top RF current adjuster 155 at a particular frequency changes the impedance to the RF ground path 141 at that particular frequency, resulting in a change in the RF field coupled to the conditioning ring 108 at that frequency. Thus, the shape of the plasma in the processing region 146 can be independently modulated along the + / - X and Y directions relative to the RF frequency associated with either the first RF generator 151 or the second RF generator 152. That is, the shape, volume, or uniformity of the plasma formed in the processing region 146 can be independently modulated for multiple RF frequencies across the surface of the substrate 110, for example, by using the conditioning ring 108, or vertically between the substrate 110 and the gas distribution showerhead 128 using the electrode 113.

[0041] The system controller 158 is configured to control the components and functions of the plasma processing chamber 100, such as the vacuum pump 114, the first RF generator 151, the second RF generator 152, the RF matcher 153, the gas source 154, the top RF current regulator 155, and the bottom RF current regulator 157. As such, the system controller 158 receives sensor inputs, e.g., voltage-current inputs, from the top RF current regulator 155 and the bottom RF current regulator 157 and sends control outputs for operation of the plasma processing chamber 100. The functionality of the system controller 158 may include any technically feasible implementation, including via software, hardware, and / or firmware, and may be divided among multiple separate controllers associated with the plasma processing chamber 100.

[0042] Without being bound by theory, it is believed that delivering RF power of different frequencies to the processing region of the plasma processing chamber during a plasma-enhanced deposition process can adjust the properties of the deposited film. For example, adjusting the low-frequency RF plasma power and / or frequency delivered to the processing region 146, i.e., forming an RF plasma in the 1 kHz to 1 MHz regime, can be beneficial for adjusting some deposited film properties, such as film stress, while adjusting the high-frequency RF plasma power and / or frequency delivered to the processing region 146, i.e., forming an RF plasma in the 1 MHz to 200 MHz regime, can be beneficial for adjusting other deposited film properties, such as thickness uniformity. According to various implementations of the present disclosure, a regulator enables RF current flow within the plasma processing chamber 100 to be independently controlled at multiple RF frequencies. In some implementations, such regulators are used in multiple locations in the plasma processing chamber 100, i.e., the top RF current regulator 155 and the bottom RF current regulator 157.

[0043] As described above, the top RF current adjuster 155 is electrically coupled to the adjusting ring 108 and terminates to ground, thereby providing a controllable RF ground path 141 to the plasma processing chamber 100. Similarly, the bottom RF current adjuster 157 is electrically coupled to the metal rods 115 and terminates to ground, thereby providing a different controllable RF ground path 142 to the plasma processing chamber 100. As described herein, the top RF current adjuster 155 and the bottom RF current adjuster 157 are each configured to control RF current flow to ground at multiple RF frequencies. Thus, the distribution of RF current at a first RF frequency between the adjusting ring 108 and the metal rods 115 can be controlled independently from the distribution of RF current at a second RF frequency between the adjusting ring 108 and the metal rods 115.

[0044] A plasma 180 is formed in the processing region 146 between the electrode 113 and the discharge electrode 126. The distance or "spacing" between the bottom surface of the electrode 113 and the top surface of the susceptor 105 is represented by "x."

[0045] Other deposition chambers may also benefit from the present disclosure, and the parameters listed above may vary depending on the particular deposition chamber used to form the amorphous carbon layer. Other deposition chambers may be larger or smaller in volume and require gas flow rates that are greater or less than those listed for the deposition chamber available from Applied Materials, Inc. In one implementation, boron-carbon films are deposited using a PRODUCER® XP Precision deposition chamber, available from Applied Materials, Inc. of Santa Clara, California. TM The deposition may be carried out using a processing system.

[0046] The atomic percentage of dopant or inert species incorporation in the amorphous carbon film is calculated as follows: (dopant concentration (cm -3 ) to the predicted 1 cm for a carbon film of a particular density. -3(divided by the number of carbon atoms per atom). The amorphous carbon film may contain at least 0.1, 1, or 10 atomic percent of dopant or inert species. The amorphous carbon film may contain up to 1, 10, or 30 atomic percent of dopant or inert species. The amorphous carbon film may contain about 1 to about 30 atomic percent of dopant or inert species. The amorphous carbon film may contain about 10 to about 30 atomic percent of dopant or inert species. The amorphous carbon film may contain at least 3, 5, or 10 atomic percent of hydrogen. The amorphous carbon film may contain up to 5, 10, or 15 atomic percent of hydrogen. The amorphous carbon film may contain about 3 to about 15 atomic percent of hydrogen.

[0047] In one implementation where the dopant is carbon, the atomic percentage of carbon incorporation in the amorphous carbon film is calculated as follows: ((C / (H+C))%). The amorphous carbon film may contain at least 85, 90, or 95 atomic percentage of carbon. The amorphous carbon film may contain up to 90, 95, or 97 atomic percentage of carbon. The amorphous carbon film may contain about 85 to about 97 atomic percentage of carbon. The amorphous carbon film may contain about 90 to about 97 atomic percentage of carbon. The amorphous carbon film may contain at least 3, 5, or 10 atomic percentage of hydrogen. The amorphous carbon film may contain up to 5, 10, or 15 atomic percentage of hydrogen. The amorphous carbon film may contain about 3 to about 15 atomic percentage of hydrogen.

[0048] Generally, the following exemplary deposition process parameters may be used for the PECVD portion of the amorphous carbon film deposition process described herein. The process parameters may range from about 100°C to about 700°C (e.g., between about 300°C and about 700°C) wafer temperature. The chamber pressure may range from about 1 Torr to about 20 Torr (between about 2 Torr and about 8 Torr; or between about 5 Torr and about 8 Torr). The flow rate of the hydrocarbon-containing gas may range from about 100 sccm to about 5,000 sccm (e.g., between about 100 sccm and about 2,000 sccm; or between about 160 sccm and about 500 sccm). The flow rates of the dilution gases may individually range from about 0 sccm to about 5,000 sccm (e.g., between about 2,000 sccm and about 4,080 sccm). The flow rate of the inert gas can individually range from about 0 sccm to about 10,000 sccm (e.g., from about 0 sccm to about 2,000 sccm; or from about 200 sccm to about 2,000 sccm). The RF power can be between 1,000 watts and 3,000 watts. The plate spacing between the top surface of the substrate 110 and the gas distribution showerhead 128 can be set to about 200 mils to about 1,000 mils (e.g., between about 200 mils and about 600 mils; between about 300 mils and about 1,000 mils; or between about 400 mils and about 600 mils). The amorphous carbon film can be deposited to have a thickness of between about 10 Å and about 50,000 Å (e.g., between about 300 Å and about 3,000 Å; or between about 500 Å and about 1,000 Å). The above process parameters provide typical deposition rates for amorphous carbon films ranging from about 100 Å / min to about 5,000 Å / min (e.g., from about 1,400 Å / min to about 3,200 Å / min) and can be performed on 300 mm substrates in a deposition chamber available from Applied Materials, Inc. of Santa Clara, California.

[0049] The as-deposited amorphous carbon film, prior to implantation, may have a refractive index (n)(633 nm) of greater than 1.9, e.g., approximately 2.2 (e.g., about 2.1 to about 2.5). The as-deposited amorphous carbon film may have a k value (k(at 633 nm)) of less than 1.0, e.g., about 0.6 to about 0.8). The as-deposited amorphous carbon film may have a Young's modulus (GPa) of about 50 to about 200 GPa (e.g., about 60 to about 140 GPa; or about 100 to about 140 GPa). The as-deposited amorphous carbon film may have a hardness (GPa) of about 10 GPa to about 22 GPa (e.g., about 10 GPa to about 15 GPa; or about 12 GPa to about 14 GPa). The as-deposited amorphous carbon film may have a stress (MPa) of about −1300 MPa to about 0 MPa (e.g., about −1300 MPa to about −250 MPa; about −1250 MPa to about −1000 MPa). The as-deposited amorphous carbon film may have a density (g / cc) of about 1.7 g / cc to about 1.87 g / cc (e.g., about 1.74 g / cc to about 1.85 g / cc).

[0050] The as-deposited amorphous carbon film after carbon implantation may have a refractive index (n)(633 nm) of greater than 2.04, e.g., approximately 2.2 (e.g., about 2.1 to 2.2). The as-deposited amorphous carbon film may have a k value (k(at 633 nm)) of less than 1.0, e.g., (e.g., about 0.5 to about 0.8; about 0.6 to about 0.7). The as-deposited amorphous carbon film after implantation may have a Young's modulus (GPa) of about 70 to about 200 GPa (e.g., about 120 to about 180 GPa; or about 130 to about 170 GPa). The as-deposited amorphous carbon film after implantation may have a hardness (GPa) of about 14 GPa to about 22 GPa (e.g., about 15 GPa to about 20 GPa; or about 16 GPa to about 19 GPa). The as-deposited amorphous carbon film after implantation may have a stress (MPa) of about −600 MPa to about 0 MPa (e.g., about −400 MPa to about 0 Pa; about −350 MPa to about 0 MPa). The as-deposited amorphous carbon film may have a density (g / cc) greater than 1.9 g / cc, for example, approximately 2.1 g / cc (e.g., about 1.95 g / cc to about 2.1 g / cc).

[0051] FIG. 2 illustrates a flow diagram of a method 200 for forming a diamond-like carbon layer on a film stack disposed on a substrate, according to one or more implementations of the present disclosure. FIGS. 3A-3H illustrate schematic cross-sectional views of a substrate structure illustrating a hard mask formation sequence according to method 200. Method 200 is described below in the context of a hard mask layer that may be formed on a film stack utilized to fabricate stair-like structures in a film stack for a three-dimensional semiconductor device, although method 200 may also be advantageously used in other device manufacturing applications. It should be further understood that the operations illustrated in FIG. 2 may be performed simultaneously and / or in a different order than that illustrated in FIG. 2.

[0052] Method 200 begins in operation 210 by positioning a substrate 302 in a processing chamber, such as plasma processing chamber 100 shown in Figure 1. Substrate 302 may be substrate 101 shown in Figure 1. Substrate 302 may be part of a film stack 300 formed thereon.

[0053] In one implementation, the surface of the substrate 110 shown in FIG. 1 is substantially flat. Alternatively, the substrate 110 may have patterned structures. For example, the substrate 110 may have a surface with trenches, holes, or vias formed therein. The substrate 110 may have a substantially flat surface with targeted stepped structures formed on or within the surface. While the substrate 110 is depicted as a single entity, it may contain one or more materials used to form semiconductor devices (such as metal contacts, trench isolation, gates, bit lines, or any other interconnect features). The substrate 110 may include one or more metal layers, one or more dielectric materials, semiconductor materials, and combinations thereof used to fabricate semiconductor devices. For example, the substrate 110 may include an oxide material, a nitride material, a polysilicon material, etc., depending on the application. In one implementation targeted for memory applications, the substrate 110 may include a silicon substrate material, an oxide material, and a nitride material (with or without polysilicon present therebetween).

[0054] In another implementation, substrate 110 may include multiple alternating oxide and nitride materials (i.e., oxide-nitride-oxide (ONO)) deposited on the surface of substrate 110 (not shown). In various implementations, substrate 110 may include multiple alternating oxide and nitride materials, one or more oxide or nitride materials, polysilicon or amorphous silicon materials, oxide alternating with amorphous carbon, oxide alternating with polysilicon, undoped silicon alternating with doped silicon, undoped polysilicon alternating with doped polysilicon, or undoped amorphous silicon alternating with doped amorphous silicon. Substrate 110 may be any substrate or material surface on which film processing is performed. For example, the substrate 110 can be a material such as crystalline silicon, silicon oxide, silicon oxynitride, silicon nitride, strained silicon, silicon germanium, tungsten, titanium nitride, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or unpatterned wafers, silicon on insulator (SOI), carbon doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, low-k dielectrics, and combinations thereof.

[0055] The film stack 300 includes a substrate 302 and an underlayer 304. As used herein, the underlayer 304 includes any layer disposed below an amorphous carbon hard mask. For example, the amorphous carbon hard mask 306 can be disposed directly above the underlayer 304 such that the amorphous carbon hard mask 306 and the underlayer 304 are in physical contact with each other. In one implementation, the underlayer 304 includes a single layer. In another implementation, the underlayer 304 includes a dielectric stack.

[0056] In operation 220, as shown in FIG. 3B, an amorphous carbon mask 306 is formed on an underlayer 304 disposed above the substrate 302. The amorphous carbon hard mask 306 is deposited above the underlayer 304 by a blanket deposition process. In some implementations, the amorphous carbon hard mask 306 is deposited according to a method 400 described in the process flow diagram of FIG. 4. The amorphous carbon hard mask 306 may be deposited to a thickness corresponding to the subsequent etching requirements of the underlayer 304. In one example, the amorphous carbon hard mask has a thickness between about 0.5 μm and about 1.5 μm, for example, about 1.0 μm.

[0057] In operation 230, an ion implantation process dopes the amorphous carbon hard mask 306 with a dopant to form a doped amorphous carbon hard mask 312 doped with the dopant, as shown in FIG. 3C . Any suitable doping technique may be used. In one implementation, a plasma immersion ion implantation technique is employed to implant the dopant or inert species. In one implementation, a beam-line implantation technique is employed to implant the dopant or inert species. In one implementation, a conformal doping technique, such as a plasma doping (PLAD) technique, may be employed to implant the dopant or inert species.

[0058] Suitable ion species can be generated from various precursor materials, such as carbon-, boron-, nitrogen-, silicon-, phosphorus-, helium-, argon-, neon-, krypton-, xenon-, beryllium-, and germanium-containing materials. In one implementation, the dopant or inert species is selected from carbon, boron-, nitrogen-, silicon-, phosphorus-, argon-, helium-, neon-, krypton-, xenon-, beryllium-, germanium-, or a combination thereof. An example of a carbon-containing precursor gas includes CH4. In one implementation, various precursor materials are generated from combinations of precursor materials, including, for example, CH4 / N2, CH4 / He, N2 / He, CH4 / Ne, CH4 / Ar, CH4 / Ne, CH4 / Kr, or CH4 / Xe.

[0059] In the schematic diagram, ions 310 bombard the amorphous carbon hard mask 306 and generally penetrate the amorphous carbon hard mask 306 to form a doped amorphous carbon hard mask 312 implanted with a dopant or inert species. The ions 310 penetrate the amorphous carbon hard mask 306 to various depths depending on the type and size of the ions and the power and bias used to activate the ions 310. The species of the ions 310 can be tailored to provide increased etch selectivity of the underlayer 304. As such, the implanted species can be any monomeric or molecular ions adapted to enhance the etch selectivity of the amorphous carbon hard mask 306.

[0060] The ion implantation process may be performed by a beamline or plasma implantation tool. Exemplary systems utilized to perform the implantation process include, for example, the VARIAN VIISta® Trident system, the VARIAN VIISta® Thermion system, the VARIAN VIISta® Medium Current Thermion system, the VIISta® 3000XP system, the VIISta® 900XP system, the VIISta® HCP system, and the VIISta® PLAD system, available from Applied Materials, Inc. of Santa Clara, California. While described with respect to the above systems, it is contemplated that systems from other manufacturers may also be utilized to perform the ion implantation process.

[0061] In one implementation, the ion implantation process implants a dopant or inert species into the amorphous carbon hard mask 306. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorous, argon, helium, neon, krypton, beryllium, germanium, xenon, or a combination thereof. In one implementation, for 3D NAND applications where the carbon hard mask thickness application is in the range of 10 kÅ to 50 kÅ, the dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorous, argon, helium, neon, krypton, beryllium, germanium, xenon, or a combination thereof. Add energy toThe implant energy utilized to modify the carbon hard mask is between about 60 keV and about 300 keV (single or multiple implant energies may be applied). As an example of a carbon implant, an energy of 300 keV will modify about 8 kÅ of the carbon hard mask. Multiple implant energies may be applied to modify the carbon hard mask. For example, multiple energies of 60 keV, 120 keV, 180 keV, 240 keV, 300 keV, or some variation may be applied. The choice of implant species and multiple energies will depend on the type of dopant utilized, the type of material utilized as the amorphous carbon hard mask 306, and the desired uniform thickness modification of the carbon hard mask. In another implementation, for DRAM or other technologies such as logic or emerging memory technologies, where the carbon hard mask thickness may range from 500 Å to 4 kÅ, the dopant Add energy to The implantation energy utilized to achieve the desired implantation is between about 1 keV and about 60 keV (e.g., between about 5 keV and about 60 keV; between about 1 keV and about 15 keV; between about 10 keV and about 35 keV; between about 20 keV and about 30 keV; or between about 20 keV and about 25 keV), depending on the type of dopant utilized, the type of material utilized as the amorphous carbon hard mask 306, and the desired implantation depth.

[0062] In one implementation, for 3D NAND applications where the carbon hard mask thickness can range from 10 kÅ to 50 kÅ, the ion dose (ions / cm 2 ) can be approximately 1×10 depending on the type of dopant used, the type of material used as the amorphous carbon hard mask 306, and the targeted implant depth. 13 ions / cm 2 and about 5 × 10 15 ions / cm 2 between (e.g., about 1 × 10 14 ions / cm 2 and about 3 x 10 15 ions / cm 2 Between; about 5 × 10 14 ions / cm 2 and approximately 2 × 10 15 ions / cm2 In another implementation, the carbon hard mask thickness can range from 500 Å to 4 kÅ, and for DRAM or other technologies, such as logic or emerging memory technologies, the ion dose (ions / cm 2 ) can be approximately 5×10 depending on the type of dopant used, the type of material used as the amorphous carbon hard mask 306, and the targeted implant depth. 13 ions / cm 2 and about 5 × 10 16 ions / cm 2 between (e.g., about 1 × 10 14 ions / cm 2 and about 5 × 10 16 ions / cm 2 Between; about 5 × 10 14 ions / cm 2 and approximately 2 × 10 16 ions / cm 2 Between approx. 1 x 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2 It is between.

[0063] In one implementation where a PLAD implantation technique is used, dopants or inert species are Add energy to The implantation energy used to achieve this is approximately 1×10 15 ions / cm 2 and about 5 × 10 17 ions / cm 2 between (e.g., about 3 × 10 15 ions / cm 2 and about 3 x 10 17 ions / cm 2 Between; about 5 × 10 15 ions / cm 2 and about 5 × 10 16 ions / cm 2 Between; about 5 × 10 15 ions / cm 2 and approximately 2 × 10 16 ions / cm 2 or approximately 5 x 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2and between about 1 kV and about 15 kV (e.g., between about 1 kV and about 15 kV; between about 1 kV and about 15 kV; between about 2 kV and about 12 kV; between about 4 kV and about 10 kV; or between about 20 kV and about 25 kV), with an ion dose range of between about 1 kV and about 15 kV (e.g., between about 1 kV and about 15 kV; between about 2 kV and about 12 kV; between about 4 kV and about 10 kV; or between about 20 kV and about 25 kV). Add energy to The implantation energy used to achieve this is approximately 1×10 15 ions / cm 2 and about 3 x 10 17 ions / cm 2 The ion dose range is between about 1 kV and about 15 kV.

[0064] In one implementation, the target temperature is between about −100° C. and about 550° C. (e.g., between about −100° C. and about 200° C.; between about −100° C. and about 0° C.; between about −100° C. and about 50° C.; between about 0° C. and about 100° C.; or between about 150° C. and about 550° C.). In another implementation, the target temperature is between about −100° C. and about 500° C. (e.g., between about −100° C. and about 200° C.; between about −100° C. and about 0° C.; between about −100° C. and about 50° C.; between about 0° C. and about 50° C.; or between about 50° C. and about 400° C.). In one example, if a low-temperature implant is performed, the target temperature for the implant is between about −100° C. and about 0° C. In another example, if a room-temperature implant is performed, the target temperature for the implant is between about 10° C. and about 100° C. In yet another example, if a hot implant is performed, the target temperature for the implant is from about 150°C to about 550°C.

[0065] Generally, increasing the hardness of the amorphous carbon hard mask 306 reduces line bending in the high aspect ratio structures of the underlying layer 304 after undoping the amorphous carbon hard mask 306. The implanted ions 310 are believed to abstract residual hydrogen atoms from dangling carbon-hydrogen bonds in the amorphous carbon hard mask 306, forming carbide structures within the amorphous carbon hard mask 306. The carbide structures exhibit increased hardness compared to an undoped hard mask. Furthermore, the implanted ions 310 are believed to occupy interstitial voids present within the amorphous carbon hard mask 306, thereby increasing the density of the amorphous carbon hard mask 306. The increased density further increases the mechanical integrity of the amorphous carbon hard mask 306.

[0066] In one implementation, following the ion implantation process, the film stack 300 is thermally treated. Suitable post-ion implantation thermal treatments include UV treatment, thermal annealing, and laser annealing. The thermal treatment of the doped amorphous carbon hard mask 312 further incorporates the implanted ions 310 into the framework of the doped amorphous carbon hard mask 312. For example, the implanted ions 310 may be redistributed within the doped amorphous carbon hard mask 312 to form a more uniform doping profile. It is believed that the thermal treatment may increase the interaction and bonding between the doped amorphous carbon hard mask 312 and the implanted ions 310. The redistribution and bonding of the implanted ions 310 may serve to further increase the hardness, density, and etch selectivity of the doped amorphous carbon hard mask 312. In one implementation, the annealing process is performed in a plasma processing chamber, such as the plasma processing chamber 100. In another implementation, the annealing process is performed in a separate annealing chamber.

[0067] In operation 240, a patterned photoresist layer 320 is formed over the doped amorphous carbon hard mask 312, which is doped with a dopant or inert species, as shown in FIG. 3D. Features or patterns can be transferred into the photoresist layer 320 from a photomask using an energy source, such as light energy. In one implementation, the photoresist layer 320 is a polymer material, and the patterning process is performed by a 193 nanometer immersion photolithography process or other similar photolithography process. Similarly, a laser can also be used to perform the patterning process.

[0068] In operation 250, the doped amorphous carbon hard mask 312 is opened, for example, by a plasma etching process, to form a doped patterned amorphous carbon hard mask 322, as shown in Figure 3E. The plasma etching process may be performed in a chamber similar to the chamber described with respect to Figure 3C.

[0069] In operation 260, photoresist layer 320 is removed, as shown in Figure 3F. Photoresist layer 320 can be removed by a variety of convenient photoresist removal processes.

[0070] In operation 270, the underlayer 304 is etched, as shown in FIG. 3G. Etching of the underlayer 304 may be performed in a plasma processing chamber, such as the chamber and system described with respect to FIG. 1B. An etchant, such as a fluorocarbon, removes exposed portions of the underlayer 304. The active species of the etchant do not substantially react with the material of the doped, patterned amorphous carbon hard mask 322, the implanted ions 310. Thus, the etchant is selective to the underlayer 304 material. Suitable examples of etchants include CF, CHF, HBr, BCl, and Cl, among others. The etchant may be provided with an inert carrier gas.

[0071] In operation 280, the doped and patterned amorphous carbon hard mask 322 is removed. The doped and patterned amorphous carbon hard mask 322 may be removed by any convenient hard mask removal process. In one example, an oxygen plasma is utilized to remove the doped and patterned amorphous carbon hard mask 322. The resulting film stack 300 includes an underlayer 304 having features 324, such as high aspect ratio features, formed therein. The film stack 300 may then undergo further processing to form a functional semiconductor device.

[0072] 4 is a process flow diagram illustrating one implementation of a method 400 for depositing an amorphous carbon film according to implementations described herein. In one implementation, the method 400 may be used to deposit the amorphous carbon film of operation 220. The method 400 begins in operation 410 by providing a substrate in a processing region of a processing chamber. The processing chamber may be the plasma processing chamber 100 shown in FIG. 1. The substrate may be the substrate 110 shown in FIG. 1 or the substrate 302 shown in FIGS. 3A-3H.

[0073] In operation 420, a hydrocarbon-containing gas mixture is flowed into the processing region 146. The hydrocarbon-containing gas mixture may be flowed from a gas source 154 through the gas distribution showerhead 128 into the processing region 146. The gas mixture may include at least one hydrocarbon source and / or carbon-containing source. The gas mixture may further include an inert gas, a diluent gas, a nitrogen-containing gas, or a combination thereof. The hydrocarbon source and / or carbon-containing source may be any liquid or gas. In one example, the precursor is a vapor at room temperature, simplifying the hardware for metering, controlling, and delivering the material to the chamber.

[0074] In one implementation, the hydrocarbon source is a gaseous hydrocarbon, e.g., a straight chain hydrocarbon. In one implementation, the hydrocarbon compound is a C x H ywhere x ranges from 1 to 20 and y ranges from 1 to 20. In one implementation, the hydrocarbon compound is an alkane. Suitable hydrocarbon compounds include, for example, methane (CH), acetylene (C2H2), ethylene (C2H4), ethane (C2H6), propylene (C3H6), and butylenes (C4H8), cyclobutane (C4H8), and methylcyclopropane (C4H8). Suitable butylenes include 1-butene, 2-butene, and isobutylene. Other suitable carbon-containing gases include carbon dioxide (CO2) and carbon tetrafluoride (CF4). In one example, C3H6 is preferred because it forms a more suitable intermediate species, allowing for improved surface mobility.

[0075] A suitable diluent gas, such as helium (He), argon (Ar), hydrogen (H), nitrogen (N), ammonia (NH), or a combination thereof, among others, may be added to the gas mixture. Ar, He, and N are used to control the density and deposition rate of the amorphous carbon layer. In some cases, the addition of N and / or NH may be used to control the hydrogen ratio of the amorphous carbon layer, as described below. Alternatively, no diluent gas may be used during deposition.

[0076] A nitrogen-containing gas may be provided along with the hydrocarbon-containing gas mixture in the plasma processing chamber 100. Suitable nitrogen-containing compounds include, for example, pyridine, aliphatic amines, amines, nitriles, ammonia, and similar compounds.

[0077] Inert gases such as argon (Ar) and / or helium (He) can be supplied into the plasma processing chamber 100 along with the hydrocarbon-containing gas mixture. Other inert gases, such as nitrogen (N) and nitric oxide (NO), can also be used to control the density and deposition rate of the amorphous carbon layer. Additionally, a wide variety of other process gases can be added to the gas mixture to modify the properties of the amorphous carbon material. In one implementation, the process gas can be a reactive gas, such as hydrogen (H), ammonia (NH), a mixture of hydrogen (H) and nitrogen (N), or a combination thereof. The addition of H and / or NH can be used to control the hydrogen ratio (e.g., carbon-to-hydrogen ratio) of the deposited amorphous carbon layer. The ratio of hydrogen present in the amorphous carbon film controls the layer properties (e.g., reflectivity).

[0078] Optionally, in operation 430, the pressure in the processing region is stabilized for a predetermined RF-on delay time period. The predetermined RF-on delay period is a fixed-time delay defined as the period between the introduction of the hydrocarbon-containing gas mixture into the processing region and the collision or generation of the plasma in operation 430. Any suitable fixed time delay may be used to achieve the target condition. The length of the RF-on delay period is typically selected so that the hydrocarbon-containing or carbon-containing gas mixture does not, or does not substantially, begin to thermally decompose in the processing region.

[0079] In operation 440, an RF plasma is generated in the processing region to deposit an amorphous carbon film, such as the amorphous carbon hard mask 306. The plasma can be formed by capacitive or inductive means and can be applied by coupling RF power to the precursor gas mixture. The RF power is dual-frequency RF power, having high-frequency and low-frequency components. The RF power is typically applied at a power level between about 50 W and about 2,500 W (e.g., between about 2,000 W and about 2,500 W), which can be all high-frequency RF power (e.g., a frequency of about 13.56 MHz) or a mixture of high-frequency and low-frequency power (e.g., a frequency of about 300 kHz). For many applications, the plasma is maintained for a period of time to deposit an amorphous carbon layer having a thickness between about 100 Å and about 5,000 Å. Once the target thickness of the amorphous carbon film is reached, the flow of the hydrocarbon-containing gas mixture can be stopped. The process of operation 440 may be performed simultaneously, sequentially, or partially overlapping with the processes of operations 420 and 430 .

[0080] In any of the PECVD implementations described herein, during deposition of the amorphous carbon film, the chamber, the wafer, or both may be maintained at a temperature between about 200°C and about 700°C (e.g., between about 400°C and about 700°C; or between about 500°C and about 700°C). The chamber pressure may range from about 1 Torr to about 10 Torr (e.g., between about 2 Torr and about 8 Torr; or between about 4 Torr and about 8 Torr). The distance (i.e., "spacing") between the susceptor and the gas distribution showerhead may be set between about 200 mils and about 1,000 mils (e.g., between about 200 mils and about 600 mils; between about 300 mils and about 1,000 mils; or between about 400 mils and about 600 mils).

[0081] The amorphous carbon film may be deposited to have a thickness between about 10 Å and about 50,000 Å (eg, between about 300 Å and about 30,000 Å; between about 500 Å and about 1,000 Å). Excess process gases and by-products from the deposition of the season layer may then be removed from the processing area by performing an optional purge / evacuation process.

[0082] FIG. 5A shows a plot 500 of in-plane strain versus film stress (MPa) for amorphous carbon films (520, 522, and 530, 532) formed in accordance with implementations of the present disclosure compared to amorphous carbon films (510, 512, and 514) formed using prior art techniques. Note that the amorphous carbon films (520, 522, and 530, 532) formed in accordance with implementations of the present disclosure are shown before carbon dopant implantation. FIG. 5B shows a plot 550 of Young's modulus (GPa) versus film stress (MPa) for the amorphous carbon film of FIG. 5A. As shown in FIGS. 5A-5B, the amorphous carbon films (520, 522, and 530, 532) formed in accordance with implementations described herein achieved low in-plane strain and improved elastic modulus despite high stress (e.g., −1200 MPa). The subsequent carbon dopant implantation process described herein reduced compressive film stress by approximately 4 times and improved elastic modulus by approximately 1.4 times.

[0083] FIG. 6 shows a flow diagram of a method 600 for forming a diamond-like carbon layer on a film stack disposed on a substrate according to one or more implementations of the present disclosure. FIGS. 7A-7I show schematic cross-sectional views of a substrate structure illustrating a hard mask formation sequence according to method 600. Method 600 and FIGS. 7A-7I illustrate a post-patterning implant in which the amorphous carbon film is implanted after patterning the amorphous carbon film. The post-patterning implant can be performed at a 0-degree implant tilt angle, or at an angle into the amorphous carbon film, with an associated twist angle from 0 degrees to about 360 degrees that allows ions to penetrate only the hard mask. In one example, if the line and space features of a carbon hard mask run in one direction rather than two perpendicular directions, the implant can be split into two implants, each implanted at half the desired dose, e.g., 1×10 16 ions / cm 2 The dose is 5.0 x 1015 ions / cm 2 The substrate is implanted every 180 degrees of rotation, so 1×10 16 ions / cm 2 6. The carbon hard mask is deposited to a desired dose of 1000 .mu.m. The result is that both sides of the carbon hard mask feature are uniformly implanted. While method 200 is described below in the context of a hard mask layer that may be formed on a film stack utilized to fabricate stair-like structures in the film stack for a three-dimensional semiconductor device, method 600 may also be advantageously used in other device fabrication applications. Furthermore, it should be understood that the operations depicted in FIG. 6 may be performed simultaneously and / or in a different order than depicted in FIG. 6.

[0084] Method 600 begins in operation 610 by positioning a substrate 702 in a processing chamber, such as plasma processing chamber 100 described in Figure 1. Substrate 702 may be substrate 101 shown in Figure 1. Substrate 702 may be part of a film stack 700 having additional layers formed thereon.

[0085] In one implementation, the surface of the substrate 702 shown in FIG. 1 is substantially flat. Alternatively, the substrate 702 may have patterned structures. For example, the substrate 702 may have a surface with trenches, holes, or vias formed therein. The substrate 702 may have a substantially flat surface with targeted stepped structures formed on or within the surface. While the substrate 702 is depicted as a single entity, it may contain one or more materials used to form semiconductor devices (such as metal contacts, trench isolation, gates, bitlines, or any other interconnect features). The substrate 702 may include one or more metal layers, one or more dielectric materials, semiconductor materials, and combinations thereof used to fabricate semiconductor devices. For example, the substrate 702 may include an oxide material, a nitride material, a polysilicon material, etc., depending on the application. In one implementation targeted for memory applications, the substrate 702 may include a silicon substrate material, an oxide material, and a nitride material (with or without polysilicon present therebetween).

[0086] In another implementation, the substrate 702 may include multiple alternating oxide and nitride materials (i.e., oxide-nitride-oxide (ONO)) deposited on the surface of the substrate 702 (not shown). In various implementations, the substrate 702 may include multiple alternating oxide and nitride materials, one or more oxide or nitride materials, polysilicon or amorphous silicon materials, oxide alternating with amorphous carbon, oxide alternating with polysilicon, undoped silicon alternating with doped silicon, undoped polysilicon alternating with doped polysilicon, or undoped amorphous silicon alternating with doped amorphous silicon. The substrate 702 may be any substrate or material surface on which film processing is performed. For example, the substrate 702 can be a material such as crystalline silicon, silicon oxide, silicon oxynitride, silicon nitride, strained silicon, silicon germanium, tungsten, titanium nitride, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or unpatterned wafers, silicon on insulator (SOI), carbon doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, low-k dielectrics, and combinations thereof.

[0087] The film stack 700 includes a substrate 702 and an underlayer 704. As used herein, the underlayer 704 includes any layer disposed below an amorphous carbon hard mask. For example, the amorphous carbon hard mask 706 can be disposed directly above the underlayer 704 such that the amorphous carbon hard mask 706 and the underlayer 704 are in physical contact with each other. In one example, the underlayer 704 includes a single layer. In another example, the underlayer 704 includes multiple layers, such as a dielectric stack.

[0088] In operation 620, as shown in FIG. 7B, an amorphous carbon mask 706 is formed on an underlayer 704 disposed above the substrate 702. The amorphous carbon hard mask 706 may be deposited above the underlayer 704 by a blanket deposition process. In some implementations, the amorphous carbon hard mask 706 is deposited according to the method 400 described in the process flow diagram of FIG. 4. The amorphous carbon hard mask 706 may be deposited to a thickness corresponding to the subsequent etching requirements of the underlayer 704. In one example, the amorphous carbon hard mask has a thickness between about 0.5 μm and about 1.5 μm, for example, about 1.0 μm.

[0089] In operation 630, a patterned photoresist layer 720 is formed over the amorphous carbon hard mask 706, as shown in FIG. 7C. Features or patterns can be transferred into the photoresist layer 720 from a photomask using an energy source, such as light energy. In one implementation, the photoresist layer 320 is a polymer material, and the patterning process is performed by a 193 nanometer immersion photolithography process or other similar photolithography process. Similarly, a laser can also be used to perform the patterning process.

[0090] In operation 640, the doped amorphous carbon hard mask 706 is opened, for example, by a plasma etching process, to form a patterned amorphous carbon hard mask 722 having openings or apertures, as shown in FIG. 7D. Any suitable plasma etching process may be used. In one example, the plasma etching process may be performed in a chamber similar to the chamber described with respect to FIG. 7F.

[0091] 7E, photoresist layer 720 is removed to expose the top surface of patterned amorphous carbon hard mask 722. Photoresist layer 320 can be removed by a variety of convenient photoresist removal processes.

[0092] In operation 660, an ion implantation process dopes the patterned amorphous carbon hard mask 722 with a dopant or inert species to form a doped, patterned amorphous carbon hard mask 732 doped with a dopant or inert species, as shown in FIG. 7F. The ion implantation process of operation 660 can be performed at an implant tilt angle of 0 degrees (perpendicular to the plane defined by the top surface of the patterned amorphous carbon hard mask 722) or at an implant tilt angle greater than 0 degrees (±θ relative to the plane defined by the top surface of the patterned amorphous carbon hard mask 722). As shown in FIG. 7F, for some ion species that enhance the etch rate of the underlayer 704, the implantation process can be performed at 0 degrees, resulting in modified and / or doped portions 742a and 742b. In some examples, the selective modification of the underlayer 704 improves the etch characteristics of the modified portions 742a, 742b. In another example, for some ion species that result in a slow etch rate of the underlayer 704, the ion implantation process can be performed at an implant tilt angle such that the exposed portions of the underlayer 704 are not modified or doped, as shown in FIG. 7G. The implant tilt angle generally depends on the size of the opening in the patterned amorphous carbon hard mask. Post-patterning implants can be performed at an implant tilt angle of 0 degrees, or at an angle into the amorphous carbon film, with an associated twist angle between 0 degrees and approximately 360 degrees that allows ions to penetrate only the hard mask. The implant can be split into multiple implants, with each implant performed at a different tilt angle. The dose for each of the multiple implants can be determined by splitting the desired total dose into multiple implants. For example, if the line and space features in the carbon hard mask run in one direction rather than two perpendicular directions, the implant can be split into two implants, with each implant at half the desired dose, e.g., 1×10 16 ions / cm 2 The dose is 5.0 x 10 15 ions / cm 2 The substrate is implanted every 180 degrees of rotation, so 1×1016 ions / cm 2 The desired dose of 1000 .ANG. is deposited onto the carbon hard mask feature, resulting in a uniform implant on both sides of the feature. A wide range of implant tilt angles is possible, for example, implant angles from about 0.1 degrees to about 80 degrees (e.g., from about 1 degree to about 80 degrees; or from about 10 degrees to about 50 degrees) excluding zero degrees may be used.

[0093] Any suitable doping technique may be used. In one example, a plasma immersion ion implantation technique is employed to implant the dopant or inert species. In another example, a beam-line implantation technique is employed to implant the dopant or inert species. In yet another example, a conformal doping technique, such as a plasma doping (PLAD) technique, is employed to implant the dopant or inert species.

[0094] Suitable ion species can be generated from various precursor materials, such as carbon-, boron-, nitrogen-, silicon-, phosphorus-, helium-, argon-, neon-, krypton-, xenon-, beryllium-, and germanium-containing materials. In one implementation, the dopant or inert species is selected from carbon, boron-, nitrogen-, silicon-, phosphorus-, argon-, helium-, neon-, krypton-, xenon-, beryllium-, germanium-, or a combination thereof. An example of a carbon-containing precursor gas includes CH4. In one implementation, various precursor materials are generated from combinations of precursor materials, including, for example, CH4 / N2, CH4 / He, N2 / He, CH4 / Ne, CH4 / Ar, CH4 / Ne, CH4 / Kr, or CH4 / Xe.

[0095] In the schematic diagram of FIG. 7F , ions 710 impact the patterned amorphous carbon hard mask 722 at a 0-degree implant tilt angle, generally penetrating the patterned amorphous carbon hard mask 722 and exposed portions of the underlayer 704 to form a doped, patterned amorphous carbon hard mask 732 and modified portions 742 a, 742 b (modified and / or implanted with dopants or inert species). The ions 710 penetrate the patterned amorphous carbon hard mask 722 and underlayer 704 to various depths, depending on the type and size of the ions and the power and bias used to activate the ions 710. The species of the ions 710 can be tailored to provide increased etch selectivity of the underlayer 704. Thus, the implanted species can be any monomeric or molecular ions adapted to enhance the etch selectivity of the patterned amorphous carbon hard mask 722.

[0096] Alternatively, as shown in the schematic diagram of FIG. 7G, the implant process or operation 660 is performed at an angle such that the exposed portions of the underlayer 704 are not modified or doped. The implant tilt angle varies depending on the size of the opening. The implant may further include a twist angle. A wide range of implant tilt angles are possible, for example, implant angles from about 0.1 degrees to about 80 degrees (e.g., about 1 degree to about 80 degrees) excluding zero degrees, and from about −0.1 degrees to about −80 degrees (e.g., −1 degree to about −80 degrees) may be used. The twist angle may be between 0 degrees and 360 degrees, which allows the ions to penetrate only the hard mask. As shown in FIG. 7G, ions 750 impact the patterned amorphous carbon hard mask 722 and generally penetrate the patterned amorphous carbon hard mask 722 but generally do not penetrate the exposed portions of the underlayer 704.

[0097] The ion implantation process may be performed by a beamline or plasma implantation tool. Exemplary systems utilized to perform the implantation process include, for example, the VARIAN VIISta® Trident system, the VARIAN VIISta® Thermion system, the VARIAN VIISta® Medium Current Thermion system, the VIISta® 3000XP system, the VIISta® 900XP system, the VIISta® HCP system, and the VIISta® PLAD system, available from Applied Materials, Inc. of Santa Clara, California. While described with respect to the above systems, it is contemplated that systems from other manufacturers may also be utilized to perform the ion implantation process.

[0098] In one implementation, the ion implantation process of operation 660 implants a dopant or inert species into the patterned amorphous carbon hard mask 722. The dopant or inert species is selected from carbon, boron, nitrogen, silicon, phosphorus, argon, helium, neon, krypton, xenon, beryllium, germanium, or a combination thereof. In one implementation, the dopant Add energy to The implantation energy utilized to implant the amorphous carbon hard mask 722 is between about 60 keV and about 300 keV (e.g., between about 60 keV and about 300 keV). The implantation can be performed at a single energy or multiple energies between 60 keV and 300 keV, depending on the type of dopant utilized, the type of material utilized as the patterned amorphous carbon hard mask 722, and the desired implant depth. In another implementation, the dopant Add energy toThe implantation energy utilized to perform the implantation is between about 1 keV and about 60 keV (e.g., between about 5 keV and about 60 keV; between about 1 keV and about 15 keV; between about 10 keV and about 35 keV; between about 20 keV and about 30 keV; or between about 20 keV and about 25 keV). The implantation can be performed at a single energy or multiple energies between 1 keV and 60 keV, depending on the type of dopant utilized, the type of material utilized as the patterned amorphous carbon hard mask 722, and the targeted implant depth.

[0099] In one implementation, the ion dose (ions / cm 2 ) can be approximately 1×10 depending on the type of dopant used, the type of material used as the amorphous carbon hard mask 306, and the targeted implant depth. 13 ions / cm 2 and about 5 × 10 17 ions / cm 2 between (e.g., about 1 × 10 15 ions / cm 2 and about 3 x 10 17 ions / cm 2 Between approx. 1 x 10 14 ions / cm 2 and about 5 × 10 16 ions / cm 2 Between approx. 1 x 10 14 ions / cm 2 and approximately 2 × 10 16 ions / cm 2 Between approx. 1 x 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2 Between; about 5 × 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2 In another implementation, the ion dose (ions / cm 2 ) can be approximately 5×10 depending on the type of dopant used, the type of material used as the patterned amorphous carbon hard mask 722, and the targeted implant depth. 13 ions / cm2 and about 5 × 10 17 ions / cm 2 between (e.g., about 1 × 10 15 ions / cm 2 and about 3 x 10 17 ions / cm 2 Between approx. 1 x 10 14 ions / cm 2 and about 5 × 10 16 ions / cm 2 Between approx. 1 x 10 14 ions / cm 2 and approximately 2 × 10 16 ions / cm 2 Between approx. 1 x 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2 Between; about 5 × 10 15 ions / cm 2 and approximately 1 x 10 16 ions / cm 2 (between ).

[0100] In one implementation, when a PLAD implantation technique is used, dopants or inert species Add energy to The implantation energy used to achieve this is approximately 1×10 15 ions / cm 2 and about 5 × 10 17 ions / cm 2 , for example, about 2 x 10 15 ions / cm 2 and about 3 x 10 17 ions / cm 2 Between; about 5 × 10 15 ions / cm 2 and about 5 × 10 16 ions / cm 2 or approximately 1 x 10 16 ions / cm 2 and approximately 1 x 10 17 ions / cm 2 and between about 1 kV and about 15 kV (e.g., between about 1 kV and about 12 kV; between about 2 kV and about 10 kV), with an ion dose range between Add energy to The implantation energy used to achieve this is approximately 1×10 15ions / cm 2 and about 3 x 10 17 ions / cm 2 The ion dose range is between about 1 kV and about 15 kV.

[0101] In one implementation, the target temperature for the implantation process or operation 660 is between about −100° C. and about 550° C. (e.g., between about −100° C. and about 200° C.; between about −100° C. and about 0° C.; between about −100° C. and about 50° C.; between about 0° C. and about 100° C.; or between about 150° C. and about 550° C.). In another implementation, the target temperature for the implantation is between about −100° C. and about 500° C. (e.g., between about −100° C. and about 200° C.; between about −100° C. and about 0° C.; between about −100° C. and about 50° C.; between about 0° C. and about 50° C.; or between about 50° C. and about 400° C.). In one example, if a low-temperature implantation is performed, the target temperature for the implantation is between about −100° C. and about 0° C. In another example, if a room-temperature implantation is performed, the target temperature for the implantation is between about 10° C. and about 100° C. In yet another example, if a hot implant is performed, the target temperature for the implant is from about 150°C to about 550°C.

[0102] In one implementation, following the ion implantation process, the film stack 700 is thermally treated. Suitable post-ion implantation thermal treatments include UV treatment, thermal annealing, and / or laser annealing. Thermal treatment of the doped-patterned amorphous carbon hard mask 732 further incorporates the implanted ions 710 into the framework of the doped-patterned amorphous carbon hard mask 732. For example, the implanted ions 710 may be redistributed within the doped-patterned amorphous carbon hard mask 732 to form a more uniform doping profile. It is believed that the thermal treatment may increase the interaction and bonding between the doped-patterned amorphous carbon hard mask 732 and the implanted ions 710. The redistribution and bonding of the implanted ions 710 may serve to further increase the hardness, density, and etch selectivity of the doped-patterned amorphous carbon hard mask 732. In one implementation, the annealing process is performed in a plasma processing chamber, such as plasma processing chamber 100. In another implementation, the annealing process is performed in a separate annealing chamber.

[0103] Generally, increasing the hardness of the doped, patterned amorphous carbon hard mask 732 reduces line bending in the high aspect ratio structures of the underlying layer 704. The implanted ions 710, 750 are believed to abstract residual hydrogen atoms from dangling carbon-hydrogen bonds in the amorphous carbon hard mask 706, forming carbide structures within the amorphous carbon hard mask 706. The carbide structures exhibit increased hardness compared to an undoped hard mask. Furthermore, the implanted ions 710, 750 are believed to occupy interstitial voids 310 present within the doped, patterned amorphous carbon hard mask 732, thereby increasing the density of the doped, patterned amorphous carbon hard mask 732. Furthermore, the implanted ions 710, 750 are believed to disrupt SPs in the amorphous carbon hard mask 706. 3 It is believed to increase carbon-to-carbon bond formation. The increased density further increases the mechanical integrity of the doped patterned amorphous carbon mask 732 .

[0104] In operation 670, the underlayer 304 is etched, as shown in FIG. 7H. Etching of the underlayer 704 may be performed in a plasma processing chamber, such as the chamber and system described with respect to FIG. 1. An etchant, such as a fluorocarbon, removes exposed portions of the underlayer 704. The active species of the etchant do not substantially react with the material of the doped, patterned amorphous carbon hard mask 732, the implanted ions 710. Thus, the etchant is selective to the underlayer 704 material. Suitable examples of etchants include CF, CHF, HBr, BCl, and Cl, among others. The etchant may be provided with an inert carrier gas.

[0105] In operation 680, the doped and patterned amorphous carbon hard mask 732 is removed, as shown in FIG. 7I. The doped and patterned amorphous carbon hard mask 732 may be removed by any convenient hard mask removal process. In one example, an oxygen plasma is utilized to remove the doped and patterned amorphous carbon hard mask 732. The resulting film stack 700 includes an underlayer 704 having features 724, such as high aspect ratio features, formed therein. The film stack 700 may then undergo further processing to form a functional semiconductor device.

[0106] Methods 200, 400, and 600 are useful for processes used in front-end (FEOL) processes before metallization processes in semiconductor device manufacturing processes. The amorphous carbon film formed by method 400 can function as a hard mask layer during etching processes due to its high etch selectivity. Suitable processes include gate fabrication applications, contact structure applications, shallow trench isolation (STI) processes, and the like. In some implementations, when the amorphous carbon film is used as an etch stop layer or as a different film for different process purposes, the mechanical or optical properties of the amorphous carbon film can be similarly tailored to meet specific process needs.

[0107] Thus, implementations described herein provide a method for forming amorphous carbon films with high etch selectivity and targeted in-plane strain and Young's modulus at low stress using a plasma deposition process followed by a carbon implantation process. This method advantageously provides amorphous carbon films with targeted mechanical properties, such as low stress and a high Young's modulus, changes in carbon-to-carbon bonding and hydrogen incorporation, and high etch selectivity. Some implementations of the present disclosure further provide a process design that uses existing hardware with little impact on throughput or implementation costs. Some implementations of the present disclosure provide a unique process for increasing the elastic modulus of amorphous carbon films by approximately two-fold (e.g., from about 64 GPa to about 138 GPa) by adjusting the plasma deposition mechanism. Ion implantation further improved the Young's modulus of the amorphous carbon films by an additional 30% (e.g., about 180 GPa) and reduced the compressive stress by approximately 75% (e.g., from about -1200 to about -300 MPa), further improving film properties. Furthermore, the combination of PECVD and ion implantation has enabled the realization of amorphous carbon films with significantly reduced in-plane distortion (<3 nanometer overlay error) compared to current-generation pure carbon hard mask films. The resulting films described herein demonstrate a 30-50% improvement in etch selectivity compared to current-generation essentially pure amorphous carbon hard mask films, meeting previous overlay requirements.

[0108] When introducing elements of the disclosure or example aspect or implementation(s) thereof, the articles "a," "an," and "the" are intended to mean the presence of one or more of the element.

[0109] The words "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0110] While the foregoing is directed to implementations of the disclosure, other and further implementations of the disclosure may be devised without departing from the basic scope thereof, the scope of which is defined by the claims that follow.

Claims

1. 1. A method for treating an underlayer, comprising: depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region; forming a doped amorphous carbon film by implanting a dopant or an inert species into the amorphous carbon film in a second processing region, the dopant or the inert species comprising at least one of beryllium or germanium, and a target temperature during implantation of the dopant or the inert species being between −100° C. and 550° C.; patterning the doped amorphous carbon film; Etching the underlayer; A method comprising:

2. The method of claim 1 , wherein the underlayer comprises a single layer or a dielectric stack.

3. depositing the amorphous carbon film on the underlayer; flowing a hydrocarbon-containing gas mixture through the first processing region; generating an RF plasma in the first processing region to form the amorphous carbon film on the underlayer; The method of claim 1 , comprising:

4. 4. The method of claim 3, wherein the distance between a gas distribution showerhead positioned in the first processing region and the susceptor is between 200 mils and 1,000 mils.

5. 5. The method of claim 4, wherein the pressure in the first processing region is between 4 Torr and 8 Torr.

6. 10. The method of claim 1, wherein the implant energy utilized to energize the dopants or the inert species is between 5 keV and 300 keV.

7. Ion dose is 1 x 10 １３ ions / cm ２ and 5 x 10 １６ ions / cm ２ The method of claim 6, wherein

8. 7. The method of claim 6, wherein implanting the dopant or the inert species into the patterned amorphous carbon film is performed at an angle between 1 degree and 80 degrees relative to a direction normal to a plane defined by a top surface of the patterned amorphous carbon film.

9. 1. A method for treating an underlayer, comprising: depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region; forming a doped amorphous carbon film by implanting a dopant or an inert species into the amorphous carbon film in a second processing region, the dopant or the inert species comprising at least one of beryllium or germanium, and a target temperature during implantation of the dopant or the inert species being between −100° C. and 550° C.; patterning the doped amorphous carbon film; etching the underlayer, wherein the doped amorphous carbon film has a refractive index of 2.1 to 2.2 at 633 nm; A method comprising:

10. 10. The method of claim 9, wherein the doped amorphous carbon film has a k value of less than 1.0 at 633 nm.

11. 10. The method of claim 9, wherein the doped amorphous carbon film has a Young's modulus (GPa) of 70 to 200 GPa.

12. 12. The method of claim 11, wherein the doped amorphous carbon film has a hardness (GPa) of 14 GPa to 22 GPa.

13. The method of claim 12, wherein the doped amorphous carbon film has a stress (MPa) of -600 MPa to 0 MPa.

14. 14. The method of claim 13, wherein the doped amorphous carbon film has a density (g / cc) of 1.95 g / cc to 2.1 g / cc.

15. 15. The method of claim 14, wherein the doped amorphous carbon film has a thickness between 10 Å and 50,000 Å.

16. 1. A method for treating an underlayer, comprising: depositing an amorphous carbon film on an underlayer positioned on a susceptor in a first processing region; forming a doped amorphous carbon film by implanting a dopant into the amorphous carbon film in a second processing region, the dopant comprising carbon and at least one of beryllium or germanium, and a target temperature during implantation of the dopant being between −100° C. and 550° C.; patterning the doped amorphous carbon film; etching the underlayer, wherein the doped amorphous carbon film has a hardness (GPa) of 14 GPa to 22 GPa; A method comprising:

17. 17. The method of claim 16, wherein the doped amorphous carbon film has a refractive index of 2.1 to 2.2 at 633 nm.

18. 18. The method of claim 17, wherein the doped amorphous carbon film has a k value of less than 1.0 at 633 nm.

19. 17. The method of claim 16, wherein the doped amorphous carbon film has a Young's modulus (GPa) of 70 to 200 GPa.

20. The doped amorphous carbon film is Stress (MPa) from -600 MPa to 0 MPa; a density (g / cc) of 1.95 g / cc to 2.1 g / cc; a thickness between 10 Å and 50,000 Å; 20. The method of claim 19, comprising:

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