A method of selective deposition to enable pattern feature size shrinkage

Abstract

The application discloses a method for selective deposition to realize pattern feature size reduction, comprising the following steps: (1) surface activation, placing a substrate in a reaction cavity, and forming reaction sites on the substrate surface by using plasma; wherein the substrate has a patterned surface, including a first surface and a second surface; the first surface is a photoresist layer; and the second surface is one or more of a dielectric layer, a metal layer, a bottom anti-reflection layer and a mask layer; (2) deposition, introducing monomers into the reaction cavity, and forming a film layer on the first surface by polymerization reaction between the monomers and the reaction sites; and (3) repeating steps (1) and (2) in proportion until target feature sizes are formed on the substrate. The selective deposition of the application can produce epitaxial growth parallel to the plane, so that the pattern size is reduced; the selective deposition method of the application realizes high-precision control of the target size of the photoresist pattern, is suitable for various monomers, is simple in process and high in compatibility.

Description

Technical Field

[0001] This application relates to the field of integrated circuit nanofabrication technology, and in particular to a method for selective deposition to achieve a reduction in the size of patterned features. Background Technology

[0002] For the past half-century, Moore's Law has been the core principle driving the rapid development of the semiconductor industry, propelling technology nodes forward continuously. However, as integrated circuit manufacturing processes advance to 5nm and even more advanced technology nodes, the continuation of Moore's Law is limited by existing technologies. After reaching the 130nm node, photolithography mask design has gradually moved beyond the "what you see is what you get" stage. To ensure that the exposed patterns are not distorted, extensive computational photolithography design, reverse lithography analysis, and mask fabrication verification are required. To address these issues, developing technologies that yield smaller process patterns at larger process scales—namely, via reduction technology—can significantly reduce the investment in photolithography mask design and manufacturing, showing promising application prospects. Most current pinhole reduction technologies are based on wet chemical methods, which involve one or more liquid chemical processing steps, significantly reducing the throughput of the process and increasing manufacturing costs (Tiron et al., Alternative-Lithography Technology, 2015, 9423, 245); or they can achieve gas-phase pattern reduction but cannot selectively deposit on the polymer substrate, making it difficult to control the yield of subsequent processing steps (Shiu et al., Adv. Res. Tech&Proc, 2002, 4690, 671).

[0003] Building upon the aperture reduction process, achieving higher-density patterns is a key challenge in overcoming the limitations of photolithography technology and reducing production costs. One of the core difficulties in advancing micro- and nano-manufacturing process nodes is density multiplication based on block copolymer-induced phase separation, which is considered one of the most promising technological pathways. However, the random perturbations inherent in phase separation make this technology difficult to overcome mass production bottlenecks, necessitating a stronger phase separation induction method to drive it. Summary of the Invention

[0004] To address the aforementioned problems in existing technologies, this invention provides a method for selective deposition to reduce the size of pattern features. This invention innovatively proposes a selective deposition substrate using photoresist-substrate as the selective deposition interface, achieving pattern size reduction through selective deposition, and exposing the photoresist substrate material after the process to cope with subsequent steps such as etching and deposition. Furthermore, based on selective photoresist deposition, this application uses an expanded monomer library to modify the photoresist surface, giving it both geometrically induced and chemically induced driving forces, thereby enhancing the yield of the block copolymer-induced phase separation density multiplication process and making it more suitable for mass production.

[0005] The technical solution of the present invention is as follows:

[0006] The first objective of this invention is to provide a method for selective deposition to achieve pattern feature size reduction, comprising the following steps:

[0007] (1) Surface activation: The substrate is placed in a reaction chamber and reaction sites are formed on the surface of the substrate using plasma; wherein the substrate has a patterned surface, including a first surface and a second surface.

[0008] The first surface is a photoresist layer;

[0009] The second surface is one or more of the following: dielectric layer, metal layer, bottom anti-reflective layer, and mask layer;

[0010] (2) Deposition: Monomer is introduced into the reaction chamber, and the monomer undergoes a polymerization reaction with the reaction site to form a film on the first surface;

[0011] (3) Repeat steps (1) and (2) proportionally until the target feature size is formed on the substrate.

[0012] In one embodiment of the present invention, in step (1), the plasma is one or more of the following: hydrogen, helium, argon, neon, krypton, xenon, oxygen, ozone, nitrogen, ammonia, nitrogen oxides, water, carbon oxides, chlorine, fluorine, boron trichloride, borane, methane, ethane, propane, butane, ethylene, acetylene, propyne, butyne, aromatic hydrocarbons, formaldehyde, methanol, ethanol, acetaldehyde, acetone, silane, siloxane, silochlorosilane, chloroethane, fluoroethane, bromoethane, fluorothioethane, fluorochloroethane, fluorobromoethane, hydrogen sulfide, sulfur oxides, thiocyanates, and sulfur carbides.

[0013] In one embodiment of the present invention, the processing method for obtaining the patterned surface in step (1) includes 365nm ultraviolet lithography, 248nm KrF deep ultraviolet lithography, 193nm ArF deep ultraviolet lithography, 193nm ArF immersion lithography, 13.5nm extreme ultraviolet lithography, ion beam lithography, electron beam lithography, nanoimprinting or block copolymer lithography.

[0014] In one embodiment of the present invention, in step (1), the photoresist of the photoresist layer is ultraviolet photoresist or electron beam photoresist.

[0015] In one embodiment of the present invention, the ultraviolet photoresist includes AZ 1505 (AZ1505), AZ 5214E ​​(AZ5214E), SPR220 (SPR220-7), OFPR-800 (Fuji OFPR-800), NR9-1500PY (Futurrex NR9-1500PY), AZ DX1100 (AZ DX1100), Sumitomo PFI-38A7 (PFI-38A7), JSR KrF-2133 (KrF-2133), TOK TArF-5120 (TArF-5120), JSR ARF-1935 (ARF-1935), AZ Aquatar 600 (Aquatar600), JSR ARF-3840 (ARF-3840), Fujifilm FEP-171M (FEP-171M), and Sumitomo. One of the following: PFI-88A7, Inpria IN-2000, Lam Research MOR-175, Fujifilm EUV-1000, and Allresist AR-N 7520.

[0016] In one embodiment of the present invention, the electron beam photoresist includes PMMA A2 / A4 / A6 / A8 (MicroChem), ZEP520A (ZEON), ZEP7000 (ZEON), AR-P 679.04 (Allresist), CSAR 62 (Allresist), Hydrogen silsesquioxane (HSQ XR-1541, Dow Corning), ma-N 2400 series (Microresist Technology), NEB-31A (TOK), and mr-L 6000 series (Microresist Technology).

[0017] In one embodiment of the present invention, in step (1), the dielectric layer material includes one or more of silicon, doped silicon, silicon nitride, silicon fluoride, silicon oxide, siloxane, silazane, polished intrinsic silicon, polished doped silicon, polished thermal silicon oxide, PECVD silicon oxide, magnetron sputtered silicon oxide, LPCVD silicon oxide, and electron beam evaporated silicon oxide.

[0018] In one embodiment of the present invention, in step (1), the material of the bottom anti-reflective layer includes one or more of Brewer ARC29A (ARC29A), ShinEtsu DUV42P (DUV42P), AZ BARLi-II 88 (BARLi-II 88), Brewer DUV44P (DUV44P), Brewer AR40A (AR40A), ShinEtsu KABR-700 (KABR-700), and Brewer EUV-ARC-01 (EUV-ARC-01).

[0019] In one embodiment of the present invention, in step (1), the material of the metal layer includes one or more of copper, cobalt, iron, aluminum, titanium, chromium, gold, silver, nickel, ruthenium, tantalum, indium, tungsten, zirconium, rhodium, palladium, rhenium, iridium, platinum, molybdenum, tin, zinc, technetium, hafnium, and erbium.

[0020] In one embodiment of the present invention, in step (1), the material of the mask layer includes one or more of TOK THM-400 (THM-400), ShinEtsu KHM-301 (KHM-301), Dongjin HM248 (HM248), TOK THM-700 (THM-700), JSRHM-EUV510 (HM-EUV510), and TOK EUV-HM620 (EUV-HM620).

[0021] In one embodiment of the present invention, in step (2), the monomer has the following structure:

[0022]

[0023] R1, R2, R3, and R4 are substituents or hydrogen atoms, respectively; any two non-para substituents can form a ring.

[0024] In one embodiment of the present invention, in step (2), the monomer is an olefin monomer containing a carbonyl group, including methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, benzyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), and polyethylene glycol monoacrylate. One or more of the following: glycol monoacrylate (PEGMA), polypropylene glycol monoacrylate (PPGMA), dimethylaminoethyl acrylate (DMAEA), glycidyl acrylate, glycidyl methacrylate, diglycidyl acrylate, and trimethylolpropanetriacrylate (TMPTA).

[0025] In one embodiment of the present invention, in step (2), the monomer is an olefin monomer containing a benzene ring, including styrene, 4-Methylstyrene, α-Methylstyrene, p-tert-Butylstyrene, p-Chlorostyrene, p-Bromostyrene, p-Methoxystyrene, p-Hydroxystyrene, p-Nitrostyrene, p-Fluorostyrene, m-Methylstyrene, o-Methylstyrene, divinylbenzene (DBV), vinyl toluene, vinylnaphthalene, styrene acrylate, and styrene acrylate. Acrylate), Methylstyrene, Vinyl hydroxybenzoate, Vinylphenol, Vinylanthracene, N-Vinylcarbazole.

[0026] In one embodiment of the present invention, in step (3), the ratio corresponds to the number of cycles, and the surface activation to deposition ratio is 1:1, which means that each cycle starts with one surface activation and ends with one deposition.

[0027] In one embodiment of the present invention, the method for forming the reaction sites includes: performing plasma treatment on the patterned surface. This application utilizes a remote plasma treatment method to form polymerizable active sites on the first and second surfaces, which interact with monomers and selectively deposit a film layer on the substrate surface, thereby achieving film layer deposition.

[0028] In one embodiment of the present invention, the above method further includes a modification step, wherein the modification is etching and / or vapor phase modification.

[0029] In one embodiment of the present invention, the deposition selectivity of the monomer on the first surface is greater than 90%;

[0030] The formula for calculating deposition selectivity c is:

[0031] c = (ab) / (a+b)

[0032] Where a represents the thickness increment of the first surface and b represents the thickness increment of the second surface.

[0033] In one embodiment of the present invention, the target feature size change is greater than or equal to 0.5 angstroms. For example, the target size change can be 0.5 angstroms, 1 angstrom, 5 angstroms, 15 angstroms, 18 angstroms, 20 angstroms, 100 angstroms, 124 angstroms, 500 angstroms, 542 angstroms, 1000 angstroms, 1563 angstroms, 2509 angstroms, etc., and the specific value is not limited. The largest target feature size change is half the target feature size.

[0034] It should be noted that in the field of polymer vapor deposition, due to the presence of polluting carbon in the atmosphere, it is difficult to characterize thin films when the film thickness is too thin. Therefore, the deposition is classified according to whether the nucleation sites extend and connect to form a film. The deposition of materials that cannot form a continuous film is described as not forming a film on the surface.

[0035] This application innovatively proposes a method for selective deposition using patterned interface combinations based on photoresist to achieve feature size reduction, leveraging the selective generation of different active site combinations at different interfaces on a substrate surface by plasma. After surface activation, monomers interact with reaction sites, generating one or more of the following: free radical polymerization, anionic polymerization, cationic polymerization, and ring-opening polymerization, which then aggregate to form a film. During the plasma treatment to form reaction sites, the type, density, and lifetime of active sites on the first and second surfaces of the patterned surface can be controlled according to the plasma type, plasma power, and pressure. The thickness of the film deposited on the first and second surfaces each time can be precisely controlled according to the reaction pressure and reaction time between the monomers and the reaction sites, resulting in selective deposition. It is understood that during the same monomer deposition process, different grafting, homopolymerization, and copolymerization processes will occur due to differences in the properties of the active sites on the surface. The rates and quantities of these processes will vary significantly due to differences in interface properties. These deposition behaviors directly affect the deposition rate, and the accumulation of deposition over time indirectly reflects the film thickness.

[0036] It should be noted that a single, complete cycle must include surface activation and deposition processes; a single, complete cycle may include modification treatments; after a single, complete cycle forms a film, the film is in a relatively stable state, and its surface no longer has reactive activity. If further film deposition is required, the next round of reaction must be initiated. It is understandable that a single surface activation and deposition process cannot form a film, because it only activates the first and second surfaces or only introduces monomers, and does not meet the essential conditions for deposition.

[0037] It is noted that this deposition method generates active sites with different compositions, activities, and densities on the first and second surfaces during the surface activation stage. Understandably, under the same monomer deposition process, the first and second surfaces will exhibit different deposition behaviors, resulting in differences in film thickness. Therefore, the method of this application can achieve selective deposition while effectively controlling film thickness. It is worth noting that because the treated interface possesses different active sites, the monomer provided in this application has a reactivity that matches the first surface, while reacting almost no with the second surface, thus selectively modifying the first surface. This modification method has the advantages of high universality, strong interface control capability, and simple process.

[0038] The above-mentioned modification steps can improve the selectivity of deposition. Since the second surface generates random nuclei over time during the reaction and gradually connects to form a film, the deposition selectivity decreases. Introducing a certain proportion of etching steps into the reaction to remove the random nuclei generated on the second surface can effectively improve the selectivity of the patterned surface. Because the substrate gradually generates new surface components during the deposition process, thereby changing the deposition rate, the deposition rate of the second surface gradually increases, leading to a decrease in selectivity. By introducing a vapor-phase modification step to modify the first and second surfaces, the active sites on the second surface are quenched, preventing and slowing down their connection to form a film. Introducing a certain proportion of modification steps into the reaction can effectively improve the selectivity of the patterned surface.

[0039] The second objective of this invention is to provide a method for doubling the pattern density using the above-described method, wherein after forming the target feature size, a block copolymer film is covered on the surface of a substrate, and the entire substrate is subjected to phase separation treatment.

[0040] After the block copolymer phases are separated, at least one of the phases is selectively removed to obtain a substrate with doubled pattern density.

[0041] In one embodiment of the present invention, density doubling refers to an increase in the number of patterns per unit area.

[0042] In one embodiment of the present invention, the block copolymers include PS-b-PMMA (21k-25k, Polymer Source), PS-b-PI (20k-20k, Polymer Source), PS-b-P2VP (19k-21k, Polymer Source), PEO-b-PS (12k-15k, Sigma-Aldrich), PB-b-PS (30k-30k, Polymer Source), PS-b-PMMA (33k-33k, Polymer Source), PS-b-PEO (35k-11k, Polymer Source), PS-b-PDMS (31k-15k, Sigma-Aldrich), PFS-b-P2VP (22k-10k, Polymer Source), PS-b-PLA (20k-20k, Polymer Source), and PS-b-PMMA (46k-21k, Polymer Source). Source), PS-b-PDMS (39k-17k, Polymer Source), PS-b-PEO (43k-11k, Sigma-Aldrich), PMMA-b-PDMS (12k-12k, ARL / Polymer Source), PS-b-PLA (30k-30k, Polymer Source) Source), PS-b-PDMS (27k-15k, ARL), PEO-b-PLA (25k-10k, PolymerSource), PS-b-PDMS-b-PS (triblock, 40k-20k-40k, JSR / ARL), PI-b-PLA (15k-25k, PolymerSource).

[0043] In one embodiment of the present invention, the annealing conditions for the block copolymer are: Vacuum Thermal Annealing (PS-b-PMMA): Vacuum degree: 0.01-100000 Pa, Temperature: 150-250℃, Time: 0.5-24h; Inert Gas Thermal Annealing (PS-b-PEO): Atmosphere: N2 or Ar protection, Temperature: 160-280℃, Time: 0.5-12h; Solvent Vapor Annealing (SVA): PEO-b-PLA, Solvent: THF, Toluene, Chloroform, Acetone; Temperature: 20-100℃, Time: 0.5-12h, Solvent saturation: 60-100%.

[0044] In one embodiment of the present invention, the doubling ratio of the pattern is characterized by atomic force microscopy. By comparing the feature size of the pattern before density doubling and the feature size of the pattern after density doubling, the doubling ratio can be obtained as 2-20.

[0045] This application utilizes a selective deposition method to selectively deposit a film while simultaneously altering the properties of the first surface, changing its surface chemical composition and thus its properties when in contact with other chemical substances. Due to the chemical characteristics of its molecules, block copolymers can undergo phase separation under certain conditions, generating microscale phases. By inducing phase separation, these phases are separated according to specific geometric shapes and patterns, allowing for density multiplication in microscale patterning.

[0046] Induction methods are mainly divided into geometric induction and chemical induction. Geometric induction uses the microscale geometry of the pattern itself, such as grooves or holes, to induce phase separation in the block copolymer loaded on it, causing it to separate into different phases according to the existing geometric shape, thereby achieving a density multiplication. Chemical induction uses patterns with different surface properties to induce phase separation in the block copolymer loaded on it, causing it to separate into different phases according to the existing patterns with different chemical compositions, thereby achieving a density multiplication.

[0047] It should be noted that after achieving induced phase separation, at least one phase needs to be removed using removal methods to enable subsequent pattern transfer. Methods for phase removal include: heat treatment, solvent treatment, dry etching, ultraviolet degradation, ozone degradation, and enzymatic degradation.

[0048] The beneficial technical effects of this invention are as follows:

[0049] This application utilizes plasma to selectively generate different combinations of active sites at different interfaces on a substrate surface. Monomers then interact with these reactive sites, producing one or more of the following: free radical polymerization, anionic polymerization, cationic polymerization, and ring-opening polymerization. This process deposits substances and aggregates to form a film. During the plasma treatment to form reactive sites, the type, density, and lifetime of active sites on the patterned first and second surfaces can be controlled based on the plasma type, plasma power, and pressure. Specifically, the plasma type, power, and pressure affect the energy state and composition of the plasma-state material, which directly influences the type of active sites generated on the first and second surfaces, such as valence and electronic states. Due to differences in processing conditions, the density of active sites can be adjusted. Based on the reaction pressure and reaction time between the monomer and the reactive sites, the thickness of the film deposited on the first and second surfaces each time can be precisely controlled, resulting in selective deposition. A single complete reaction must include surface activation and deposition processes; a single complete reaction may include modification treatments; after a single complete reaction forms a film, the film is in a relatively stable state, and its surface no longer has reactive activity. If further film deposition is required, the next round of reaction must be initiated. It is understandable that surface activation, deposition processes, and modification treatments alone cannot form a film deposition because they only activate the first and second surfaces or only introduce monomers, which does not meet the necessary conditions for deposition.

[0050] It is noted that this deposition method generates active sites with different compositions, activities, and densities on the first and second surfaces during the surface activation stage. Understandably, under the same monomer deposition process, the first and second surfaces will exhibit different deposition behaviors, resulting in differences in film thickness. Therefore, the method of this application can achieve selective deposition while effectively controlling film thickness. It is worth noting that because the deposited monomers have different compositions, they alter the interfacial behavior during deposition, thereby selectively modifying the first surface.

[0051] The above-mentioned modification steps can improve the selectivity of deposition. Since the second surface generates random nuclei over time during the reaction and gradually connects to form a film, the deposition selectivity decreases. Introducing a certain proportion of etching steps into the reaction to remove the random nuclei generated on the second surface can effectively improve the selectivity of the patterned surface. Because the substrate gradually generates new surface components during the deposition process, thereby changing the deposition rate, the deposition rate of the second surface gradually increases, leading to a decrease in selectivity. By introducing a vapor-phase modification step to modify the first and second surfaces, the active sites on the second surface are quenched, preventing and slowing down their connection to form a film. Introducing a certain proportion of modification steps into the reaction can effectively improve the selectivity of the patterned surface. Attached Figure Description

[0052] Figure 1 This is a schematic flowchart of the selective deposition method for reducing the size of pattern features according to the present invention;

[0053] Figure 2 This is a schematic diagram of the process of increasing pattern density according to the present invention;

[0054] Figure 3 This is a schematic diagram of the in-situ mass change of the first and second surfaces of the quartz crystal microbalance (QCM) during the selective deposition process of the present invention.

[0055] Figure 4 This invention provides a post-deposition SEM image obtained through selective deposition to achieve pattern size reduction.

[0056] Figure 5 These are two-dimensional AFM images before and after selective deposition of the strip-shaped pattern of the present invention;

[0057] Figure 6 The images show two-dimensional AFM images of the selective deposition of the strip-shaped pattern of the present invention before and after deposition, as well as schematic diagrams of the heights of the first and second surfaces before and after deposition.

[0058] Figure 7 This is a data graph showing how the linewidth feature parameters LWR and LER of the strip structure change with the linewidth size as the feature size shrinks in this invention;

[0059] In the figure, 11 is the first surface; 12 is the second surface; 13 is the substrate supporting the first and second surfaces; 14 is the film selectively deposited on the first surface; 15 is the block copolymer; 16 is the first phase after phase separation of the block copolymer; and 17 is the second phase after phase separation of the block copolymer. Detailed Implementation

[0060] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0061] Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this application. In the description of the embodiments in this application, unless otherwise stated, " / " means "or," for example, A / B can mean A or B; the word "and / or" in the text is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, and B alone. Furthermore, in the description of the embodiments in this application, "multiple" refers to two or more than two.

[0062] The terms "first" and "second" are used for descriptive purposes only and should not be construed as implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of this application, unless otherwise stated, "multiple" means two or more.

[0063] It should be noted that, due to the good reproducibility and stable deposition rate of this selective deposition method, a stable process curve can be obtained after preliminary experiments. Before specific embodiments, preliminary experiments are conducted on the specific substrate to determine the deposition behavior under the process parameters, and the deposition behavior is used as the basis for the specific experimental process ratio. Specifically, in some embodiments, since previous preliminary experiments showed that, under certain process parameters, when the first surface electron beam photoresist PMMA A4 950k and the second surface 300 nm thermally oxidized silicon are deposited using monomer methyl methacrylate, with a surface activation to deposition step ratio of 1:1, the thickness of the photoresist deposited on the photoresist surface in each cycle is 0.5 nm, and the epitaxial growth is 0.47 nm, then when the target feature size change is determined to be 94 nm, the corresponding deposition cycle number is 100 cycles.

[0064] The ratio refers to the specific number of cycles. For example, a 1:1 surface activation to deposition ratio indicates that in this embodiment, each cycle begins with one surface activation cycle and ends with one deposition cycle, until the set number of cycles is reached. In some embodiments, additional etching and vapor phase modification steps are added. For example, a 1:1:0.1+1:0.1+2 ratio for surface activation, deposition, etching, and vapor phase modification indicates that in this embodiment, after ten cycles of surface activation and deposition, an etching step is added. After etching, another ten cycles of surface activation and etching are performed, followed by a vapor phase modification step. This completes one large cycle, and the large cycle continues to repeat until the set endpoint is reached.

[0065] It should be noted that in some embodiments, since the reduction in pattern feature size originates from epitaxial growth due to the sidewalls, the influence of both sidewalls needs to be considered when calculating the pattern thickness variation and epitaxial growth variation. For example, in a strip-shaped feature pattern morphology, if the ratio of film thickness variation to epitaxial growth is 1:1, then when the film thickness changes by 50 nm, the feature size changes by 50 nm. 2 = 100nm.

[0066] It should be noted that in some embodiments, a circulating water device is also used to control the substrate temperature of the reaction chamber and the bottom temperature of the quartz crystal microbalance, ensuring that the two temperatures remain consistent. During the deposition of the same batch of thin films, two quartz crystal microbalances are used simultaneously to detect the film increment on the first and second surfaces, respectively. Figure 3This is a schematic diagram illustrating the mass change of a quartz crystal microbalance during the regional selective deposition of a thin film, as provided in an embodiment of this application. Figure 3 As shown, the quality difference between the thin films on the first and second surfaces gradually increases with the increase of the number of deposition cycles, indicating that the regional selective deposition method of this application embodiment effectively forms deposition selectivity on the two surfaces.

[0067] Example 1

[0068] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0069] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose on 70 nm PMMA A2 photoresist was 100-2000 pC, and the beam current was 0.02-20 nA. The feature size of the resulting pattern was 10-100000 nm.

[0070] (1) Surface activation: The patterned surface is placed in the reaction chamber. The first and second surfaces of the patterned surface are activated using argon plasma for 2.5-250 seconds. After active sites are generated on the treated surface, the surface is purged with argon gas for 1-300 seconds. The material of the first surface is polymethyl methacrylate, and the material of the second surface is 300nm thermally oxidized silicon. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purging gas is 1-25 sccm.

[0071] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0072] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, until the set target feature size changes.

[0073] In Example 1, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 99.1%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.94. The epitaxial growth of the film thickness was obtained by scanning an atomic force microscope to compare the pattern dimensions before and after growth.

[0074] Example 2

[0075] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0076] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose on a 250 nm PMMA A4 photoresist was 100-2000 pC, and the beam current was 0.02-20 nA. The resulting pattern feature size was 10-100000 nm.

[0077] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polymethyl methacrylate and the material of the second surface is intrinsic silicon. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0078] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0079] Repeat steps (1) and (2) proportionally, with a ratio of 1:2, until the set target feature size changes.

[0080] In Example 2, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 96.3%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 1.02. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope.

[0081] Example 3

[0082] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0083] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose was 50-1500 pC and the beam current was 0.02-20 nA on a 100 nm random copolymer of polymethyl methacrylate-polymethacrylate-polyglycerol methacrylate obtained by spin coating. The feature size of the pattern obtained by exposure was 10-100000 nm.

[0084] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is a random copolymer of polymethyl methacrylate-polymethyl methacrylate-polyglycerol methacrylate (self-made 193nm photoresist), and the material of the second surface is silicon nitride. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0085] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0086] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, until the set target feature size changes.

[0087] In Example 3, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 90.2%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.51. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope.

[0088] Example 4

[0089] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0090] Patterning: Electron beam lithography was used with an electron energy of 50 eV and LC60 mode. The exposure dose was 500-5000 pC and the beam current was 0.2-200 nA on a 200 nm polystyrene film obtained by spin coating. The feature size of the pattern obtained by exposure was 10-100000 nm.

[0091] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon / oxygen plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The first surface is made of polystyrene, and the second surface is made of silicon oxide film doped with 5% by mass of titanium oxide. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm. The argon / oxygen ratio is 0.2-5.

[0092] (2) Deposition: Ethyl methacrylate (EMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0093] Repeat steps (1) and (2) proportionally, with a ratio of 2:1, until the set target feature size changes.

[0094] In Example 4, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the EMA monomer and maintain it at 20-75°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 92.4%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.33. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope.

[0095] Example 5

[0096] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0097] Patterning process: Electron beam lithography was used with an electron energy of 50 eV, LC60 mode, and an exposure dose of 100-1500 pC and a beam current of 0.02-20 nA on a 70 nm PMMA A2 substrate. The resulting pattern feature size ranged from 10 to 100,000 nm.

[0098] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polymethyl methacrylate and the material of the second surface is aluminum. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0099] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0100] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, until the set target feature size changes.

[0101] In Example 5, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 97.6%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.97. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope.

[0102] Example 6

[0103] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0104] Patterning process: Electron beam lithography was used with an electron energy of 50 eV, LC60 mode, and an exposure dose of 100-1500 pC and a beam current of 0.02-20 nA on a 70 nm PMMA A2 substrate. The resulting pattern feature size ranged from 10 to 100,000 nm.

[0105] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polymethyl methacrylate and the material of the second surface is gold. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0106] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0107] (3) Etching: The patterned surface is etched using an argon-oxygen mixed plasma. The etching time is 0.5-500 seconds and the etching power is 5-500 watts. The ratio of argon to oxygen is 0.2-5. After etching, the chamber is purged with argon for 1-300 seconds. The etching interval is every 1-10 surface activation-deposition cycles.

[0108] Repeat steps (1), (2), and (3) proportionally, with a ratio of 1:1:0.05+1, until the set target feature size changes.

[0109] In Example 6, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 99.6%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.72. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope.

[0110] In contrast, a comparative experiment was conducted using a substrate with the same patterned surface to highlight the enhancing effect of the modification step on selectivity. Compared to the above embodiment, steps (1) and (2) were repeated proportionally at a ratio of 1:1. The total number of cycles, except for the etching step, was the same as in this embodiment. The film thickness before and after deposition was measured using an ellipsometer. After calculation using the above formula, the selectivity was found to be 93.5%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.70. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope. Notably, the introduction of the etching step reduced the deposited film thickness by 4.9%.

[0111] Example 7

[0112] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0113] Patterning process: Electron beam lithography was used with an electron energy of 50 eV, LC60 mode, and an exposure dose of 100-1500 pC and a beam current of 0.02-20 nA on a 70 nm PMMA A2 substrate. The resulting pattern feature size ranged from 10 to 100,000 nm.

[0114] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polymethyl methacrylate and the material of the second surface is LPCVD silicon oxide. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0115] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0116] (3) Etching: The patterned surface is etched using an argon-oxygen mixed plasma. The etching time is 0.5-500 seconds and the etching power is 5-500 watts. The ratio of argon to oxygen is 0.2-5. After etching, the chamber is purged with argon for 1-300 seconds. The etching interval is every 1-10 surface activation-deposition cycles.

[0117] (4) Gas-phase modification: An oxygen-nitric oxide mixture is introduced into the reaction chamber. After reaching the detection pressure, the valve is closed to create a sealed environment inside the chamber. This is maintained for 1-10,000 s, then the valve is opened, and argon gas is used to purge for 1-300 s. This process is repeated 1-100 times. The detection pressure is 10-10,000 mT. The ratio of the oxygen-nitric oxide mixture is 0.1-10. The modification interval is every 1-10 surface activation-deposition cycles.

[0118] Repeat steps (1), (2), (3), and (4) proportionally, with a ratio of 1:1:0.1+1:0.05+2, until the set target feature size changes.

[0119] In Example 7, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 99.9%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.89. The epitaxial growth of the film thickness was obtained by scanning an atomic force microscope to compare the pattern dimensions before and after growth.

[0120] In contrast, a comparative experiment was conducted using a substrate with the same patterned surface to highlight the enhancement effect of the modification steps on selectivity. Compared to the above embodiment, steps (1) and (2) were repeated proportionally at a ratio of 1:1. The total number of cycles was the same as in this embodiment, except for the etching and vapor phase modification steps. The film thickness before and after deposition was measured using an ellipsometry, and the selectivity was calculated to be 92.8% using the above formula. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.91. The epitaxial growth of the film thickness was obtained by comparing the pattern dimensions before and after growth using an atomic force microscope. Notably, the introduction of etching and vapor phase modification steps reduced the deposited film thickness by 7.6%.

[0121] Example 8

[0122] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0123] Patterning process: 248 nm KrF deep ultraviolet lithography, exposure dose 5-100 mJ / cm 2 Light intensity 0.5-50 mW / cm 2 Exposure time: 0.1-10 seconds; DOF: -0.4-0.4 μm; photoresist thickness: 150-1000 nm; pattern feature size obtained by exposure: 150-100000 nm.

[0124] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is TOK TArF-7021 and the material of the second surface is BrewerARC® 29A. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 0.5-50 sccm.

[0125] (2) Deposition: Styrene is introduced into the reaction chamber as a polymerizable monomer for 1-3000 seconds to generate a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0126] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, until the set target feature size changes.

[0127] In Example 8, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the styrene monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 91.2%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.32. The epitaxial growth of the film thickness was obtained by scanning an atomic force microscope to compare the pattern dimensions before and after growth.

[0128] Example 9

[0129] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0130] Patterning process: 248 nm KrF deep ultraviolet lithography, exposure dose 5-100 mJ / cm 2 Light intensity 0.5-50 mW / cm 2 Exposure time: 0.1-10 seconds; DOF: -0.4-0.4 μm; photoresist thickness: 150-1000 nm; pattern feature size obtained by exposure: 150-100000 nm.

[0131] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is TOK TArF-7021 and the material of the second surface is BrewerARC® 29A. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 0.5-50 sccm.

[0132] (2) Deposition: 4-vinylpyridine (4-VP) is introduced into the reaction chamber as a polymerizable monomer for 1-3000 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0133] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, until the set target feature size changes.

[0134] In Example 9, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the 4-VP monomer and maintain it at 20-80°C. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 90.5%. The ratio between the vertical growth of the film thickness and the epitaxial growth dimension was 0.45. The epitaxial growth of the film thickness was obtained by scanning an atomic force microscope to compare the pattern dimensions before and after growth.

[0135] Example 10

[0136] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0137] Patterning: Electron beam lithography was used with an electron energy of 50 eV and LC60 mode. The exposure dose was 500-5000 pC and the beam current was 0.2-200 nA on a 200 nm polystyrene film obtained by spin coating. The feature size of the pattern obtained by exposure was 10-100000 nm.

[0138] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polystyrene and the material of the second surface is LPCVD silicon oxide. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0139] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0140] Repeat steps (1) and (2) proportionally, with a ratio of 1:2, until the set number of cycles is reached.

[0141] In Example 10, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 watts, and the reflected power was 1-5 watts. Furthermore, a heating mantle was used to heat the MMA monomer and maintain it at 20-80°C. The contact angle of the first surface before deposition was 91 degrees, and the contact angle after deposition was 63 degrees. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 97.4%.

[0142] Example 11

[0143] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0144] Patterning process: Electron beam lithography was used with an electron energy of 50 eV, LC60 mode, and an exposure dose of 100-1500 pC and a beam current of 0.02-20 nA on a 70 nm PMMA A2 substrate. The resulting pattern feature size ranged from 10 to 100,000 nm.

[0145] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is PMMA A2 and the material of the second surface is LPCVD silicon oxide. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0146] (2) Deposition: Styrene is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0147] Repeat steps (1) and (2) proportionally, with a ratio of 1:1, until the set number of cycles is reached.

[0148] In Example 11, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 watts, and the reflected power was 1-5 watts. Furthermore, a heating mantle was used to heat the styrene monomer and maintain it at 20-80°C. The contact angle of the first surface before deposition was 67 degrees, and the contact angle after deposition was 95 degrees. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity, calculated using the above formula, was 98.6%.

[0149] Example 12

[0150] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0151] Patterning: Electron beam lithography was used with an electron energy of 50 eV and LC60 mode. The exposure dose was 500-5000 pC and the beam current was 0.2-200 nA on a 200 nm polystyrene film obtained by spin coating. The feature size of the pattern obtained by exposure was 10-100000 nm.

[0152] (1) Surface activation: The patterned surface is placed in the reaction chamber. Argon plasma is used to activate the first and second surfaces of the patterned surface for 2.5-250 seconds. After active sites are generated on the treated surface, argon gas is used to purge for 1-300 seconds. The material of the first surface is polystyrene and the material of the second surface is LPCVD silicon oxide. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purge gas is 1-25 sccm.

[0153] (2) Deposition: Hydroxyethyl methacrylate (HEMA) is introduced into the reaction chamber as a polymerizable monomer for 1-300 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0154] Repeat steps (1) and (2) proportionally, with a ratio of 1:1, until the set number of cycles is reached.

[0155] In Example 12, the reaction chamber temperature was 10-100°C, the substrate temperature supporting the patterned surface was 5-100°C, the plasma power supply power was 5-500 watts, and the reflected power was 1-5 watts. Furthermore, a heating mantle was used to heat the HEMA monomer and maintain it at 20-80°C. The contact angle of the first surface before deposition was 91 degrees, and the contact angle after deposition was 15 degrees. The film thickness before and after deposition was measured using an ellipsometer, and the selectivity was calculated to be 98.4% using the above formula.

[0156] Example 13

[0157] A method for doubling pattern density specifically includes the following steps:

[0158] In this embodiment, the substrate is selectively deposited according to the process described in Example 11 to obtain the modified interface. The resulting substrate is a polystyrene-modified polymethyl acrylate photoresist first surface.

[0159] In this embodiment, the block copolymer used is PS-b-PMMA (33k-33k, Polymer Source), dispersed in toluene solvent at a mass fraction of 0.2-2%wt. The block copolymer film is dispersed onto the substrate by spin coating to form a film. The spin coating temperature is 10-50℃, the acceleration is 500-10000 rpm / s, the rotation speed is 500-8000 rpm, and the spin coating time is 20-500 seconds.

[0160] The block copolymer was subjected to inert atmosphere thermal annealing. The substrate was placed in a commercial atomic layer deposition chamber, and nitrogen was introduced for 30 minutes to replace the air. The chamber was then heated to 100-250 degrees Celsius and held at that temperature for 0.5-24 hours.

[0161] After phase separation by annealing of the block copolymer, the PMMA phase is selectively removed using reactive plasma etching. The specific process involves an ICP power of 100-800 W, a CCP power of 10-200 W, an etching gas of O2 at 1-50 sccm, an etching time of 3-30 seconds, a substrate temperature of 15-50°C, and a back helium flow rate of 1-10 sccm.

[0162] After selectively removing the PMMA phase, the pattern size before and after density multiplication was compared using atomic force microscopy to obtain a pattern multiplication ratio of 2-5.

[0163] Example 14

[0164] A method for doubling pattern density specifically includes the following steps:

[0165] In this embodiment, the substrate used is selectively deposited according to the process described in Example 10 to obtain the modified interface. The resulting substrate is a polymethyl methacrylate modified polystyrene patterned substrate with a first surface.

[0166] In this embodiment, the block copolymer used is PS-b-PMMA (25k-21k, Polymer Source), dispersed in toluene solvent at a mass fraction of 0.2-2%wt. The block copolymer film is dispersed onto the substrate by spin coating to form a film. The spin coating temperature is 10-50℃, the acceleration is 500-10000 rpm / s, the rotation speed is 500-8000 rpm, and the spin coating time is 20-500 seconds.

[0167] The block copolymer was subjected to solvothermal annealing. The substrate was placed in a commercial atomic layer deposition chamber, and nitrogen gas was introduced for 30 minutes to purge the air. After purging, toluene flow rate was controlled to 0.5-50 sccm using an MFC and allowed to stabilize for 15 minutes. The partial pressure of toluene vapor was adjusted to 0.01-0.5 ppm by adjusting the butterfly valve. The chamber was then heated to 20-150°C and maintained at this temperature for 0.5-24 hours.

[0168] After phase separation during annealing of the block copolymer, the PMMA phase is selectively removed using reactive plasma etching. The specific process involves an ICP power of 100-800 W, a CCP power of 10-200 W, an etching gas of O2 at 1-50 sccm, an etching time of 3-30 seconds, a substrate temperature of 15-50 degrees Celsius, and a back helium flow rate of 1-10 sccm.

[0169] After selectively removing the PMMA phase, the pattern size before and after density multiplication was compared using atomic force microscopy to obtain a pattern multiplication ratio of 2-10.

[0170] Example 15

[0171] A method for selective deposition to achieve pattern feature size reduction includes the following steps:

[0172] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. Exposure doses of 100-1000 pC (each exposure dose corresponds to a complete test pattern) were applied to a spin-coated 70 nm photoresist PMMA A2, with a beam current of 2-4 pA. The resulting patterns exhibited characteristic dimensions of different geometric shapes (line, circle, ellipse, square, cross, or T-shape) with linewidth distributions of 100-1000 nm.

[0173] (1) Surface activation: The patterned surface is placed in the reaction chamber. The first and second surfaces of the patterned surface are activated using argon plasma for 15 seconds. After active sites are generated on the treated surface, it is purged with argon gas for 150 seconds. The material of the first surface is PMMA A2 photoresist, and the material of the second surface is lightly boron-doped silicon. The base pressure of the reaction chamber is 50 mT. The flow rate of the plasma purge gas is 10 sccm.

[0174] (2) Deposition: Methyl methacrylate (MMA) is introduced into the reaction chamber as a polymerizable monomer for 30 seconds to form a polymer film on the first surface of the patterned surface. At this time, no film is deposited on the second surface. After the reaction, the chamber is purged with argon gas for 300 seconds.

[0175] Repeat steps (1) and (2) proportionally, at a ratio of 1:1, for 35 cycles.

[0176] After the selective deposition process, the sample was purged with 20 sccm background purge gas for 30 min to remove small molecules from the surface.

[0177] In this embodiment, the reaction chamber temperature is 50°C, the substrate temperature supporting the patterned surface is 60°C, and the plasma power supply power is 100 watts. Furthermore, a heating mantle is used to heat the MMA monomer and maintain it at 80°C. The film thickness before and after deposition is measured using an ellipsometer; the thickness change on the photoresist is 50.96 nm, and the thickness change on lightly boron-doped silicon is 0.24 nm. Calculations using the above formula yield a selectivity of 99.0%.

[0178] like Figure 4 The images are shrunk electron microscope images of square holes with a side length of 309 nm and a side length of 186 nm, which are pattern combinations with an exposure dose of 550 pC. The SEM electron gun voltage is 3 kV and 10 uA (because the electron gun of the electron microscope will expose the photoresist, characterization and comparison cannot be performed before deposition).

[0179] AFM morphology scanning was performed on pattern combinations with an exposure dose of 600 pC before deposition; such as Figure 6As shown, the light-colored areas in the two-dimensional image represent the first surface component of the patterned surface, while the dark-colored areas represent the second surface component. Cross-sectional line scans reveal that the second surface component is exposed both before and after deposition, indicating effective selective deposition. Line scan images before and after deposition show that the characteristic size of one linear pattern is 227 nm. After deposition, scanning the same stripe pattern with the same exposure dose yields a characteristic size of 140 nm, indicating a significant reduction in the pattern's characteristic size, with a reduction ratio of 1.17. Other geometries also exhibit conformal size reduction.

[0180] Comparative Example 1

[0181] A method for controlling the regional selective deposition of thin films specifically includes the following steps:

[0182] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose on 70 nm PMMA A2 photoresist was 100-2000 pC, and the beam current was 0.02-20 nA. The feature size of the resulting pattern was 10-100000 nm.

[0183] (1) Surface activation: The patterned surface is placed in the reaction chamber. The first and second surfaces of the patterned surface are activated using argon plasma for 2.5-250 seconds. After active sites are generated on the treated surface, the surface is purged with argon gas for 1-300 seconds. The material of the first surface is polymethyl methacrylate, and the material of the second surface is 300nm thermally oxidized silicon. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purging gas is 1-50 sccm.

[0184] (2) Deposition: Aniline is introduced into the reaction chamber as a non-polymerizable monomer for 1-300 seconds. There is no obvious thickness change on the first and second surfaces of the patterned surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0185] In Comparative Example 1, the reaction chamber temperature was 10-100℃, the substrate temperature supporting the patterned surface was 5-100℃, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. Furthermore, a heating mantle was used to heat the aniline monomer and maintain it at 20-80℃. The film thickness before and after deposition was measured using an ellipsometer; the thickness changes at both interfaces were within the error limit, indicating that no deposition occurred.

[0186] Comparative Example 2

[0187] A method for controlling the regional selective deposition of thin films specifically includes the following steps:

[0188] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose on 70 nm PMMA A2 photoresist was 100-2000 pC, and the beam current was 0.02-20 nA. The feature size of the resulting pattern was 10-100000 nm.

[0189] (1) Selective deposition: The patterned surface is placed in the reaction chamber. C4F8 and argon are introduced into a quartz tube at a flow rate ratio of 0.00-200 using an MFC. The radio frequency generator is activated to generate plasma in the above mixture; the plasma deposits a thin film on the patterned surface for 2.5-250 seconds. After surface treatment, the surface is purged with argon for 1-300 seconds. The material of the first surface is polymethyl methacrylate, and the material of the second surface is 300 nm thermally oxidized silicon. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purging gas is 1-50 sccm.

[0190] In Comparative Example 2, the reaction chamber temperature was 10-100℃, the substrate temperature supporting the patterned surface was 5-100℃, the plasma power supply power was 5-500 W, and the reflected power was 1-5 W. The film thickness before and after deposition was measured using an ellipsometer, and according to the above formula, the selectivity was 26.6%.

[0191] Comparative Example 3

[0192] A method for controlling the regional selective deposition of thin films specifically includes the following steps:

[0193] Patterning: Electron beam lithography was used with an electron energy of 50 eV in LC60 mode. The exposure dose on 70 nm PMMA A2 photoresist was 100-2000 pC, and the beam current was 0.02-20 nA. The feature size of the resulting pattern was 10-100000 nm. Notably, after patterning, reactive plasma etching was used with a plasma containing CF4 / C4F8 / O2 / Ar in a ratio of 1-50:1-100:1-20:1-20 to transfer the photoresist pattern, thus obtaining the target patterned substrate, i.e., patterned homogeneous silicon oxide.

[0194] (1) Surface activation: The patterned surface is placed in the reaction chamber. The first and second surfaces of the patterned surface are activated using argon plasma for 2.5-250 seconds. After active sites are generated on the treated surface, the surface is purged with argon gas for 1-300 seconds. The material of the first surface is thermally oxidized silicon, and the material of the second surface is thermally oxidized silicon. The pressure of the reaction chamber is 10-10000 mT. The flow rate of the plasma purging gas is 1-50 sccm.

[0195] (2) Deposition: Methyl methacrylate (MMA) polymerizable monomers are introduced into the reaction chamber for 1-300 seconds. There is no obvious thickness change on the first and second surfaces of the patterned surface. After the reaction, the chamber is purged with argon gas for 1-300 seconds.

[0196] In Comparative Example 3, the reaction chamber temperature was 10-100℃, the substrate temperature supporting the patterned surface was 5-100℃, the plasma power supply power was 5-500 watts, and the reflected power was 1-5 watts. The film thickness before and after deposition was measured using an ellipsometer; the thickness changes at both interfaces were within the error limit, indicating that no deposition occurred.

[0197] As can be seen from the embodiments, good selectivity was achieved on the first and second surfaces of the patterned surface in embodiments 1-9 of this application. Among them, embodiments 6-7 achieved improved selectivity on the patterned surface by introducing modification treatment, and the patterned size was significantly reduced.

[0198] Examples 10-12 demonstrate how nanoscale deposition on substrates alters the composition and properties of the interface. Significant changes in the contact angle of the substrate before and after modification indicate that the method successfully modifies the interface.

[0199] Examples 13-14 describe how, by applying block copolymers to the substrate modified in Examples 10-11 and annealing it under suitable conditions, phase separation was achieved based on the dual driving forces of geometric induction and chemical induction after surface modification, resulting in patterns with good morphological uniformity and increased density. This demonstrates the superiority of the present application in terms of density multiplication.

[0200] Figure 5 This application provides AFM two-dimensional images of a patterned surface with a striped structure on the first surface before and after selective deposition of a thin film. The light-colored areas represent the first surface, and the dark-colored areas represent the second surface with the striped structure. In-situ AFM scanning of the patterned surface before and after deposition clearly shows that the feature size of the pattern on the patterned surface is significantly reduced, and the components on the second surface remain exposed without obvious deposition nucleation leading to defects. This demonstrates that the area-selective deposition method of this application is highly feasible and effective for reducing the pattern size.

[0201] like Figure 7As shown in the figure, during the selective deposition of pinholes on a patterned surface, the LWR and LER of the strip-shaped feature morphology change with the feature size. It can be seen that as the pinhole process gradually reduces the pattern size, its LWR and LER do not increase, which means that its linewidth distribution is narrow and it can be used in further micro / nano manufacturing processes.

[0202] The pairing of the examples and comparative examples, along with the test data, are shown in Table 1 below.

[0203] Table 1

[0204]

[0205] As can be seen from Table 1, the examples with added etching and vapor phase modification showed higher selectivity than the other control groups, but due to the additional etching effect and the polymerization inhibition effect brought by vapor phase modification, their film thickness was smaller compared to the equivalent control group.

[0206] In Comparative Example 1, because the monomer aniline does not have at least one polymerizable double bond, it cannot undergo a polymerization reaction to produce deposition even after activation of the first surface. In Comparative Example 2, due to the PECVD reaction, a CFx polymer film was uniformly generated on both the first and second surfaces, but it did not exhibit good selectivity (>90%). In Comparative Example 3, because the first surface was thermally oxidized silicon, there was no significant difference in activity between it and the second surface after activation, and its activity was inherently weak and difficult to polymerize, so no film deposition could be produced under this treatment.

[0207] As can be seen from Table 1, compared with Comparative Examples 1-3, the thickness variation of the thin film deposited on the first surface in the embodiments of this application is significantly higher than that on the second surface, and the pattern size is significantly reduced, indicating that the embodiments of this application can achieve selective deposition to achieve scale reduction.

[0208] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.

Claims

1. A method of selective deposition to enable pattern feature size shrinkage, characterized by, The method comprises the following steps: forming a second surface on a substrate, forming a first surface on the second surface, and exposing part of the second surface by patterning the first surface; (1) surface activation, placing the substrate in a reaction cavity, and forming reaction sites on the substrate surface by using plasma; the first surface is a photoresist layer; the second surface is one or more of a dielectric layer, a metal layer, an anti-reflective layer, and a mask layer; (2) deposition, introducing monomers into the reaction cavity, and allowing the monomers to undergo polymerization reaction with the reaction sites to form a film layer on the first surface; the deposition selectivity of the monomers on the first surface is greater than 90%; the calculation formula of the deposition selectivity c is: c=(a-b) / (a+b) wherein, a represents the thickness increment of the first surface, and b represents the thickness increment of the second surface; (3) repeating steps (1) and (2) in proportion until the target feature size is formed on the substrate.

2. The method of claim 1, wherein, In step (1), the plasma is argon and / or oxygen.

3. The method of claim 1, wherein, In step (1), the processing method for obtaining the patterned surface includes 365 nm ultraviolet lithography, 248 nm KrF deep ultraviolet lithography, 193 nm ArF deep ultraviolet lithography, 193 nm ArF immersion lithography, 13.5 nm extreme ultraviolet lithography, ion beam lithography, electron beam lithography, nanoimprint lithography, or block copolymer lithography.

4. The method of claim 1, wherein, In step (1), the photoresist of the photoresist layer is ultraviolet photoresist or electron beam photoresist.

5. The method of claim 1, wherein, In step (2), the monomer has the following structure: wherein, R1, R2, R3, R4 are substituent groups or hydrogen atoms; any two non-para substituents form a ring.

6. The method of claim 1, wherein, In step (3), the proportion corresponds to the number of cycles, and the surface activation and deposition ratio is 1:1, which means that each cycle starts with one surface activation and ends with one deposition.

7. The method of claim 1, wherein, Before step (2) deposition, a modification step is further included, and the modification is etching and / or vapor phase modification.

8. A method of multiplying the density of a pattern using the method of claim 1, wherein, After forming the target feature size, a block copolymer film is covered on the substrate surface, and the whole is subjected to phase separation treatment; After phase separation of the block copolymer, at least one phase is selectively removed to obtain a substrate with doubled pattern density.

9. The method of claim 8, wherein, Density multiplication is the increase in the number of patterns per unit area.

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