Deposition of iodine-containing carbon films

Abstract

The method for depositing an iodine-containing film on a substrate material comprises: a H x I y F z (wherein a=1-10, x≧0, y≧1, z≧0, x+y+z=a, 2a, or 2a+2; with the proviso that when a=1, x=2, and z=0, y is not equal to 2), to a vapor of a film-forming composition including an iodine-containing precursor having the formula: and depositing an iodine-containing film formed by the iodine-containing precursor on the substrate material by a vapor deposition process. x H y F z NH a (wherein x=1 to 6, y=0 to 13, z=0 to 13, and a=1 to 2) or C x H y F z NR 1 (In the formula, x=1 to 6, y=0 to 13, z=0 to 13, and R 1 The method further comprises exposing the reactant to a vapor of a nitrogen-containing molecule having a co-reactant nitrogen-containing molecule, the nitrogen-containing molecule having a co-reactant nitrogen-containing molecule being a C1-C5 hydrocarbon.

Description

[Technical field]

[0001] cross references This application claims the benefit of priority under 35 U.S.C. §119(a) and (b) to U.S. patent application Ser. No. 17 / 555,140, ​​filed December 17, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a method for depositing an iodine-containing film on a substrate material, in particular a method for depositing an iodine-containing film on a substrate material by a thermal or plasma method, a H x I y F z wherein a=1-10, x≧0, y≧1, z≧0, and x+y+z=a, 2a, or 2a+2; and iodine-containing precursors having the general formula C x H y F z NH a (wherein x=1 to 6, y=0 to 13, z=0 to 13, and a=1 to 2) or C x H y F z NR 1 (In the formula, x=1 to 6, y=0 to 13, z=0 to 13, and R 1 is a C1-C5 hydrocarbon), where the deposition step modifies or dopes iodine into the substrate material. [Background technology]

[0003] Extreme ultraviolet (EUV) lithography (13.5 nm) is becoming the primary method of choice for <32 nm half-pitch device fabrication. Significant challenges for novel EUV resist design include EUV quantum yield, photospeed, etc., which limit the use of current carbon iodide layers / chemically amplified resists (CARs) for <7 nm half-pitch nodes (Li, et al., Chem. Soc. Rev., 2017, 2, 4855-4866). The photon density in 13.5 nm optical lithography is much lower than that used in conventional 193 nm ArF patterning with the same dose. Thinner films also result in a tremendous reduction in total light absorption. One significant obstacle for further development of polymer-based CARs for EUV patterning is their low photon absorption due to poor EUV absorption cross-sections from carbon and oxygen, as well as high photon shot noise from high photon energy. There is a need to develop new non-chemically amplified resist materials / layers to improve such EUV absorption to achieve sub-5 nm patterning.

[0004] Resist sensitivity, or photospeed, is strongly dependent on the photoacid generator, which is modified with elements with high EUV photon efficiency, such as indium (In), tin (Sn), antimony (Sb), tellurium (Te), iodine (I), xenon (Xe), and cesium (Cs), which have high photon absorption at 91.6 eV (13.5 nm). Among these elements, iodine has been shown to be a promising candidate for improving EUV sensitivity (Grzeskowiak, et al., G. Proc. SPIE 9779, Advances in Patterning Materials and Processes XXXIII, 97790C (21 March 2016)). Iodine can be doped into the carbon matrix to enhance the EUV absorption of the layer during the patterning process (e.g., resistless lithography). The iodine-containing polymer and / or amorphous carbon thus formed may be utilized to enhance the critical dimensions of semiconductor features.

[0005] US Patent Application Publication No. 2017 / 0178923 discloses a compound of formula C a H x F y I z Disclosed is a method for etching silicon-containing films using an iodine-containing etching compound having the formula: (wherein a=1-3, x=0-6, y=1-7, z=1-2; when a=1, x+y+z=4; when a=2, x+y+z=4 or 6; when a=3, x+y+z=6 or 8), and deposition of an iodine-containing polymer as a sidewall passivation layer.

[0006] US20170278709 discloses the deposition of conformal organic materials on features formed in photoresist or hardmask to reduce critical dimensions and line edge roughness. In various embodiments, a superconformal carbon-based material is deposited on features formed in high resolution photoresist. The carbon layer is synthesized by hydrocarbon gases including halogenated hydrocarbons, such as carbon tetrachloride (CCl4), diiodomethane (CH2I2), chlorofluorocarbons (CFCs), bromotrichloromethane (BrCCl3), 1,1-dichloroethylene, bromobenzene, or derivatives thereof. The hydrocarbon compounds can be partially or fully doped derivatives of hydrocarbon compounds, including fluorine-containing, oxygen-containing, hydroxyl-containing, and boron-containing derivatives of hydrocarbon compounds. The carbon layer is prepared by a PECVD method using C x H y N z Nitrogen element can be doped via molecules.

[0007] US Patent No. 10,074,534 discloses the deposition of conformal carbon-based materials. The deposition temperature can be from about 80°C to about 550°C. The carbon layer can be formed via hydrocarbon precursors including halogenated hydrocarbons, such as carbon tetrachloride (CCl4), diiodomethane (CH2I2), chlorofluorocarbons (CFCs), bromotrichloromethane (BrCCl3), 1,1-dichloroethylene, bromobenzene, or derivatives thereof. The carbon layer can be formed by the PECVD method using C x H y N z Nitrogen element can be doped via molecules.

[0008] Au et.al (“Filling Narrow Trenches by Iodine-Catalyzed CVD of Copper and Manganese on Manganese Nitride Barrier / Adhesion Layers”, J Electrochem Soc, 158(5)D248-D253(2011)) discloses a process for void-free filling of sub-100 nm trenches with copper or copper-manganese alloy by CVD. Conformally deposited manganese nitride serves as an underlayer to which iodine is initially chemisorbed. CVD of copper or copper-manganese alloy releases adsorbed iodine atoms from the manganese nitride surface, allowing the iodine to act as a surfactant catalyst floating on the surface of the growing copper layer. The iodine source disclosed is ethyl iodide, CH3CH2I.

[0009] US Patent Publication No. 20190390340 discloses a method for depositing a metal film having high purity, utilizing a thermal ALD process including an alkyl halide and a metal precursor, selectively depositing a metal film having high purity on a metal surface on a dielectric surface, selectively depositing a metal film having high purity on a dielectric surface on a metal surface, depositing a metal film with greater than 99% of the metal atoms on an atomic basis. The alkyl halide source has the general formula RX, where R is an alkyl, alkenyl, aryl, or other carbonaceous group. In some embodiments, R includes 1-2, 1-4, or 1-6 carbon atoms. In some embodiments, the alkyl halide includes or consists essentially of iodoethane (H5C2I) or diiodomethane (CH2I2).

[0010] US20210285102 discloses a method for depositing a metal film formed on the bottom of a feature having a metal bottom and dielectric sidewalls using a metal precursor and an alkyl halide catalyst while maintaining a substrate at a deposition temperature. The metal precursor has a decomposition temperature above the deposition temperature. The alkyl halide comprises carbon and a halogen, the halogen comprising bromine or iodine.

[0011] US Patent No. 7,041,596 discloses excited surfactant species obtained by generating a plasma discharge in a surfactant precursor gas. The surfactant species includes at least one of iodine, lead, tin, gallium, and indium. The surface of an integrated circuit substrate is exposed to the excited surfactant species to form a plasma-treated surface. A ruthenium thin film is deposited on the plasma-treated surface using CVD techniques.

[0012] US Patent No. 5,277,750 discloses a method for anisotropic dry etching of metallization layers containing aluminum or aluminum alloys using an etching layer. An aluminum etching process based on iodine chemistry, i.e., economical use of molecular iodine (I2) as an etching gas in a practical manner, since iodine is a solid at room temperature. Furthermore, etching chemistries based on iodine, e.g., IF7, do not seem promising. Therefore, the use of hydrogen iodide as an etching gas has been proposed in recent years, simply for reactive ion etching of silicon and tin layers on semiconductor substrates.

[0013] U.S. Pat. No. 1,033,1033 discloses a film composition comprising a first material including one of an aromatic ring-containing monomer and a polymer containing a repeat unit including an aromatic ring-containing monomer, a second material including at least one of hexagonal boron nitride and precursors thereof, chalcogenide-based materials and precursors thereof, and two-dimensional carbon nanostructures and precursors thereof, and two-dimensional carbon nanostructures containing about 0.01 atomic percent to about 40 atomic percent oxygen, and a solvent.

[0014] US Patent Publication No. 2014084219 discloses carbon nanotube fibers including one or more fiber yarns. The fiber yarns include doped multi-walled carbon nanotubes, such as doped double-walled carbon nanotubes. The carbon nanotubes are functionalized with one or more functional groups. The carbon nanotube fibers are doped with various dopants, such as iodine and antimony pentafluoride.

[0015] US 2011 / 0059617 discloses methods for etching high aspect ratio features in dielectric materials, such as silicon oxide. These methods may include the concurrent introduction of a fluorocarbon precursor and an iodo-fluorocarbon precursor into a substrate processing system containing a substrate. The fluorocarbon precursor may have an F:C atomic ratio of about 2:1 or less, and the iodo-fluorocarbon may have an F:C ratio of about 1.75:1 to about 1.5:1. Exemplary precursors may include CF, CFs, and CFI, among others. The substrate may have an overlying patterned iodized carbon layer exposing areas of exposed silicon oxide and narrow areas of silicon oxide. The plasma produces one or more etching species and one or more polymeric deposition precursors. The polymeric deposition precursors may react to form a fluorocarbon layer on the sidewalls of the trench. Although CFI is believed to generate CF fragments, its inclusion in the process plasma also contributes to polymers because it generates CF″ and I″ fragments that aid in the etch process.

[0016] US Pat. No. 9,659,788 B2 to Surla et al. discloses a method for etching silicon-containing films using organofluorine compounds as precursors containing at least one C≡N or C═N functional group.

[0017] Falaise et al. ("Capture of iodine in highly stable metal-organic frameworks: a systematic study", Chem. Commun., 2013, 49, 10320) disclose the use of two novel etching chemistries, iodotrifluoroethylene and 1-iodoheptafluoropropane, belonging to the iodofluorocarbon family in dielectric etching applications. The etching method (50G magnetic field, 93mTorr pressure, 600W RF power, and 25sccm IFC etch gas flow) shows atm I%: 7.2% by C2F5I, 10.74% by C2F3I, 4.99% by 2-C3F7I, and 4.42% by 1-C3F7I.

[0018] Karecki et al. ("Plasma etching of dielectric films with novel iodofluorocarbon chemistries: Iodotrifluoroethylene and 1-iodoheptafluoropropane", J Vac Sci&Tech A 16,755(1998)) disclose the use of two etching chemicals belonging to the iodofluorocarbon family, iodotrifluoroethylene and 1-iodoheptafluoropropane, in dielectric etching applications. The iodofluorocarbons, such as those disclosed, are currently believed to have no long-term environmental impacts. Under the conditions tested, both of the two iodofluorocarbons disclosed have been found to readily etch silicon dioxide films. 1-iodoheptafluoropropane has also been found to be capable of etching silicon nitride films under such conditions.

[0019] U.S. Pat. No. 6,508,948 to Scott et al. discloses a method for etching features in a substrate by using halogenated heterocyclic hydrocarbon species to remove substrate material from selected areas while leaving the substrate substantially unaffected in other areas.

[0020] U.S. Pat. No. 1,041,0878 to Sun et al. describes 2,2,2-trifluoroethanamine (C2H4F3N), 1,1,2-trifluoroethan-1-amine (iso-C2H4F3N), 2,2,3,3,3-pentafluoropropylamine (C3H4F5N), 1,1,1,3,3-pentafluoro-2-propanamine (iso-C3H4F5N), 1,1,1,3,3-pentafluoro-2-propanamine (iso-C3H4F5N), 1,2,3,3-pentafluoropropylamine (C3H4F5N), 1, ... Disclosed is a method of using a hydrofluorocarbon etching compound selected from the group consisting of 1,1,3,3-pentafluoro-(2R)-2-propanamine (iso-2R-C3H4F5N) and 1,1,1,3,3-pentafluoro-(2S)-2-propanamine (iso-2S-C3H4F5N), 1,1,1,3,3,3-hexafluoroisopropylamine (C3H3F6N) and 1,1,2,3,3,3-hexafluoro-1-propanamine (iso-C3H3F6N), wherein a photoresist layer is enhanced and SiO / SiN and / or SiO / p-Si are non-selectively etched.

[0021] Li et al. ("Extreme ultraviolet resist materials for sub-7nm patterning", Chem. Soc. Rev., 2017, 2, 4855-4866) discloses the continuous ongoing development of high density integrated circuits, which requires significant advances in nanoscale patterning technology. The progress in novel resist materials is reviewed and design criteria for the establishment of next-generation resist platforms are identified. Development strategies and challenges in next-generation resist materials are summarized and discussed.

[0022] Yu et al. ("Positive tone oxide nanoparticle EUV (ONE) photoresists", Proc. SPIE 9779, Advances in patterning materials and processes XXXIII, 977905, 21 March 2016) discloses negative tone patterning using nanoparticles with various organic / inorganic combinations and EUV irradiation. Zirconium methacrylate (ZrMAA) nanoparticles have a 4.2 mJ / cm 2 The laser had a sensitivity with EUV exposure as high as 100 nm, a resolution down to 22 nm, and an LER of 5.6 nm. Summary of the Invention [Problem to be solved by the invention]

[0023] There is a disclosed method for depositing an iodine-containing film on a substrate material, the method comprising: a) C a H x I y F z wherein a=1-10, x≧0, y≧1, z≧0, and x+y+z=a, 2a, or 2a+2; provided that when a=1, x=2, and z=0, y is not equal to 2; b) depositing an iodine-containing film formed by an iodine-containing precursor on a substrate material by vapor deposition; The disclosed methods may include one or more of the following aspects: step b) comprises modifying the substrate material and / or doping iodine into the substrate material; step b) comprises modifying the substrate material; step b) comprises doping iodine into the substrate material; · further, when a=0 and x=0, the iodine-containing precursors include I2, IF3, IF5, and IF7; · further, when a=0 and z=0, the iodine-containing precursor comprises HI; The iodine-containing precursor is CH3I, iodomethane; The iodine-containing precursor is C2H2F3I, 2-iodo-1,1,1-trifluoroethane; further comprising exposing the carbon-containing material to vapor of a co-reactant, either sequentially or simultaneously with step a); further comprising exposing the substrate material to a vapor of a co-reactant sequentially with step a), i.e. after step a) and before step b); · simultaneously with step a), further comprising exposing the substrate material to a vapor of a co-reactant; The coreactant is of the general formula C x H y F z NH a (wherein x=1 to 6, y=0 to 13, z=0 to 13, and a=1 to 2) or C x H y F z NR 1 (In the formula, x=1 to 6, y=0 to 13, z=0 to 13, and R 1 is a C1-C5 hydrocarbon); Nitrogen-containing molecules are N≡CR 1 (In the formula, R 1 is the formula H a F b C cwherein a=1 to 11, b=1 to 11, and c=1 to 5; Nitrogen-containing molecules are (N≡C-)-(R 2 )-(-C≡N)(wherein, R 2 is the formula H m F n C o wherein m=0, n=1-11, and o=1-5; Nitrogen-containing molecules are R 3 x [-C=N(R 4 z )] y (In the formula, x=1 to 2, y=1 to 2, z=0 to 1, and x+z=1 to 3; R 3 and R 4 are each independently represented by the formula H e F f C g wherein e=0 to 11, f=0 to 11, and g=0 to 5; The nitrogen-containing molecule is 2,3,3,3-tetrafluoropropanenitrile, C3HF4N; Nitrogen-containing molecules include 3-pentanamine, 1,1,1-trifluoro-4-methyl-, CH 12 Being an F3N; The nitrogen-containing molecule is 2-butanamine, 1,1,3,3,4,4,4-heptafluoro-, C4H4F7N; The nitrogen-containing molecule is 1-butanamine, 1,1,2,2,3,3,4,4,4-nonafluoro-, C4H2F9N; The nitrogen-containing molecule is 1-butanamine, 2,2,3,3,4,4,4-heptafluoro-, C4H4F7N; The nitrogen-containing molecule is 1,1,1,3,3,3-hexafluoroisopropylamine, C3H3F6N; The nitrogen-containing molecule is 2,3,5,6-tetrafluoropyridine, C5HF4N; The nitrogen-containing molecule is 2,3,4,5,6-pentafluoropyridine, C5F5N; The nitrogen-containing molecule is 2,4,6-trifluoro-1,3,5-triazine, C3F3N3; The nitrogen-containing molecule is 2,3,5,6-tetrafluoropyrazine, C4N2F4; The nitrogen-containing molecule is 3,4,5,6-tetrafluoropyridazine, C4N2F4; The nitrogen-containing molecule is 2,4,5,6-tetrafluoropyrimidine, C4N2F4; The nitrogen-containing molecule is 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, C6F9N3; The nitrogen-containing molecule is 2,3,6-trifluoropyridine, C5H2F3N; The nitrogen-containing molecule is 3,4,5-trifluoropyridine, C5H2F3N; The nitrogen-containing molecule is 2,3,5-trifluoropyridine, C5H2F3N; The nitrogen-containing molecule is 2,4,5-trifluoropyridine, C5F3H2N; The nitrogen-containing molecule is 2,4-difluoro-1,3,5-triazine, C3HF2N3; The nitrogen-containing molecule is 3,6-difluoro-1,2,4-triazine, C3HF2N3; The nitrogen-containing molecule is 2-fluoro-1,3,5-triazine, C3H2FN3; The nitrogen-containing molecule is 2,4-difluoro-6-(1,1,2,2,2-pentafluoroethyl)-1,3,5-triazine, C5F7N3; The nitrogen-containing molecule is 2-fluoro-4,6-bis(trifluoromethyl)-1,3,5-triazine, C5F7N3; The nitrogen-containing molecule is 2,4-difluoro-6-(trifluoromethyl)-1,3,5-triazine, C4F5N3; The nitrogen-containing molecule is 2-iodopyridine, C5H4NI; The nitrogen-containing molecule is 3-pyridyl iodide, C5H4NI; The nitrogen-containing molecule is 4-iodopyridine, C5H4NI; The nitrogen-containing molecule is 1,3,4,5-tetrafluoro-1H-pyrazole, C3F4N2; The nitrogen-containing molecule is 1,2,4,5-tetrafluoro-1H-imidazole, C3F4N2; The nitrogen-containing molecule is 1,2,3,4,5-pentafluoro-1H-pyrrole, C4NF5; The nitrogen-containing molecule is 3-fluoropyridine, C5H4FN; The nitrogen-containing molecule is pyridine, C5H5N; the co-reactant is a nitrogen-containing molecule selected from N2, NH3, hydrazine N2H4, dimethylhydrazine C2H8N2, guanidine CH5N3, primary and secondary amines, e.g., ethylenediamine or imino, e.g., diiminopyridine; The nitrogen-containing molecule is N2; The nitrogen-containing molecule is NH3; · The nitrogen-containing molecule is hydrazine, N2H4; · The nitrogen-containing molecule is dimethylhydrazine, C2H8N2; The nitrogen-containing molecule is guanidine, CH5N3; The nitrogen-containing molecules are primary and secondary amines, e.g., ethylenediamine; The nitrogen-containing molecule is ethylenediamine; the nitrogen-containing molecule is an imino, such as a diiminopyridine; The nitrogen-containing molecule is, for example, a diiminopyridine; · The co-reactant is an oxidizing agent; the oxidant is selected from O2, O3, CO, CO2, NO, N2O, NO2, H2O, H2O2, COS, SO2, compressed air or combinations thereof; · The oxidizing agent is O2; · The oxidizing agent is O3; The co-reactant is an inert gas; The inert gas is selected from He, Ar, N2, Xe, Kr, Ne, or a combination thereof; The inert gas is Ar; The co-reactant is an added gas; the additive gas is selected from CF4, CH3F, C2F6, C3F8, C2HF5, C5F8, C6F6, C4F6, or C4F8; The added gas is C1~C 10 be saturated or unsaturated, linear, branched or cyclic hydrofluorocarbons; The added gas is C4H2F6, C3H2F6, CHF3, CH2F2, or a combination thereof; The added gas is of formula C b H m I n F o (wherein b=1-10, m≧0, n≧1, o≧0, and m+n+o=2b+2, 2b, or b; provided that when b=0 and m=0, the iodine-containing additives include I2, IF3, IF5, and IF7; and when b=0 and o=0, the iodine-containing additives include HI). a H x I y F z Any iodine-containing additive other than those listed above; When the substrate material is exposed to an iodine-containing precursor and an iodine-containing additive gas, the iodine-containing additive C b H m I n F o However, iodine-containing precursor C a H x I y F z To be different from; The deposition method is a thermal or plasma deposition process; The deposition method is a thermal deposition process; The deposition method is a plasma deposition process; The deposition method is plasma equipment; The deposition method is to use an etcher; The deposition method is to use a LAM tool etcher; The deposition method is plasma-enhanced ALD; The deposition method is plasma-enhanced CVD; The deposition method is thermal ALD; The deposition method is thermal CVD; The iodine atom concentration in the iodine-containing film is in the range of approximately 0.01% to approximately 99.9%, with a uniform concentration due to the iodine-containing film; The iodine atom concentration in the iodine-containing film is in the range of approximately 0.01% to approximately 50%, with a uniform concentration through the iodine-containing film; The iodine atom concentration in the iodine-containing film is in the range of approximately 7% to approximately 30%, with a uniform concentration through the iodine-containing film; The iodine atomic concentration in the substrate material is in the range of approximately 0.01% to approximately 50%; The iodine atomic concentration in the substrate material is in the range of approximately 7% to approximately 30%; The deposition pressure is about 10 -3 torr to 1000 torr range; · The deposition pressure is in the range of about 1 mTorr to 760 Torr; The deposition temperature is in the range of approximately -110°C to 1100°C; - Plasma power is in the range of about 25W to about 100,000W; · Plasma power is in the range of approximately 100W to 25000W; The gas flow of the iodine-containing gas is in the range of approximately 0.01% to approximately 99.9%; The substrate material is the bottom layer; The substrate material is a silicon-containing layer; the substrate material is a carbon-containing layer; and The substrate material is an amorphous carbon layer. [Means for solving the problem]

[0024] There is a disclosed method for depositing iodine-containing and nitrogen-containing films on a substrate material, the method comprising: a) sequentially or simultaneously exposing a substrate material to a vapor of a film-forming composition and a vapor of a nitrogen-containing molecule; (wherein the film-forming composition is C a H x I y F z wherein a=1-10, x≧0, y≧1, z≧0, and x+y+z=a, 2a, or 2a+2, with the proviso that when a=1, x=2, and z=0, then y is not equal to 2; Nitrogen-containing molecules have the general formula C m H n F o NH b Or C x H y F z NR 1 (In the formula, m=1 to 6, n=0 to 13, o=0 to 13, b=1 to 2, and R 1 is a C1 to C5 hydrocarbon); b) depositing an iodine-containing film formed by an iodine-containing precursor on a substrate material by a thermal or plasma method; The disclosed methods may include one or more of the following aspects: step b) comprises modifying the substrate material and / or doping iodine into the substrate material; step b) comprises modifying the substrate material; step b) comprises doping iodine into the substrate material; The iodine-containing precursor is CH3I, iodomethane; The iodine-containing precursor is C2H2F3I, 2-iodo-1,1,1-trifluoroethane; The nitrogen-containing molecule is C3HF4N; The iodine atom concentration in the iodine-containing film is in the range of approximately 0.01% to approximately 99.9%, with a uniform concentration due to the iodine-containing film; The iodine atom concentration in the iodine-containing film is in the range of approximately 0.01% to approximately 50%, with a uniform concentration through the iodine-containing film; The iodine atom concentration in the iodine-containing film is in the range of approximately 7% to approximately 30%, with a uniform concentration through the iodine-containing film; The iodine atomic concentration in the substrate material is in the range of approximately 0.01% to approximately 50%; and The iodine atomic concentration in the substrate material is in the range of approximately 7% to approximately 30%.

[0025] There is a disclosed method for depositing an iodine-containing film on a substrate material, the method comprising: a) sequentially or simultaneously exposing a substrate material to vapors of CH3I or C2H2F3I and vapors of C3HF4N; b) depositing a layer of an iodine-containing polymer formed by CH3I or C2H2F3I on a substrate material by thermal or plasma methods, wherein step b) comprises modifying the substrate material and / or doping iodine into the substrate material. The disclosed method may include one or more of the following aspects: The concentration of iodine atoms in the iodine-containing polymer is in the range of approximately 0.01% to approximately 99.9%, with a uniform concentration through the iodine-containing polymer; The concentration of iodine atoms in the iodine-containing polymer is in the range of approximately 0.011% to approximately 50%, with a uniform concentration through the layer of the iodine-containing polymer; The concentration of iodine atoms doped into the iodine-containing polymer is in the range of approximately 7% to approximately 30% with a uniform concentration through the layer of the iodine-containing polymer; The iodine atomic concentration in the substrate material is in the range of approximately 0.01% to approximately 50%; and The iodine atomic concentration in the substrate material is in the range of approximately 7% to approximately 30%.

[0026] Notation and Nomenclature In the following detailed description and claims, numerous abbreviations, symbols and terms that are commonly known in the art are utilized, including the following:

[0027] As used herein, the indefinite articles "a" or "an" mean one or more.

[0028] As used herein, in the text or claims, "about" or "approximately" or "approximately" means ±10% of the stated value.

[0029] As used herein, "room temperature" in the text and claims means about 20°C to about 25°C.

[0030] The term "wafer" or "patterned wafer" refers to a wafer having a silicon-containing film stack on a substrate, and a patterned film on the silicon-containing film stack formed for pattern etching.

[0031] The term "substrate" refers to one or more materials on which a process is performed. A substrate may refer to a wafer having one or more materials on which a process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductors, solar cells, flat panels, or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited thereon from a previous manufacturing step. For example, the wafer may include a silicon layer (including but not limited to crystalline, amorphous, porous, etc.), a silicon-containing layer (including but not limited to SiO2, SiN, SiON, SiCOH, etc.), a metal or metal-containing layer (including but not limited to copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Furthermore, the substrate may be flat or patterned. The substrate may be a patterned organic carbon iodide layer film. The substrate may include a layer of oxide used for dielectric materials in field effect transistors (FETs), such as FinFETs, MOFSETs, GAAFETs (gate-all-around FETs), ribbon-FETs, nanosheets, fork-sheet FETs, complementary FETs (CFETs), MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) or nitride-based films (e.g., TaN, tin, NbN) used as electrodes. As used herein, the term "film" or "layer" refers to a thickness of some material that is placed or spread over a surface, and those skilled in the art will recognize that the surface may be a trench or line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates. The substrate can be any solid having functional groups on its surface that tend to undergo reaction with the reactive heads of the SAM, and can include, but is not limited to, a 3D object or a powder.

[0032] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, at least the top film having topographical features produced in a step prior to the deposition of the indium-containing film.

[0033] The term "processing" as used herein includes deposition, patterning, exposing, developing, etching, washing, and / or removal of materials or carbon iodide layers as required in forming the described structures.

[0034] The term "deposit" or "deposition" refers to a series of processes in which materials at the atomic or molecular level are deposited as thin layers from a gaseous state (vapor) to a solid state on a wafer surface or substrate. Chemical reactions are involved in the process, which occurs after the generation of plasma of the reactive gas or the activation of the reactive gas by heat. The plasma can be a capacitively coupled plasma (CCP), typically generated by a radio frequency (RF) (alternating current (AC)) frequency or direct current (DC) discharge between two electrodes, the space between which is filled with the reactive gas. The plasma can also be a microwave plasma. Furthermore, deposition processes for EUV lithography are also performed in etch chambers. Suitable commercially available plasma etch chambers include, but are not limited to, the Applied Materials magnetically enhanced reactive ion etcher sold under the trademark eMAX™, or the Lam Research Dual CCP reactive ion etcher dielectric etch line sold under the trademark 2300® Flex™.

[0035] The term "aspect ratio" refers to the ratio of the height of a trench (or opening) to the width of the trench (or the diameter of the opening).

[0036] It should be noted that, as used herein, the terms "film" and "layer" may be used interchangeably. It is understood that a film may correspond to or relate to a layer, and a layer may refer to a film. Furthermore, one of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of any material disposed or spread over a surface, which may be as large as an entire wafer or as small as a trench or line.

[0037] It should be noted that, in this specification, the terms "aperture," "via," "hole," and "trench" may be used interchangeably to refer to an opening formed in a semiconductor structure.

[0038] The term "additive," as used herein, refers to a compound or gas that is added to other etching compounds and that provides some improved characteristic of the etch, e.g., improving profile characteristics such as bowing, CD, ellipticity, etc.

[0039] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" gate; the abbreviation "2D" refers to a two-dimensional gate structure on a flat substrate; and the abbreviation "3D" refers to a three-dimensional or vertical gate structure in which the gate structures are stacked vertically.

[0040] It should be noted that, in this specification, the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0041] It is noted that, as used herein, the terms "precursor," "deposition compound," and "deposition gas" can be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor can correspond to or be associated with a deposition compound or deposition gas, and a deposition compound or deposition gas can refer to a precursor.

[0042] It should be noted that the term "doping" is used interchangeably herein to refer to the process of incorporation of one or more elements into a film by various methods, and that the elements may be chemically bonded or physically bound. The elements may be interstitially or substitutionally doped into the film.

[0043] Standard abbreviations of elements from the periodic table are used herein. It should be understood that elements can be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0044] To identify the particular molecules disclosed, unique CAS Registry Numbers assigned by the Chemical Abstract Service (or "CAS") are provided.

[0045] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms. As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Furthermore, the term "alkyl group" refers to a linear, branched, or cyclic alkyl group. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and the like. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, and the like.

[0046] As used herein, the abbreviation "Me" means a methyl group; the abbreviation "Et" means an ethyl group; the abbreviation "Pr" means any propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" means an isopropyl group; the abbreviation "Bu" means any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation "tBu" means a tert-butyl group; the abbreviation "sBu" means a sec-butyl group; the abbreviation "iBu" means an iso-butyl group; the abbreviation "Ph" means a phenyl group; the abbreviation "Am" means an amyl group (iso-amyl, sec-amyl, tert-amyl); the abbreviation "Cy" means a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); and the abbreviation "Ar" means an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.).

[0047] As used herein, the term "doping" refers to the process of intentionally incorporating atoms of different elements into a film composition.

[0048] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said ranges. All ranges recited herein include their endpoints (i.e., x=1-4 or x is a range from 1-4 includes x=1, x=4, and x=any number therebetween), regardless of whether the term "inclusive" is used.

[0049] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification do not necessarily all refer to the same embodiment, and alternative or alternate embodiments are not necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0050] As used herein, the term "independently" when used in connection with a description of an R group should be understood to indicate that the R group in question is independently selected not only from another R group having the same or different subscript or superscript, but also from any additional variations of that same R group. For example, the formula MR 1 x (NR 2 R 3 ) (4-x) (wherein x is 2 or 3), and two or three R 1 The groups may be mutually or R 2 Or R 3 Additionally, unless otherwise specified, it should be understood that the values ​​of R groups are independent of each other when used in different formulas.

[0051] As used in this application, the term "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete form.

[0052] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive permutations. That is, if X uses A, if X uses B, or if X uses both A and B; in any of the foregoing cases, "X uses A or B" is satisfied. In addition, the articles "a" and "an" as used in this application and the appended claims should generally be construed to mean "one or more" unless otherwise specified or clear from the context to refer to the singular form.

[0053] "Comprising" in the claims is an open transitional term meaning that the claim elements identified thereafter are a non-exclusive list (i.e., others may additionally be included and still fall within the scope of "comprising"). "Comprising" is defined herein as necessarily including the more restrictive transitional terms "consisting essentially of" and "consisting of." Thus, "comprising" may be replaced with "consisting essentially of" or "consisting of" and still fall within the expressly defined scope of "comprising."

[0054] "Provifing" in the claims is defined to mean furnishing, supplying, making available, or preparing something. This step may be performed by any actor, unless the claim contains express language to the contrary.

[0055] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are given the same or similar reference numerals and in which: [Brief description of the drawings]

[0056] [Figure 1a] Figure 1a shows the atomic XPS concentration of iodine in the aC material versus the plasma source power (W) at 27 MHz for the deposition of CH3I; [Figure 1b] Figure 1b shows the atomic XPS concentration of iodine in the aC material versus plasma bias power (W) at 2 MHz for the deposition of CH3I; [Diagram 2] Figure 2 shows the iodine concentration on the surface of carbon-containing materials due to the volatilization of iodine and iodine-containing species with the deposition of CH3I; [Diagram 3]Figure 3 shows the increase in iodine atomic concentration (14%) for CH3I deposition as the pressure increases from 30 to 200 mTorr; [Figure 4] FIG. 4 shows that the iodine atomic concentration is optimized at 70 / 150sccm condition for the deposition of CH3I; [Diagram 5] FIG. 5 shows that the iodine atomic concentration remains roughly constant after 1 week of exposure during the moisture and light test for CH3I deposition; [Figure 6a] Figure 6a shows iodine I3d5 / 2 with deposition of CH3I; [Figure 6b] Figure 6b shows the carbon C1 spectrum with CH3I deposition; [Figure 7a] Figure 7a shows that the optimal iodine atomic concentration can be achieved by adjusting the source power at 1000 W using C2H2F3I; [Figure 7b] Figure 7b shows that the optimal iodine atomic concentration can be achieved by adjusting the bias power at 1000 W using C2H2F3I; [Figure 8a] FIG. 8a illustrates an exemplary cross-sectional side view of an exemplary layer in a DRAM stack for producing a DRAM memory; [Figure 8b] FIG. 8b illustrates an exemplary cross-sectional side view of an exemplary layer in a 3D NAND stack to create a 3D NAND gate; [Figure 9] Figure 9 shows the XPS results showing the iodine atom concentration on the aC surface; [Figure 10] FIG. 10 shows that iodine I3d5 / 2 has three types of bonds on the aC surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0057] Disclosed are iodine-containing film-forming compositions comprising iodine-containing precursors that may or may not contain halogens other than iodine, and methods of using the iodine-containing film-forming compositions to deposit thin films on substrate materials, such as carbon-containing materials (e.g., amorphous carbon materials), modify the surface of substrate materials, and / or dope iodine into substrate materials by vapor deposition methods, such as thermal or plasma vapor deposition processes, plasma equipment, such as etchers (e.g., LAM tool etchers), plasma-enhanced ALD or CVD, and / or thermal ALD or CVD. In some embodiments, nitrogen-containing molecules can be used as co-reactants to enhance the deposition of iodine-containing films, the modification of substrate materials, and the doping of iodine into substrate materials.

[0058] The substrate material having an iodine-containing thin film deposited thereon or the modified and / or doped substrate material may be used as a carbon iodide film for the etching process. The deposited iodine-containing thin film may be disposed on the substrate material layer to be etched. Exemplary substrate materials may include carbon-containing materials. Exemplary carbon-containing materials may include amorphous carbon (aC), or boron and metal doped aC or silicon doped aC, etc.

[0059] The disclosed method provides a new / novel chemical reaction for depositing iodine-containing films on the surface of carbon materials, as well as a method for enhancing the iodine concentration in the carbon materials. Such iodine-modified layers can be utilized in various applications in semiconductor fabrication equipment. The disclosed iodine-containing precursors and the disclosed film-forming compositions can be used to form high-speed, high-sensitivity semiconductor films in, for example, CMOS systems, DARM memories, 3D NAND channels, or photodetectors.

[0060] The disclosed iodine-containing precursors and the disclosed film-forming compositions are suitable for depositing corresponding element-containing films and their deposition methods for synthesizing corresponding element-containing films.The films deposited using the disclosed methods can be uniformly deposited on flat or patterned wafers, or in "gap-fill" or "bottom-up gap-fill" approaches.

[0061] The disclosed method provides a novel chemical reaction to modify the surface of carbon materials with iodine-containing molecules or to deposit thin layers of iodine-containing polymers using a combination of iodine and nitrogen-containing molecules, and iodine and oxygen-containing molecules.

[0062] The iodine-containing precursors disclosed are: a H x I y F z where a=1-10, x≧0, y≧1, z≧0, x+y+z=a, 2a, or 2a+2; with the proviso that when a=1, x=2, and z=0, y is not equal to 2; with the proviso that when a=0 and x=0, the iodine-containing precursors include I2, IF3, IF5, and IF7; with the proviso that when a=0, z=0, the iodine-containing precursors include HI. Two examples of iodine-containing precursors that are disclosed are CH3I and C2H2F3I, as shown in Table 1.

[0063] [Table 1]

[0064] The disclosed film-forming compositions may include nitrogen-containing molecules, such as N-containing hydrofluorocarbons (HFCs) and / or fluorocarbons. The addition of nitrogen in the deposition process increases the iodine composition of the deposited film and the iodine concentration doped into the underlayer, such as carbon-containing materials, which may play a beneficial role in EUV processes. The nitrogen may be in the form of N2, NH3, or in the form of a hydrocarbon, hydrofluorocarbon molecule, where the nitrogen is bonded to carbon and the nitrogen functional group is -C≡N, C=N, or -CNR, where R is carbon or hydrogen (-NH or -NH2 groups), or the nitrogen is in a ring structure bonded to carbon or another nitrogen molecule. Within any of these molecules, iodine may be contained within the molecule. The elements contained in the thin film deposited by the disclosed method using a plasma source are not limited to C, I, N, or C, I, O on the substrate, where the substrate is a carbon or silicon-containing material. Thin films may be deposited using any gas containing, but not limited to, C, I, N, or C, I, O, or using a combination of an iodine-containing gas and a nitrogen- or oxygen-containing gas.

[0065] The nitrogen-containing molecules used in the disclosed methods have the general formula C x H y F z NH a (wherein x=1 to 6, y=0 to 13, z=0 to 13, and a=1 to 2) or C x H y F z NR 1 (In the formula, R 1 The nitrogen-containing molecules used in the disclosed methods may have the formula N≡CR 1 (In the formula, R 1 is the formula H a F b C c where a=1 to 11, b=1 to 11, and c=1 to 5; (N≡C-)-(R 2 )-(-C≡N)(wherein, R 2 is the formula H m F n C owhere m=0, n=1 to 11, and o=1 to 5); R 3 x [-C=N(R 4 z )] y (In the formula, x=1 to 2, y=1 to 2, z=0 to 1, and x+z=1 to 3; R 3 and R 4 are each independently represented by the formula H e F f C g where e=0-11, f=0-11, and g=0-5. Examples of the disclosed nitrogen-containing molecules are listed in Table 2. The nitrogen-containing molecule used in the disclosed method can be 2,3,3,3-tetrafluoropropanenitrile, C3HF4N.

[0066] [Table 2]

[0067] [Table 3]

[0068] [Table 4]

[0069] Additionally, the nitrogen-containing molecules used in the disclosed methods can be N2, NH3, hydrazine N2H4, dimethylhydrazine C2H8N2, guanidine CH5N3, primary and secondary amines, such as ethylenediamine and iminos, such as diiminopyridine, and the like.

[0070] The oxygen-containing molecule used in the disclosed method is H p OC-R 1 (wherein p may be 0 or 1; R 1 is the formula H a F b C c O owhere a=1 to 11, b=1 to 11, o=1 to 2, and c=1 to 5; (R 2 -)-(O)-(-R 3 )(wherein, R 2 is the formula H e F f C g O h where e=1 to 11, f=1 to 11, o=1 to 2, and g=1 to 5; R 3 is the formula H m F n C o O p where m=0, n=1 to 11, p=1 to 2, and o=1 to 5); R 4 x [-C=O(R 5 z )] y (In the formula, x=1 to 2, y=1 to 2, z=0 to 1, and x+z=1 to 3; R 4 and R 5 are each independently represented by the formula H u F v C w O z where u=0-11, v=0-11, z=1-2 and w=0-5. Examples of oxygen-containing molecules disclosed include COF2, C2O2F2, (CF3)3COH, and the like.

[0071] Generally, in the manufacture of integrated circuit semiconductor devices, liquid crystal displays, plasma displays, etc., it is required to form a predetermined material pattern on a semiconductor wafer or glass substrate. The formation of the predetermined material pattern involves coating a carbon iodide layer on a material layer deposited on the semiconductor wafer or glass substrate, forming the carbon iodide layer pattern by exposure, and etching the material layer into the predetermined material pattern using the carbon iodide layer pattern as an etching layer.

[0072] In some embodiments, the substrate 100 may include a stack of multiple layers thereon as shown in FIG. 8a, which is an exemplary cross-sectional side view of an exemplary layer in a DRAM stack resulting in a DRAM memory. As shown, a stack of four layers is disposed on a silicon wafer substrate 102. A hard mask layer 106 is disposed on a SiO layer 104. The SiO layer 104 can be replaced with alternating SiO / SiN layers or alternating SiO / poly-Si layers (see FIG. 8b). Note that the layer 104 may or may not be present in the actual experiment. The hard mask layer 106 may be referred to as a substrate material, which may be a layer of CVD, PECVD, ALD, PEALD, or spin-on deposition (SOD) amorphous carbon or doped amorphous carbon, CVD, PECVD, ALD, PEALD, or spin-on deposition (SOD) amorphous carbon or doped amorphous silicon, a silicon-containing spin-on mask, or a carbon-containing spin-on mask. The hard mask layer 106 may contain C and H, as well as other elements, such as silicon, boron, nitrogen, sulfur, chlorine, fluorine, or metals (Al, Zr, Ti, W, Y), etc. Alternatively, the hard mask layer 106 is a doped aC layer, such as a boron-doped aC layer, a tungsten-doped aC layer, etc. In addition, the hard mask layer 106 may also include SiCOH, SiC, SiCN, SiCON, etc. An iodized carbon layer 108 is deposited on the hard mask layer 106. The stack in FIG. 8a is provided for illustrative purposes only, and one skilled in the art will recognize that the disclosed iodine-containing film-forming compositions may be used to deposit an iodized carbon layer 108 on the hard mask layer 106, modify the hard mask layer 106, and / or dope iodine into the hard mask layer 106. Additionally, the hard mask layer 106 may be deposited over any possible layer of 104 applied in a semiconductor fabrication process, such as over a stack of multiple layers as shown in FIG. 8b, which is an exemplary cross-sectional side view of exemplary layers in a 3D NAND stack resulting in a 3D NAND gate.As shown, a stack of seven alternating SiO / SiN (i.e., 204a / 204b) layers 204 is deposited on a silicon wafer 202 (i.e., ONON or TCAT techniques). Those skilled in the art will recognize that some techniques replace the SiN layer 204b with a p-Si layer (e.g., SiO / p-Si or P-BICS techniques). A hardmask layer 206 is deposited on the seven SiO / SiN layers 204. The hardmask layer 206 can be an amorphous carbon (aC) hardmask layer with or without dopants. The hardmask layer 206 can be a layer of CVD, PECVD, ALD, PEALD, or spin-on-deposited (SOD) amorphous carbon or doped amorphous carbon, silicon-containing spin-on mask, or carbon-containing spin-on mask. The hard mask layer 206 may contain C and H, as well as other elements, such as boron, nitrogen, sulfur, chlorine, fluorine, or metals (Al, Zr, Ti, W, Y), to improve etch resistance during the SiO / SiN layer etch. In this case, the hard mask layer 206 is an aC layer or a doped aC layer, such as a boron doped aC layer, a tungsten doped aC layer, etc. An iodized carbon layer 208 is deposited on the hard mask layer 206. The layer stack in FIG. 8b is provided for illustrative purposes only, and one skilled in the art will recognize that the disclosed iodine-containing film-forming compositions may be used to form the iodized carbon layer 208 on the hard mask layer 206, deposit the iodized carbon layer 208 on the hard mask layer 206, modify the hard mask layer 206, and / or dope iodine into the hard mask layer 206.

[0073] As discussed above, elemental iodine can be bonded / doped into aC films or carbon materials or carbon matrices to enhance EUV absorption of films or layers deposited using the disclosed methods during patterning processes (e.g., resistless lithography). Such formed iodine-containing polymers and / or amorphous carbon can be used to enhance the critical dimensions of semiconductor features.

[0074] During the plasma process, the disclosed iodine-containing gas or precursor may be evolved into the following forms: 1) iodine ions (I + , I - );2) Iodine radical (I );3) Iodine-containing polymer ion ( + C x H y I z F d , - C x H y I z F d ); and 4) iodine-containing polymer radicals (·C x H y I z F d ). The first and third forms of iodine can be deposited onto the carbon surface by controlling the bias power. Furthermore, these chemical forms are deposited as a polymer layer that can enhance the EUV absorption of the layer during the patterning process. Furthermore, these chemical forms can penetrate iodine into the carbon-containing material, modify the carbon-containing material, or modify the surface of the carbon-containing material and dope iodine into the carbon-containing material.

[0075] Also disclosed is a method for forming iodine-containing polymers on carbon-containing materials using plasma deposition processes. Applicants believe that the disclosed film-forming compositions are suitable for thermal or plasma deposition processes, such as thermal ALD and PEALD, thermal CVD and PECVD, plasma equipment, such as LAM tool etchers. The disclosed methods can be useful in the manufacture of semiconductor, solar cell, LCD-TFT, flat panel type devices.

[0076] In the disclosed method, the iodine atom concentration in the iodine-containing polymer or film deposited on the carbon-containing material or the surface of the carbon-containing material can be in the range of about 0.01% to about 99.9%, preferably about 0.01% to about 50%, more preferably about 7% to about 30%. Furthermore, the iodine atom concentration in the iodine-containing polymer deposited on the carbon-containing material by the disclosed method is maintained at a uniform concentration by the iodine-containing polymer or film. In the disclosed method, the iodine atom concentration doped in the carbon-containing material can be in the range of about 0.01% to about 99.9%, preferably about 0.01% to about 50%, more preferably about 7% to about 30%.

[0077] The plasma method includes providing a plasma reaction chamber having a substrate disposed therein. The plasma reaction chamber can be any enclosure or chamber in a device in which an etching method is performed, such as, but not limited to, a LAM tool etcher, reactive ion etch (RIE), dual capacitively coupled plasma (CCP) with single or multiple frequency RF sources, inductively coupled plasma (ICP), or microwave plasma reactor, low temperature RIE, or other type of etching system capable of selectively removing portions of a Si-containing layer or generating activated species. The etch chamber may also have a temperature controlled stage, where the temperature may be controlled from -110°C to 1100°C. One skilled in the art will recognize that different plasma reaction chamber designs provide different electronic temperature control.

[0078] The disclosed iodine-containing film-forming composition is provided with a purity of more than 95 v / v%, preferably more than 99.99 v / v%, more preferably more than 99.999 v / v%. The disclosed iodine-containing film-forming composition contains less than 5 v / v%, preferably less than 1 v / v%, more preferably less than 0.1 v / v%, even more preferably less than 0.01 v / v% of any of its analogs or other reaction products. This embodiment may achieve better process repeatability. This embodiment may result from purification (e.g., distillation, sublimation, chromatography, etc.) of the iodine-containing film-forming composition. The disclosed iodine-containing compound contains less than 5% by volume of trace gas impurities, and less than 150 ppm by volume of impurity gas, such as H2O and / or CO2, is contained in said trace gas impurities. Preferably, the water content in the plasma etching gas is less than 20 ppm by weight. Purified products may be produced by distillation and / or passing the gas or liquid through a suitable adsorbent, for example 4 Å molecular sieves.

[0079] The disclosed iodine-containing film-forming compositions contain less than 10 v / v %, preferably less than 1 v / v %, more preferably less than 0.1 v / v %, even more preferably less than 0.01 v / v % of any of its isomers, and they can be purified by gas or liquid distillation to remove the isomers and achieve better process reproducibility.

[0080] Alternatively, the disclosed iodine-containing film-forming compositions may contain 0.01% v / v to 99.99% v / v of the target isomer, particularly when the isomer mixture provides improved process parameters or when isolation of the target isomer is difficult or expensive. The isomer mixture may also reduce the need for two or more gas lines to the reaction chamber.

[0081] Some of the disclosed iodine-containing film-forming compositions are gaseous at room temperature and atmospheric pressure. For non-gaseous (i.e., liquid or solid) compounds, their gaseous forms can be generated by vaporizing the compound through a conventional vaporization step, for example, by direct vaporization or by bubbling inert gas (e.g., Ar, He, Kr, Xe, Ne). Non-gaseous compounds can be fed in liquid state to a vaporizer, where they are vaporized before being introduced into the reaction chamber.

[0082] The disclosed iodine-containing film-forming compositions can be supplied in solvent-free form or in blends with suitable solvents, such as hydrocarbons, e.g., ethylbenzene, xylene, mesitylene, decalin, decane, dodecane, alcohols, e.g., methanol, ethanol, etc. The disclosed precursors can be present in the solvent in various concentrations.

[0083] The neat or blended iodine-containing film-forming composition is introduced into the reactor in vapor form by conventional means such as piping and / or flow meters. The vapor form may be produced by vaporizing the neat or blended composition by conventional vaporization steps by direct vaporization, distillation, bubbling, or by using a sublimator. The neat blended composition may be fed in liquid form to a vaporizer that vaporizes it before being introduced into the reactor. Alternatively, the neat or blended composition may be vaporized by bubbling the carrier gas into the composition by flowing the carrier gas through a vessel containing the composition. The carrier gas may include, but is not limited to, Ar, He, Ne, Kr, Xe, and mixtures thereof. Bubbling the carrier gas may also remove any dissolved oxygen present in the neat or blended composition solution. The carrier gas and the composition are then introduced into the reactor as vapors.

[0084] If necessary, the container containing the disclosed film-forming composition can be heated to a temperature at which the composition can have sufficient vapor pressure. The container can be maintained at a temperature within the range of, for example, about 0° C. to about 250° C. One skilled in the art will recognize that the temperature of the container can be adjusted in known manner to control the amount of precursor vaporized.

[0085] The reactor contains one or more substrates (including but not limited to carbon layers, Si or Si-containing layers) on which the iodine-containing film is deposited. Substrate is generally defined as the material on which the process is performed. The substrate can be any suitable substrate used in semiconductor, solar cell, flat panel, LCD-TFT device manufacturing. Examples of suitable substrates include wafers, e.g., silicon, silica, glass, GaAs wafers. The wafer can have one or more layers of different materials deposited thereon from previous manufacturing steps, as shown in Figures 8a and 8b. For example, the wafer can include an aC (amorphous, doped, porous, spin-on) layer and a dielectric layer. Additionally, the wafer may include a-C layers over silicon layers (crystalline, amorphous, doped, porous, etc.), germanium layers, Si-Ge, silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon doped silicon oxide (SiCOH) layers, metals, metal oxides, high-k materials (e.g., Al2O3, HfO2, ZrO2, etc.), metal nitride layers (Ti, Ru, Ta, etc.), alternating SiO and SiN layers, and combinations thereof. Additionally, the wafer may include a-C layers over copper layers, noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafer may include a-C layers over barrier layers, e.g., manganese, manganese oxide, tin, TaN, etc. Plastic layers, e.g., poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) [PEDOT:PSS], may also be used under the a-C hard layer. The layers may be flat or patterned. The disclosed process may deposit an iodine-containing layer directly on the wafer or directly on one or more layers on the wafer when a patterned layer is formed on the substrate. Furthermore, the terms "film" and "layer" as used herein refer to the thickness of some material placed or spread on a surface, and those skilled in the art will recognize that the surface may be a trench, hole, line, or via. Throughout the specification and claims, the wafer and any associated layer thereon are referred to as a substrate. For example, an iodine-containing film may be deposited onto a carbon-containing material aC layer for modification of the carbon-containing material.

[0086] While the end use of the substrate is not limited to the present invention, this technology may find particular benefit with the following types of substrates: silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0087] The temperature and pressure in the reaction chamber are maintained at conditions suitable for deposition, such as ALD and CVD. In other words, after introducing the vaporized disclosed film-forming composition into the reaction chamber, the conditions in the reaction chamber are such that a portion of the precursor deposits on the substrate to form a layer. For example, the pressure in the reactor or deposition pressure can be about 10 to 2000 psi, as needed, in accordance with the deposition parameters. -3 torr to about 1000 torr, more preferably about 10 -2 The pressure in the reactor may be maintained between about 110° C. and about 1100° C., preferably between about 110° C. and about 500° C. One of ordinary skill in the art will recognize that "at least a portion of the precursor is deposited" means that some or all of the precursor reacts with or adheres to the substrate.

[0088] The temperature at which optimal film growth occurs can be controlled by either controlling the temperature of the substrate holder. Devices used to heat or cool the substrate are well known in the art. The substrate is heated or cooled to a temperature sufficient to obtain the desired film having the desired physical state and composition at a sufficient deposition rate. Non-limiting representative temperature ranges to which the substrate may be subjected include about 110°C to about 1100°C.

[0089] Alternatively, the substrate can be heated to a sufficient temperature to obtain the desired iodine-containing film at a sufficient deposition rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated or cooled include heating from room temperature to approximately 1100°C and cooling from room temperature to approximately -110°C.

[0090] Depending on the particular process parameters, deposition may occur for varying periods of time. In general, deposition may continue for as long as desired, as needed to produce a film with the required properties. Typical film thicknesses may vary from a few angstroms to hundreds of microns, preferably from 0.1 nm to several thousand nm, more preferably from a monolayer (about 0.1 nm) to 1 nm, i.e., 0.1 to 1 nm, depending on the particular deposition process. The deposition process may also be performed as many times as necessary to obtain the desired thickness of the film.

[0091] The disclosed method for depositing an iodine-containing layer on a carbon-containing material substrate includes placing the substrate in a reactor, delivering a vapor of the disclosed iodine-containing film-forming composition into the reactor, contacting / adsorbing the vapor with the surface of the substrate (typically directing the vapor toward the substrate), and forming an iodine-containing layer on the surface of the substrate by a vapor deposition process, where the contacting / adsorbing step modifies the carbon-containing material and / or dopes iodine into the carbon-containing material. Alternatively, the disclosed method for depositing an iodine-containing layer on a carbon-containing material substrate includes placing the substrate in a reactor, delivering a vapor of the disclosed iodine-containing film-forming composition and a vapor of a nitrogen-containing molecule into the reactor, sequentially or simultaneously, contacting / adsorbing the vapor with the surface of the substrate (typically directing the vapor toward the substrate), and forming an iodine-containing layer on the surface of the substrate by a vapor deposition process, where the contacting / adsorbing step modifies the carbon-containing material substrate and / or dopes iodine into the carbon-containing material. Alternatively, the disclosed method for depositing an iodine-containing layer on a carbon-containing material substrate includes exposing the substrate to a vapor of the disclosed iodine-containing film-forming composition and depositing / contacting / adsorbing an iodine-containing layer on the surface of the substrate by a vapor deposition method, where the contacting / adsorbing step modifies the carbon-containing material substrate and / or dopes iodine in the carbon-containing material. Alternatively, the disclosed method for depositing an iodine-containing layer on a carbon-containing material substrate includes exposing the substrate to a vapor of the disclosed iodine-containing film-forming composition and a vapor of a nitrogen-containing molecule, sequentially or simultaneously, and depositing / contacting / adsorbing an iodine-containing layer on the surface of the substrate by a vapor deposition method, where the contacting / adsorbing step modifies the carbon-containing material substrate and / or dopes iodine in the carbon-containing material.

[0092] The vapor of the iodine-containing film-forming composition is generated and then introduced into a reaction chamber containing a substrate. The temperature and pressure in the reaction chamber and the temperature of the substrate are maintained at suitable conditions to deposit at least a portion of the disclosed iodine-containing precursor on the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, the conditions in the reaction chamber are adjusted so that at least a portion of the precursor deposits on the substrate to form an iodine-containing layer. Those skilled in the art will recognize that "at least a portion of the precursor deposits" means that some or all of the precursor reacts with or adheres to the substrate.

[0093] Co-reactants may also be used herein to aid in the formation of the iodine-containing layer and in the doping of iodine.

[0094] The co-reactant can be a nitrogen-containing molecule as described above and listed in Table 2.

[0095] The co-reactant can be an oxidant, such as O2, O3, CO, CO2, NO, NO, NO, NO2, H2O, H2O2, COS, SO2, and combinations thereof. The disclosed film-forming composition and oxidant can be mixed together prior to introduction into the reaction chamber. Alternatively, the oxidant can be continuously introduced into the chamber, the film-forming composition can be pulsed into the chamber, or vice versa. The oxidant can comprise between about 0.01 v / v% and about 99.99 v / v% of the mixture introduced into the chamber (99.99 v / v% represents the introduction of nearly pure oxidant for the continuous introduction alternative).

[0096] The co-reactant can be an additive gas or an additive chemical. The additive gas can be a fluorocarbon and / or a hydrofluorocarbon. Exemplary disclosed fluorocarbons and / or hydrofluorocarbons used for the additive include CF4, CH3F, C2F6, C3F8, C2HF5, C5F8, C6F6, C4F6, C4F8, C1-C 10The additive gas may also include saturated or unsaturated linear, branched, or cyclic hydrofluorocarbons, such as C4H2F6, CHF3, CH2F2, or combinations thereof. a H x I y F z (wherein a=1-10, x≧0, y≧1, z≧0, and x+y+z=a, 2a, or 2a+2), but the iodine-containing additive gas delivered to the reaction chamber is different from the iodine-containing precursor delivered to the reaction chamber. a H x I y F z Iodine-containing molecules having the formula (wherein a=1-10, x≧0, y≧1, z≧0, x+y+z=a, 2a or 2a+2) are not used simultaneously as precursors and additive gases. The iodine-containing additive gas may be CH3I, C2H5I, CF3I, C2F5I, C2H2F3I, saturated or unsaturated linear, branched, cyclic, such as C6H5I, C6H4I2, C3F5I, C2F3I, etc., or combinations thereof. When CH3I is used as the iodine-containing precursor, the iodine-containing additive gas is not CH3I. Similarly, when C2H2F3I is used as the iodine-containing precursor, the iodine-containing additive gas is not C2H2F3I. That is, the iodine-containing precursor and the iodine-containing additive gas are not the same molecule when they are used in the deposition process.

[0097] The co-reactant may be an oxygen-containing molecule as described above.

[0098] The disclosed iodine-containing film-forming composition and the co-reactant can be introduced into the reactor simultaneously (CVD), sequentially (ALD), or different combinations thereof. The reactor can be purged with an inert gas (e.g., Ar, He, Kr, Xe, Ne) between the introduction of the film-forming composition and the introduction of the co-reactant. Alternatively, the co-reactant and the film-forming composition can be mixed together to form a co-reactant / compound mixture and then introduced into the reactor in the form of a mixture. Another example is to continuously introduce the co-reactant and to pulse the disclosed film-forming composition (pulsed CVD). Another example is to continuously introduce the co-reactant and to pulse the film-forming composition while sequentially activating the co-reactant with plasma, provided that the film-forming composition and the non-activated co-reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).

[0099] An inert gas is also introduced into the reaction chamber as a co-reactant to maintain the plasma. The inert gas can be He, Ar, Xe, Kr, Ne, or a combination thereof. The film-forming composition and the inert gas may be mixed prior to introduction into the chamber, with the inert gas comprising from about 0.01 v / v% to about 99.9 v / v% of the thus obtained mixture. Alternatively, the inert gas can be continuously introduced into the chamber, while the film-forming composition is pulsed into the chamber.

[0100] The disclosed film-forming composition and co-reactant may be delivered in pulses into the reaction chamber. Each pulse of the disclosed film-forming composition, if applied, may last for a period ranging from about 0.001 seconds to about 30 minutes, alternatively from about 1 second to about 120 seconds, alternatively from about 5 seconds to about 60 seconds. The co-reactant may also be pulsed into the reactor, and in such embodiments, each pulse may last for a period ranging from about 0.01 seconds to about 30 minutes, alternatively from about 1 second to about 120 seconds, alternatively from about 2 seconds to about 60 seconds. In another alternative, the vaporized film-forming composition and co-reactant may be sprayed simultaneously (without mixing of the composition and reactants) from different sectors of a showerhead under which a susceptor holding several wafers rotates (spatial ALD).

[0101] The disclosed iodine-containing film-forming compositions and co-reactants may be mixed with other gases prior to introduction into the reaction chamber or within the reaction chamber. Preferably, the gases are mixed prior to introduction into the chamber to provide a uniform concentration of incoming gas.

[0102] In another alternative, vapors of the disclosed iodine-containing film-forming compositions and co-reactants may be introduced into the chamber independently of other gases (e.g., when two or more gases react or are easy to deliver independently).

[0103] In another alternative, the disclosed iodine-containing film-forming composition and co-reactant vapors are the only gases used during the deposition process.

[0104] In another alternative, the disclosed iodine-containing film-forming compositions and nitrogen-containing molecules are the only two gases used during the deposition process.

[0105] In another alternative, the disclosed iodine-containing film-forming composition, nitrogen-containing molecule, and inert gas are the only three gases used during the deposition process.

[0106] In another alternative, the disclosed iodine-containing film-forming composition, nitrogen-containing molecule, and oxidizer are the only three gases used during the deposition process.

[0107] In another alternative, the disclosed iodine-containing film-forming compositions, nitrogen-containing molecules, additive gases and oxidizers are the only gases used during the deposition process.

[0108] In another alternative, the disclosed iodine-containing film-forming compositions, nitrogen-containing molecules, additive gases and inert gases are the only gases used during the deposition process.

[0109] The vapor of the disclosed film-forming composition is activated by the plasma to generate an activated film-forming composition. The plasma breaks down the film-forming composition into radical form (i.e., activated film-forming composition). The same plasma treatment process can be applied to co-reactants including inert gases, nitrogen-containing molecules, oxidizers, and additive gases. The plasma can be generated by applying RF or DC power. The plasma can be generated with RF power ranging from about 25 W to about 100,000 W, preferably from about 100 W to about 25,000 W. The plasma can be generated remotely or within the reactor itself. The plasma can be generated in dual CCP or ICP mode with RF applied to both electrodes. The RF frequency of the plasma can range from 100 KHz to 1 GHz. Different RF sources at different frequencies can be coupled and applied at the same electrode. Plasma RF pulsing can further be used to control the fragmentation and reaction of molecules at the substrate. Those skilled in the art are aware of methods and apparatus suitable for such plasma treatment.

[0110] A quadrupole mass spectrometer (QMS), optical emission spectrometer (OES), FTIR, XPS, or other radical / ion measurement tool may be used to measure the activated film-forming composition from the chamber exhaust to determine the type and number of species generated. If necessary, the flow rates of the film-forming composition and / or inert gas may be adjusted to increase or decrease the number of radical species generated.

[0111] Upon obtaining the desired film thickness, the film may be subjected to further processing such as thermal annealing, furnace annealing, rapid thermal annealing, photonic curing, UV curing, UV e-beam curing, laser curing, microwave curing, capping layers and / or plasma gas exposure.

[0112] After annealing, films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of about 1 μohm.cm to about 1 Mohm.cm. Room temperature is about 20°C to about 25°C depending on the season. Bulk resistivity is also known as volume resistivity. Those skilled in the art will recognize that bulk resistivity is typically measured at room temperature for films that are about 50 nm thick. Bulk resistivity typically increases for thinner films due to changes in electron transport mechanisms. Bulk resistivity also increases at higher temperatures. EXAMPLES

[0113] The following non-limiting examples are provided to further illustrate embodiments of the present invention, but are not intended to be all-inclusive and are not intended to limit the scope of the invention described herein.

[0114] The experiments were carried out on a commercial LAM Tools 4520XLe 200 mm plasma etch tool (CCP dual frequency plasma with 10 gas lines).

[0115] The flat wafers tested were: · 350nm PE-CVD amorphous carbon (aC) on Si substrate (purchased from Advantive Tech). 300nm spin-on carbon (SOC) on Si substrate (purchased from SKW) It is.

[0116] For planar testing, atomic polymer compositions were evaluated by Kratos Axis Supra X-ray photoelectron spectroscopy (XPS) at different conditions prepared on a LAM tool (e.g., partial pressure of test molecule, chuck / bottom temperature, source power of 27 MHz, and bias power of 2 MHz). The two gases used during the process were test molecule and Ar.

[0117] To calculate the atomic concentrations of elements in the films, the following XPS method is used: monochromatic Al Kα (1486.6 eV), emission current of 10 mA, full band pass of 160, step size of 0.5 eV. In addition, XPS high resolution spectra were also used to determine the presence of different bonds, such spectra were collected by the following method: monochromatic Al Kα (1486.6 eV), emission current of 10 mA, full band pass of 20, step size of 0.1 eV.

[0118] Two commercially available molecules, CH3I and C2H2F3I, were tested under various plasma process conditions using a Lam 200 mm etch chamber by varying plasma power, temperature, flow rate, and pressure. Additionally, we tested 2-C3F7I (CAS#677-69-0) as a baseline process.

[0119] Baseline reference data: 2-C3F7I was evaluated as the baseline etch compound to quantify the iodine concentration in the aC layer. To simulate the polymer layer formation that appears on the top surface and sidewalls during the plasma treatment etch of the pattern, the process conditions were adjusted: aC layer coupons were etched at 30 mTorr for 60 seconds at a source power of 750 W (27 MHz) and bias power of 0 W (2 MHz) on the substrate. The process feed mixture contained 250 sccm Ar, 15 sccm 2-C3F7I, and no O2. Neutrals and activated species that reach the surface stick to the surface and deposit a thin polymer layer based on their sticking coefficients. Table 3 shows the XPS results, showing the iodine, carbon, fluorine, and oxygen atomic concentrations on the amorphous carbon surface. The atomic concentration of iodine is 1.8%.

[0120] Atomic concentrations of elements detected by XPS at the surface of aC. XPS data are collected with monochromated Al Kα (1486.6 eV), emission current of 10 mA, full band pass of 160, and step size of 0.5 eV. This XPS method is used to collect atomic concentration results for subsequent data.

[0121] [Table 5]

[0122] Example 1: PECVD using CH3I During the plasma process, the iodine-containing gas can be evolved into the following forms: 1) iodine ions (I + , I - );2) Iodine radical (I );3) Iodine-containing polymer ion ( + C x H y I z F d , - C x H y I z F d ), and 4) iodine-containing polymer radicals (·C x H y I z F d ). The first form of iodine can be deposited on the carbon surface by controlling the bias power. Further forms are deposited as polymer layers. In this exemplary experiment, iodine-containing gas CH3I is used as a film-forming precursor to deposit iodine-containing polymer layers on flat wafers (350 nm PE-CVD aC on Si substrate (purchased from Advantive Tech) or 300 nm spin-on carbon (SOC) on Si substrate (purchased from SKW)). Table 4 shows the process conditions of varying bottom electrode power of the LAM tool for deposition of CH3I by PE-CVD.

[0123] [Table 6]

[0124] 1a and 1b show the atomic XPS concentration of iodine on aC material at various source powers and various bias powers with CH3I deposition, respectively. The atomic XPS concentration is collected with monochromatic Al Kα (1486.6 eV), emission current of 10 mA, full band pass of 160, step size of 0.5 eV. The XPS results show the iodine atomic concentration on the aC surface at various bias powers while keeping the top power and source power at 500 W, while keeping the bias power at 500 W. For the conditions screened, the bias and source power seem to have a minor effect on the iodine concentration, except for the 500w / 500w source / bias, which shows an increase of about 15%.

[0125] The substrate temperature can be controlled by the chuck / bottom electrode temperature. Such process conditions shown in Table 5, varying bottom electrode temperature process conditions, can adjust the iodine concentration on the surface of the carbon-containing material due to the volatility of iodine and iodine-containing species as shown in Figure 2. As shown, the iodine atomic concentration decreases while the chuck temperature increases. The temperature effect shows a clear trend, at least for a bias of 0 W. As the temperature increases, the iodine atomic % decreases. The best results of about 10% were obtained at 5°C. AFM results show a uniform layer (Rq=0.2-0.3 nm). The modified process shows a smooth layer post-process (Rq=0.2-0.3 nm).

[0126] [Table 7]

[0127] The process pressure and the flow ratio of CH3I and Ar can be adjusted to improve the iodine concentration. Such process conditions, i.e., process pressure adjustment, are shown in Table 6, and flow ratio adjustments shown in Table 7 can adjust the iodine concentration on the surface of the carbon-containing material. Figure 3 shows the result of 14% increase in iodine atomic concentration when the pressure increases from 30 mTorr to 200 mTorr. Figure 4 shows that the iodine atomic concentration result is optimized at 150 / 70 sccm condition.

[0128] [Table 8]

[0129] [Table 9]

[0130] Example 2: Stability test of deposited iodine-containing carbon films using CH3I Iodine-containing molecules are known to be unstable under light and moisture. Therefore, it is important to test the formed films under such conditions. The tested iodine-containing carbon films were prepared under the following conditions: source power 500W / bias power 500W, source temperature 30°C, bias / chuck electrode temperature 20°C, gap 1.35cm, variable pressure, Ar / CHI, 150 / 70sccm, reaction time 15s. Two stability tests were performed on these synthesized films: 1) moisture test (samples were left in ambient conditions [air], at room temperature, in a dark box, for one week of exposure), and light test (samples were left in N2 conditions, at room temperature, for one week of exposure to room lighting). The iodine concentration stability results can be found in Figure 5, which shows that the iodine atom concentration remains roughly constant (approximately 7%) after one week of exposure during moisture and light tests for CHI. This finding indicates the stability of the synthesized films.

[0131] XPS data analysis: The deposited iodine-containing carbon film is further analyzed by XPS (monochromatic Al Kα (1486.6 eV), 10 mA emission current, 20 full band pass, 0.1 eV step size). The analyzed iodine-containing carbon film was prepared under the following conditions: source power 500 W / bias power 500 W, source temperature 30 °C, bias / chuck electrode temperature 20 °C, gap 1.35 cm, varying pressure, Ar / CHI, 150 / 70 sccm, reaction time 15 s. As shown in Figure 6a, iodine I3d5 / 2 has three types of bonds on the aC surface: organic iodine (IC, ICO) and a very small amount of absorbed I2 molecules. In the carbon C1 spectrum shown in Figure 6b, CI (285.1 eV) bonds were also found in the C1 peak overlap, which confirms the iodine bond to the carbon matrix. This bond further ensures film stability, ie, the film is uniform and has a stable iodine atom concentration.

[0132] Example 3: Plasma deposition using C2H2F3I with a Lam tool etcher C2H2F3I was used as a film-forming precursor to deposit iodine-containing polymer film on aC layer.As discussed in previous examples, iodine ions, iodine radicals and iodine-containing species can be controlled by source power and bias power.This process control (shown in Table 8) results in optimal conditions for iodine concentration on carbon-containing material, as shown in Figure 7a and Figure 7b, which indicates that optimal iodine atomic concentration can be achieved by adjusting source and bias power at 1000W (27MHz source power) / 1000W (2MHz bias power), respectively, using C2H2F3I.

[0133] [Table 10]

[0134] Example 4: Plasma deposition using CH3I and C3HF4N with a LAM tool etcher An iodine-containing polymer film was deposited on the aC layer using CH3I and C3HF4N as the film-forming precursor and N-containing co-reactant. For comparison, an iodine-containing polymer film was deposited on the aC layer using CH3I and N2 as the film-forming precursor and N-containing co-reactant. As discussed in the previous examples, during the plasma process, the iodine-containing gas is converted into three forms: 1) iodine ions (I + , I - );2) Iodine radical (I );3) Iodine-containing polymer ion ( + C x H y I z Fd, - C x H y I z Fd), and 4) iodine-containing polymer radicals (·C x H y I z F d ) into the first and third forms of iodine. The first and third forms of iodine can be deposited on the carbon surface by controlling the bias power. Furthermore, these chemical forms are deposited as a polymer layer that can enhance the EUV absorption of the layer during the patterning process. These iodine forms can be further captured by nitrogen species from C3HF4N in the gas phase and on the surface of the deposited polymer, forming a deposited iodine and nitrogen-containing carbon film. Such process conditions for the LAM tool etcher are shown in Table 9.

[0135] [Table 11]

[0136] The deposited iodine and nitrogen-containing carbon films are further analyzed by Kratos Axis Supra X-ray photoelectron spectroscopy (XPS). Figure 9 shows the atomic XPS concentration of iodine on the aC surface at various bias powers. The mixture of CH3I and C3HF4N shows an improvement in iodine atomic % (about 25% increase) compared to CH3I alone and CH3I+N2. To calculate the atomic concentration of elements in the deposited films, the following XPS method was used: monochromatic Al Kα (1486.6 eV), 10 mA emission current, full band pass of 160, step size of 0.5 eV. In addition, XPS high resolution spectra were also used to determine the presence of different bonds, but such spectra were collected by the following method: monochromatic Al Kα (1486.6 eV), 10 mA emission current, full band pass of 20, step size of 0.1 eV.

[0137] The analyzed iodine-containing carbon films were prepared under the following conditions: source power 500W / bias power 500W, source temperature 30°C, bias / chuck electrode temperature 20°C, gap 1.35cm, pressure 200mTorr, Ar / CH3I / C3HF4N, 150 / 70 / 15sccm, or reaction time 15s. As shown in Figure 10, the N1 peak of Ar / CH3I / C3HF4N has three types of bonds on the aC surface: C-NH2, C-NH3, and CN. These bonds suggest the trapping of iodine species based on the increase in iodine concentration. In the case of nitrogen mixing (Ar / CH3I / N2, 150 / 70 / 15sccm), nitrogen is not well incorporated into the carbon film (Figure 9), and therefore there is no increase in iodine concentration.

[0138] In summary, the disclosed method provides a new / novel chemical reaction to deposit iodine films on carbon surfaces as well as a method to enhance the concentration of iodine doped on the carbon surface. Such iodine modified layers can be utilized in a variety of applications in semiconductor fabrication equipment.

[0139] Although the subject matter described herein may be described in relation to example implementations for processing one or more computing application functions / operations for a computing application having a user-interactive component, the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management method, system, platform, and / or device.

[0140] It will be understood that many further modifications of the details, materials, steps and arrangements of parts described and illustrated herein to explain the nature of the invention may be made by those skilled in the art without departing from the principles and scope of the invention as set forth in the appended claims.Accordingly, the invention is not intended to be limited to the specific embodiments in the foregoing examples and / or accompanying drawings.

[0141] While embodiments of the present invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit or teaching of the present invention. The embodiments described herein are merely illustrative and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Thus, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, the scope of which includes all equivalents of the subject matter of the claims.

Claims

1. 1. A method for depositing an iodine-containing film on a substrate material, comprising: a) C ａ H ｘ I ｙ F ｚ exposing said substrate material to vapor of a film-forming composition comprising an iodine-containing precursor having the formula: b) depositing the iodine-containing film formed by the iodine-containing precursor on the substrate material by a vapor deposition method; A method comprising:

2. The method of claim 1 , wherein step b) comprises modifying the substrate material or doping iodine from the iodine-containing precursor into the substrate material.

3. Further, when a=0 and x=0, the iodine-containing precursor is ２ , I.F. ３ , I.F. ５ , and I.F. ７ 2. The method of claim 1 , wherein when a=0, z=0, the iodine-containing precursor comprises HI.

4. 10. The method of claim 1, further comprising exposing the substrate material to a vapor of a co-reactant, either sequentially or simultaneously with step a).

5. The coreactant has the general formula C ｘ H ｙ F ｚ N.H. ａ (wherein x=1 to 6, y=0 to 13, z=0 to 13, and a=1 to 2) or C ｘ H ｙ F ｚ N-R １ (wherein x=1 to 6, y=0 to 13, z=0 to 13, and R １ is C １ ~C ５ 5. The method of claim 4, wherein the nitrogen-containing molecule is a hydrocarbon.

6. The nitrogen-containing molecule is C ３ H.F. ４ The method of claim 5 , wherein N is N.

7. The coreactant is O ２ , O ３ , CO, CO ２ , NO, N ２ O, NO ２ , H ２ O, H ２ O ２ , COS, SO ２ 5. The method of claim 4, wherein the oxidizing agent is selected from the group consisting of oxidizing gas, compressed air, or a combination thereof.

8. The coreactant is He, Ar, N ２ 5. The method of claim 4, wherein the inert gas is selected from the group consisting of Xe, Kr, Ne, or combinations thereof.

9. The coreactant is CF ４ , C.H. ３ F.C. ２ F ６ , C ３ F ８ , C ２ H.F. ５ , C ５ F ８ , C ６ F ６ , C ４ F ６ , C ４ F ８ , C １ ~C １０ Saturated or unsaturated linear, branched or cyclic hydrofluorocarbons, e.g., C ４ H ２ F ６ , C ３ H ２ F ６ , C.H.F. ３ , C.H. ２ F ２ or a combination thereof; ａ H ｘ I ｙ F ｚ The iodine-containing additive other than the above is represented by the formula C ｂ H ｍ I ｎ F ｏ (wherein b=1 to 10, m≧0, n≧1, o≧0, m+n+o=b, 2b, or 2b+2; provided that when a=1, x=2, and z=0, y is not equal to 2, provided that when b=0 and m=0, the iodine-containing additive is I ２ , I.F. ３ , I.F. ５ , and I.F. ７ and when b=0, o=0, the iodine-containing additive comprises HI.

10. The iodine-containing precursor is CH ３ I and C ２ H ２ F ３ The method according to any one of claims 1 to 9, wherein the compound is selected from the group consisting of I.

11. 10. The method of any one of claims 1 to 9, wherein the iodine atomic concentration in the iodine-containing film ranges from about 0.01% to about 50%, with a uniform concentration through the iodine-containing film.

12. 1. A method for depositing an iodine-containing and nitrogen-containing film on a substrate material, comprising: a) sequentially or simultaneously exposing said substrate material to a vapor of a film-forming composition and a vapor of a nitrogen-containing molecule; (wherein the film-forming composition is C ａ H ｘ I ｙ F ｚ wherein a=1-10, x≧0, y≧1, z≧0, and x+y+z=a, 2a, or 2a+2, with the proviso that when a=1, x=2, and z=0, then y is not equal to 2; The nitrogen-containing molecule has the general formula C ｍ H ｎ F ｏ N.H. ｂ Or C ｘ H ｙ F ｚ N-R １ (In the formula, m=1 to 6, n=0 to 13, o=0 to 13, b=1 to 2, and R １ is C １ ~C ５ ) which is a hydrocarbon; b) depositing an iodine-containing film formed by said iodine-containing precursor on said substrate material by a thermal or plasma method; A method comprising:

13. The method of claim 12 , wherein step b) comprises modifying the substrate material or doping iodine into the substrate material.

14. The iodine-containing precursor is CH ３ I and C ２ H ２ F ３ 14. The method of claim 12 or 13, wherein the compound is selected from the group consisting of I.

15. The nitrogen-containing molecule is C ３ H.F. ４ The method of claim 12 or 13, wherein N is N.

16. 1. A method for depositing an iodine-containing film on a substrate material, comprising: a) CH ３ I or C ２ H ２ F ３ Steam of I and C ３ H.F. ４ sequentially or simultaneously exposing the substrate material to N vapor; b) forming CH on said substrate material by thermal or plasma methods; ３ I or C ２ H ２ F ３ depositing a layer of an iodine-containing polymer formed by I; wherein said step b) comprises modifying or doping iodine into said substrate material.

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