Method for photoresist material deposition

Abstract

The disclosed and claimed subject matter relates to bismuth-based and antimony-based compounds and compositions that can be used to deposit bismuth-containing films and antimony-containing films on substrates.

Description

background Technical Field

[0001] The disclosed and claimed subject matter relates to bismuth-based and antimony-based compositions that can be used to deposit bismuth-containing and antimony-containing films on substrates. In particular, the disclosed and claimed subject matter relates to bismuth-based and antimony-based compositions and materials, as well as methods for forming metal-organic photoresists. Background Technology

[0002] The goal of the modern semiconductor industry is to develop nanolithography technologies and related materials for achieving higher resolution in photolithography. This goal has received increasing attention because there is a need to manufacture integrated circuits with higher electronic component density to enable more advanced electronic technologies.

[0003] The size of the elemental units constituting photoresist is considered a constraint on achieving patterned feature sizes with the desired quality in terms of edge roughness (LER), linewidth roughness (LWR), and resolution. For the past few decades, chemically amplified resists (CARs) based on photoacids and reactive organic polymers have dominated the semiconductor industry. The hydrodynamics and / or large radius of gyration of polymers make it inherently difficult to achieve feature sizes <10 nm with polymer-based CARs. Furthermore, acid diffusion in CARs can be another problem in achieving nanopatterns with the desired low LER.

[0004] Currently, the market needs non-CAR photoresist materials suitable for EUV lithography that allow for node widths of <20 nm. However, developing such photoresists presents significant technical challenges and requires consideration of several photochemical factors. Due to the extremely short wavelength of EUV light (13.5 nm), EUV photons carry a high energy of 92 eV, more than ten times higher than the energy of deep UV (DUV) photons with wavelengths of 193–248 nm. Because of this high energy (92 eV), EUV photons can interact with atoms and emit one of their core electrons. The resulting photoelectron recombines with the photoresist material and scatters, emitting another electron. These absorption and emission events (accompanied by energy dissipation at each step) continue in a cascade manner until the electron energy drops below approximately 30 eV. The secondary electron with low energy can ultimately induce bond breaking to generate free radicals, which can be used for chemical events such as bond formation / crosslinking.

[0005] Recently, organometallic molecules, coordination molecules, and nanoclusters have been developed for effective EUV photoresist materials. Certain metal-containing photoresists can possess high EUV absorption cross-sections, thus improving sensitivity and reducing the roughness of patterned structures caused by photon shot noise. Two main design strategies have been employed to develop coordination EUV photoresists, both of which have shown potential utility for EUV nanolithography. Recent research on EUV photoresists classifies materials into metal nanoclusters or organometallic / coordinating small molecules. Metal nanoclusters consist of many metal atoms, while organometallic or coordination complexes typically contain one or two metal centers and associated ligands. In EUV photoresists, the size and composition of the basic unit particles are key factors influencing dose, sensitivity, and pattern shape. For example, when the unit particles contain a high density of metal atoms, they exhibit improved sensitivity and require a lower dose for solubility transition. Furthermore, uniform and small unit particle sizes help reduce line edge roughness in the final pattern.

[0006] Metal nanoclusters Metal nanoclusters with diameters of a few nanometers (2-3 nm) are a promising class of photoresist materials for EUV lithography, potentially achieving half-pitch lines <20 nm. The key mechanism of photolysis of metal nanoclusters during EUV lithography typically relies on the generation of free radicals via homolytic cleavage of metal-carbon bonds and subsequent free radical-free radical coupling to induce the aggregation and condensation of nanoclusters with a solubility switch. Therefore, the rational design of metals and organic ligands is crucial. As the desired nanopattern size and LER (Left-to-Ratio) become smaller, especially at the <10 nm node, the size of the nanoclusters needs to be further reduced. See also... Coord. Chem. Rev. 493,215307 (2023).

[0007] Tin oxide clusters have been used in EUV lithography. EUV light at a wavelength of 13.5 nm induced the formation of [(RSn)] clusters. 12 O 14 The photolysis reaction of tin-oxygen nanoclusters [OH]₆X₂. See also Microelectron. Eng. , 127, 44-50 (2014). Tin oxide clusters were synthesized in a one-step reaction using alkyl stanonic acid [RSn(=O)OH, where R = aliphatic hydrocarbon] or aryl stannic acid (RSnCl3, where R = aryl). The effects of the R and X structures on EUV-induced photolysis were investigated. Although patterning of lines around 18 nm has been reported, it remains unclear whether smaller lines can be achieved using tin oxide nanoclusters.

[0008] Zr and Hf atoms can be used to generate EUV photoresists. HfO2-based nanoclusters (with hydrodynamic diameters of 2-3 nm) coated with various organic ligands can be prepared via a sol-gel process and used in EUV photoresists. See also Proc. SPIE , 10146, 101460I (2017). Although no experimental data were reported, the authors noted that all nanoclusters could be patterned at a critical size of 20-25 nm in 13.4 nm EUV lithography. It is unclear whether patterning at <20 nm can be achieved with hafnium oxide nanoclusters.

[0009] Zinc nanoclusters have been studied for use in EUV lithography and exhibit high EUV absorption compared to Zr and Hf atoms. For this reason, zinc nanoclusters have recently emerged as a novel class of nanocluster photoresists. Zn-oxygen nanocluster photoresist films were prepared by hydrolysis in a spin-coating aqueous solution containing methacrylic acid. See also J. Mater. Chem. C., 52611 （2017） Deep-UV radiation induces the aggregation of nanoclusters; however, thermal annealing is required after the development step to induce nucleation and growth of zinc oxide crystals. Thermal annealing at high temperatures (>300°C) results in a line pattern (bimodal distribution) with indentations on the surface. This is attributed to the difference in thermal reactivity between the internal and external structures, which exposes the surface to contractile forces.

[0010] Synthesis of zinc-containing building blocks for metal-organic frameworks using monodentate ligands of benzoic acid derivatives. See also Chem. Mater., 30(12), 4124 (2018) The Zn-containing building blocks interact strongly with soft X-rays at a wavelength of 13 nm. In contrast to previously reported resist materials based on ZrO2 or HfO2 nanoparticles, the zinc m-methylbenzoic acid clusters exhibit good resolution (15 nm) in their nanopatterns due to their small size (1-2 nm), narrow size distribution, and uniform film formation.

[0011] Previous work has disclosed the potential applications of hydrogen silsesquioxane (HSQ)-based silicon nanoclusters in electron beam lithography. See [link to previous work]. J. Vac. Sci. Technol. B., 16, 69-76 (1998) The prepared HSQ photoresist films had thicknesses of 50-100 nm, and their photolithographic properties were compared with those of CAR-based resists. While HSQ-based silicon clusters exhibited good resolution in photolithographic nanopatterning, their photosensitivity needs improvement to make them more suitable for practical industrial applications. See also Front. Nanosci. , Vol.11, 349 (2016).

[0012] Organometallic / Coordination Small Molecule Low molecular weight organometallic compounds (commonly referred to as "molecular organometallic resists," denoted as "MORE" in the literature) are smaller than nanoclusters but still contain EUV-absorbing metal atoms. By utilizing atomic-level structural design in organometallic synthesis, those skilled in the art can finely tune the structure of photoresists at the atomic scale to obtain optimal molecular photoresists for EUV lithography. The strategies used to design low molecular weight organometallic photoresists are similar to those used for metal-oxygen nanoclusters. In many cases, using low molecular weight organometallic compounds, the metal-carbon bond undergoes photochemical homolytic cleavage to generate free radical material contained in the structure, while the remaining chelating sites at the metal center are occupied by heteroatoms such as oxygen and nitrogen. Organometallic and inorganic complexes can form one-dimensional, two-dimensional, and three-dimensional structures called coordination polymers.

[0013] Organometallic complexes with the structure R₂Sn(O₂CR')₂ were synthesized, where R = butyl, phenyl, or benzyl, and O₂CR' = acetate, acrylate, methacrylate, neopentyl ester, or benzoate. One study examined the effects of ligand volume and Sn-R bond energy on photosensitivity and photolithography properties. See also Master Chem. Front. , 1, 2613-2619 (2017). The results indicate a trade-off between sensitivity and resolution. Most of the complexes studied exhibited poor sensitivity (dose = 50-600 mJ / cm). 2 (), but with good resolution and LER. The complex of R=benzyl and O2CR'=neovale ester shows a 16-nm half-pitch dense line with an LER of 2.1 nm and a 22-nm half-pitch dense line with an LER of 1.4 nm in negative lithography by EUV.

[0014] Other studies tested different metal atoms in the complex form RnM(O2CR)2, where M is antimony, bismuth, tin, or tellurium. The studies showed that antimony and tellurium complexes exhibited the best and worst sensitivity, respectively; the reason for this observation remains unclear. See also J. of Micro / Nanolithography, MEMS, and MOEMS Volume 14, Issue 41, Article No. 043503 (2015). Triphenylantimony diacrylate was used to obtain a solution with 5.6 mJ / cm². 2 Dense 35-nm lines were generated. The pattern size could be further reduced to 16-nm; however, pattern collapse was observed.

[0015] U.S. Patent Application Publication No. 2024 / 0210821A1 discloses precursors and methods related to bismuth oxycarbon photoresists. The precursors described in this disclosure are nitrogen-containing precursors having the formula R'Bi(NR2)2 or R'2BiNR2, wherein R and R' comprise various alkyl and / or trialkylsilyl groups. The methods involve reacting the bismuth precursor with an oxygen-containing co-agent to form a thin film.

[0016] U.S. Patent Application Publication No. 2022 / 0317572A1 discloses an organometallic photoresist suitable for deep ultraviolet or extreme ultraviolet lithography. The photoresist precursor comprises an organometallic molecule containing a metal selected from bismuth or antimony with an oxidation state of 3 or higher and at least one polymerizable group R.

[0017] Triphenylbismuth reacts with a series of aromatic carboxylic acids (RCO2H) with different pKa and functionalities [R=PhCH=CH, o-MeOC6H4, m-MeOC6H4, o-H2NC6H, o-O2NC6H4, p-O2NC6H4, 2-(C5H4N)] in toluene under reflux to form bismuth tri(carboxylic acid) complexes. Several mixed phenyl / carboxylic acid complexes have also been observed with certain carboxylic acids. See also Dalton Trans , 4852-4858 (2006). The reactivity with heterocoordinated alkyl / aryl bismuth compounds is not described in this report.

[0018] The presence of water in the reaction of triphenylbismuth and carboxylic acid results in large bismuth clusters rather than unimolecular complexes or coordination polymers. See also Angew. Chem. Int. Ed. ,45,563 8-5642 (2006).

[0019] Oxalic acid is the simplest dicarboxylic acid form, and the oxalate ion (C2O4) 2- Organotin compounds can be used as polydentate ligands for various metals. While organotin compounds have attracted significant attention as potential EUV photoresists, different metal complexes, such as platinum and palladium mononuclear complexes with the structure L2M(C2O4) (where M = Pt or Pd, and L is a neutral phosphine ligand), have also been studied. See also J. of Micro / Nanolilhography, MEMS, and MOEMS Volume 14, Issue 4, 043511 (2015). The complex was spin-coated and exposed to EUV as a positive photoresist. Optimal sensitivity was observed for (dppm) Pd(C2O4) with 54 mJ / cm². 2 (dppm = bis(diphenylphosphine)methane); at 50 mJ / cm 2 E 尺寸 (E) 尺寸: Dosage versus size (the amount of dosage required to produce the appropriate resist characteristic size) to obtain a 30-nm half-pitch. It should be noted that Pd and Pt are extremely expensive relative to other transition metals (e.g., Co) and quasi-metals (e.g., Sb / Bi).

[0020] Therefore, although two main strategies have been proposed to enhance photosensitivity while reducing the patterning size in photolithography, namely, (1) molecular and (2) nanocluster design based on organometallic coordination chemistry, photochemical reaction mechanisms, photolithography performance, and advances to address resolution limits, these are active research topics in the semiconductor industry. Several problems remain unsolved in the long process of achieving industrially demanding nanoscale patterns with high quality and yield, and many fundamental questions about photochemical mechanisms need to be addressed.

[0021] Some elements with good EUV atomic light absorption cross-sections at EUV wavelengths (e.g., 13.5 nm) have not been extensively studied. These include antimony (Sb) and bismuth (Bi).

[0022] Most EUV photoresist materials developed to date rely on a top-down approach, particularly spin coating, which produces thin films with amorphous structures. In such films, the elemental unit particles of the material are randomly distributed and react with each other through cross-linking, making it difficult to achieve the desired line edge roughness (LER) for sub-10 nm patterns. Therefore, new design paradigms for both materials and film structures are needed to overcome these problems. Summary of the Invention

[0023] In one embodiment, the disclosed and claimed subject matter relates to bismuth-based and antimony-based compounds that can be used to deposit bismuth-containing and antimony-containing films on a substrate. In a further aspect of this embodiment, the disclosed and claimed subject matter includes formulations comprising the disclosed and claimed bismuth-based and antimony-based compounds.

[0024] In another embodiment, the disclosed and claimed subject matter includes a deposition method comprising exposing a bismuth-containing and / or antimony-containing film to extreme ultraviolet (EUV) light, wherein the film is formed from the disclosed and claimed bismuth-containing and antimony-containing compounds and / or formulations thereof. In one aspect of this embodiment, the film is deposited on a substrate via a spin-coating process. In another aspect of this embodiment, the film is deposited on a substrate via a vapor deposition process such as CVD, CCVD, and ALD.

[0025] In another embodiment, the disclosed and claimed subject matter includes thin films formed by exposing the disclosed and claimed bismuth- and antimony-containing compounds and / or their formulations to extreme ultraviolet (EUV) light.

[0026] In another embodiment, the disclosed and claimed subject matter includes the use of bismuth-based and antimony-based clusters to form films. A related embodiment is the use of thin film formation techniques (such as spin-coating deposition) to form bismuth-containing and antimony-containing films.

[0027] In another embodiment, a heterocomplex used in the metal-organic resist method is synthesized by selectively replacing aryl ligands with alkyl ligands using novel ligands. Attached Figure Description

[0028] The accompanying drawings, included to provide a further understanding of the disclosed subject matter and incorporated in and forming part of this specification, illustrate embodiments of the disclosed subject matter and, together with the specification, serve to explain the principles of the disclosed subject matter. In the drawings: Figure 1 The synthesis and acid-catalyzed coupling of nanoclusters of unsaturated groups in the form of aryl- and vinyl-sulfonic acids are shown. Figure 2 The crosslinking of individual nanoclusters to form a network polymer film of nanoclusters is shown; Figure 3 The use of functionalized nanoclusters in the patterning process is demonstrated; Figure 4 The use of functionalized nanoclusters in the patterning process is demonstrated; Figure 5 The image shows [Bi(neopentyl)2(OAc)]. n The molecular structure; Figure 6a shows [Bi(methyl)(OAc)2] n (Left), [Bi(isopropyl)(OAc)2] n (Middle) and [Bi(neopentyl)(OAc)2] n (Right) Asymmetric molecular structure; Figure 6b shows [Bi(methyl)(OAc)2] n The extended molecular structure; and Figure 7 The patterning of the developing wafer of Example 23 is shown. Detailed Implementation

[0029] All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference to the same extent that each reference is individually and specifically cited and incorporated herein by reference and fully elaborated herein.

[0030] Unless otherwise stated herein or clearly contradicted by the context, the terms “a” and “an” and “the”, and similar indicators, used in the context of describing the disclosed and claimed subject matter (particularly in the context of the following claims) should be interpreted as covering both singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise stated herein, the descriptions of numerical ranges herein are intended only as a way of abbreviating each individual value falling within that range, and each individual value is incorporated into this specification as if it were described separately herein. Unless otherwise stated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order. The use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the disclosed and claimed subject matter and does not constitute a limitation on the scope of the disclosed and claimed subject matter unless otherwise required. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in the specification and claims includes the narrower terms "consistent with substantially" and "consisting with".

[0031] This document describes implementations of the disclosed and claimed subject matter, including the best modes known to the inventors for carrying out the disclosed and claimed subject matter. Variations of those implementations will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately adopt these variations, and the inventors intend to practice the disclosed and claimed subject matter in ways different from those specifically described herein. Therefore, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter described in the appended claims, as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the disclosed and claimed subject matter encompasses any combination of the foregoing elements in all possible variations.

[0032] For ease of reference, "microelectronic device" or "semiconductor device" refers to semiconductor wafers having integrated circuits, memories, and other electronic structures manufactured thereon, as well as flat panel displays, phase-change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS), manufactured for microelectronic, integrated circuit, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the terms "microelectronic device" or "semiconductor device" are not intended to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0033] "Substantially free of" is defined herein as less than 0.001% by weight. "Substantially free of" also includes 0.000% by weight. The term "free of" refers to 0.000% by weight. As used herein, "about" or "approximately" is intended to correspond to within ±5% of the stated value.

[0034] In all such compositions, where specific components of the composition are discussed with reference to a range including a zero lower limit of weight percentage (or "wt%)", it should be understood that such components may or may not be present in various specific embodiments of the composition, and where such components are present, they may be present at concentrations as low as 0.001 wt%, based on the total weight of the composition in which such components are used. It should be noted that all percentages of components are weight percentages and are based on the total weight of the composition, i.e., 100%. Any reference to "one or more" or "at least one" includes "two or more" and "three or more," etc.

[0035] Where applicable, unless otherwise stated, all weight percentages are “net”, meaning they do not include the aqueous solution in which they are present when added to the composition. For example, “net” means the amount of undiluted acid or other material by weight % (i.e., 100g of 85% phosphoric acid constitutes 85g of acid and 15g of diluent).

[0036] Furthermore, when the compositions described herein are referred to by weight percent, it should be understood that, in any case, the total weight percent of all components (including non-essential components, such as impurities) should not exceed 100% by weight. In compositions “consisting substantially of the said components,” such components may total 100% by weight of the composition or may total less than 100% by weight. When the total weight percent of components is less than 100% by weight, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2% by weight or less of impurities. In another embodiment, the formulation may contain 1% by weight or less of impurities. In a further embodiment, the formulation may contain 0.05% by weight or less of impurities. In other such embodiments, the constituent components may form at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, most preferably at least 99.9% by weight, and may include other components that do not substantially affect performance. Otherwise, in the absence of significant non-essential impurity components, it should be understood that the composition of all essential constituent components substantially totals 100% by weight.

[0037] In addition to the known and understood join point notation for covalent bonds, the symbol "– –” also signifies the connection point of a covalent bond.

[0038] The headings used in this article are not intended to be restrictive; rather, they are included for organizational purposes only.

[0039] As described above, the disclosed and claimed subject matter relates to bismuth-based and antimony-based compounds and compositions thereof (described below) that can be used to deposit bismuth-containing and antimony-containing films on substrates.

[0040] The complexes or compositions described herein are suitable as volatile precursors for ALD, CVD, pulsed CVD, plasma-enhanced ALD (PEALD), or plasma-enhanced CVD (PECVD) for the fabrication of semiconductor-type microelectronic devices. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal-organic CVD), thermochemical vapor deposition, plasma-enhanced chemical vapor deposition (“PECVD”), high-density PECVD, photon-assisted CVD, plasma-photon-assisted (“PPECVD”), low-temperature chemical vapor deposition, chemical-assisted vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, supercritical fluid deposition, and low-energy CVD (LECVD). In some embodiments, films are deposited via atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) processes. As used herein, the term "chemical vapor deposition process" refers to any process in which the substrate is exposed to one or more volatile precursors, which react and / or decompose on the substrate surface to produce the desired deposition. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited is constant in each reaction cycle) sequential surface chemistry that deposits a film of material onto a substrate of varying compositions. Although precursors, reagents, and sources used herein may sometimes be described as "gaseous," it should be understood that precursors may be liquid or solid, delivered to the reactor with or without an inert gas by direct evaporation, bubbling, or sublimation. In some cases, the evaporated precursor may pass through a plasma generator. In one embodiment, a metal-containing film is deposited using an ALD process. In another embodiment, a metal-containing film is deposited using a CCVD process. In a further embodiment, a metal-containing film is deposited using a thermal CVD process. The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

[0041] Bismuth- and antimony-containing compositions can be used in several embodiments, including but not limited to “single-source” precursors that exhibit sufficient vapor pressure and thermal stability to deposit thin bismuth-containing films on substrates via ALD or CVD. These compositions contain at least one photosensitive ligand that promotes crosslinking and / or bond breaking during EUV exposure. The methods disclosed herein avoid premature reaction of the metal precursors by using ALD or CCVD methods that separate the precursors before and / or during introduction into the reactor. Methods for depositing photoresist films generally include, substantially consist of, or consist of the following steps: (a) Providing a substrate in the reaction chamber (b) Providing one or more bismuth-containing reactants or antimony-containing reactants and one or more co-reactants to the reaction chamber to initiate a reaction between the reactants and co-reactants, thereby depositing a photoresist film on the substrate.

[0042] Co-reactants are selected to preferentially react with at least one type of ligand present in bismuth- or antimony-containing reactants. Examples of co-reactants include, but are not limited to, molecular oxygen, ozone, water, and carboxylic acids.

[0043] In one embodiment, the disclosed and claimed subject matter also includes a method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, said method comprising, substantially comprising, or comprising the following steps: (a) Providing a substrate to the reactor; (b) Contacting the substrate with one or more bismuth-containing compounds and antimony-containing compounds disclosed herein, as well as one or more co-reactants; and (c) Forming a bismuth-containing film or an antimony-containing film on a substrate.

[0044] In a further aspect of this embodiment, the substrate is contacted with one or more bismuth-containing compounds. In a further aspect of this embodiment, the substrate is contacted with one or more antimony-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of oxygen-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of, one or more of water, oxygen, ozone, carboxylic acids, alcohols, and peroxides. In a further aspect of this embodiment, the substrate is selected from metals, metal oxides, metal nitrides, metal silicides, silicon oxide, silicon nitride, fluorosilicate glass (FSG), organosilicon glass (OSG), carbon-doped oxides (CDO), porous low-k materials, and combinations thereof.

[0045] In a further embodiment, the disclosed and claimed subject matter also includes a method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, said method comprising, substantially comprising, or comprising the following steps: (a) Providing a substrate to the reactor; (b) Pretreatment is performed to remove contaminants from the surface of the substrate; (c) Contacting the substrate with one or more bismuth-containing compounds and antimony-containing compounds disclosed herein, as well as one or more co-reactants; and (d) Forming a bismuth-containing film or an antimony-containing film on a substrate.

[0046] In a further aspect of this embodiment, the substrate is contacted with one or more bismuth-containing compounds. In a further aspect of this embodiment, the substrate is contacted with one or more antimony-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of oxygen-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of, one or more of water, oxygen, ozone, carboxylic acids, alcohols, and peroxides. In a further aspect of this embodiment, the substrate is selected from metals, metal oxides, metal nitrides, metal silicides, silicon oxide, silicon nitride, fluorosilicate glass (FSG), organosilicon glass (OSG), carbon-doped oxides (CDO), porous low-k materials, and combinations thereof.

[0047] In a further embodiment, the disclosed and claimed subject matter also includes a method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, said method comprising, substantially comprising, or comprising the following steps: (a) Providing a substrate to the reactor; (b) Contacting the substrate with one or more bismuth-containing compounds and antimony-containing compounds disclosed herein, as well as one or more co-reactants; (c) Exposing a substrate, one or more bismuth-containing compounds and antimony-containing compounds, and one or more co-reactants to plasma; and (d) Forming a bismuth-containing film or an antimony-containing film on a substrate.

[0048] In a further aspect of this embodiment, the substrate is contacted with one or more bismuth-containing compounds. In a further aspect of this embodiment, the substrate is contacted with one or more antimony-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of oxygen-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of, one or more of water, oxygen, ozone, carboxylic acids, alcohols, and peroxides. In a further aspect of this embodiment, the substrate is selected from metals, metal oxides, metal nitrides, metal silicides, silicon oxide, silicon nitride, fluorosilicate glass (FSG), organosilicon glass (OSG), carbon-doped oxides (CDO), porous low-k materials, and combinations thereof.

[0049] In a further embodiment, the disclosed and claimed subject matter also includes a method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, said method comprising, substantially comprising, or comprising the following steps: (a) Providing a substrate to the reactor; (b) Contacting the substrate with one or more bismuth-containing compounds and antimony-containing compounds, as well as one or more co-reactants; (c) Forming a bismuth-containing film or an antimony-containing film on a substrate; (d) Expose a portion of the membrane to extreme ultraviolet (EUV) light. (e) Remove a portion of the membrane.

[0050] In a further aspect of this embodiment, the substrate is contacted with one or more bismuth-containing compounds. In a further aspect of this embodiment, the substrate is contacted with one or more antimony-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of oxygen-containing compounds. In a further aspect of this embodiment, one or more co-reactants include, are substantially composed of, or are composed of, one or more of water, oxygen, ozone, carboxylic acids, alcohols, and peroxides. In a further aspect of this embodiment, the substrate is selected from metals, metal oxides, metal nitrides, metal silicides, silicon oxide, silicon nitride, fluorosilicate glass (FSG), organosilicon glass (OSG), carbon-doped oxides (CDO), porous low-k materials, and combinations thereof.

[0051] In some embodiments, the method uses a reducing agent. The reducing agent is typically introduced in gaseous form. Examples of suitable reducing agents include, but are not limited to, hydrogen, hydrogen plasma, remote hydrogen plasma, silanes (i.e., diethylsilane, ethylsilane, dimethylsilane, phenylsilane, silane, diethylsilane, aminosilane, chlorosilane), boranes (i.e., borane, diborane), aluminum alkyl, germane, hydrazine, ammonia, and / or mixtures thereof.

[0052] The deposition methods disclosed herein may include one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon (Ne), and / or mixtures thereof. In some embodiments, a purge gas (such as Ar) is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 10,000 seconds to purge unreacted material and any byproducts that may remain in the reactor.

[0053] Energy can be applied to at least one of a precursor, reducing agent, other precursors, or combinations thereof to induce a reaction and form a metal-containing film or coating on a substrate. This energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helical wave plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation process can include a direct plasma generation process, wherein the plasma is generated directly in the reactor, or optionally, a remote plasma generation process, wherein the plasma is generated outside the reactor and supplied to the reactor.

[0054] Precursors can be delivered to the reaction chamber in various ways. In one embodiment, a liquid delivery system can be used. In another embodiment, a combined liquid delivery and flash evaporation process unit can be employed, such as a turbine evaporator manufactured by MSP Corporation of Shoreview, MN, to enable volumetric delivery of low-volatility materials, resulting in repeatable delivery and deposition without thermal decomposition of the precursor. The bismuth-containing and antimony-containing compounds (and / or combinations thereof) described herein can be effectively used as source reagents in direct liquid injection mode to provide a vapor stream of these precursors to the ALD or CVD reactor.

[0055] In some embodiments, these compositions include those utilizing hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used in the disclosed and claimed methods include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (naphthalene). The bismuth-containing and antimony-containing compounds (and / or combinations thereof) described herein can also be stored and used in stainless steel containers. In some embodiments, the hydrocarbon solvent in the composition is a high-boiling solvent or has a boiling point of 100°C or higher.

[0056] In some embodiments, the gas line connecting the precursor tank to the reaction chamber is heated to one or more temperatures according to process requirements, and the container containing the composition is maintained at one or more temperatures for bubbling. In other embodiments, the precursor is injected into an evaporator maintained at one or more temperatures for direct liquid injection.

[0057] A stream of argon and / or other gases can be used as a carrier gas to help deliver the vapor of at least one precursor to the reaction chamber during precursor pulses. In some embodiments, the process pressure of the reaction chamber is between 1 Torr and 50 Torr, preferably between 5 Torr and 20 Torr.

[0058] The deposited film may contain varying levels of hydrogen, oxygen, carbon, and nitrogen. The carbon content in the deposited film should preferably be >5 atomic percent (at.%), more preferably >10 at.%, and most preferably >12 at.%. A high carbon content in the film can produce a film that is reactive to electron beams and / or ultraviolet light. The reactivity of the film to electron beams and / or ultraviolet light can be enhanced by the presence of carbonaceous groups directly bonded to bismuth in the deposited film.

[0059] In the deposition of high-quality films, substrate temperature is a crucial process variable. Typical substrate temperatures range from approximately 150°C to approximately 350°C. Higher temperatures promote higher film growth rates. However, higher temperatures can also result in films with lower carbon content. Therefore, it is desirable to find film precursors and process conditions that enable high-growth-rate film deposition while maintaining an appropriate amount of carbon in the film.

[0060] In another embodiment, a bismuth-containing film or an antimony-containing film on the substrate is developed to produce a patterned substrate. The development process includes wet methods and dry methods.

[0061] One embodiment of the wet development method involves contacting the film with one or more solvents that selectively dissolve a portion of the film, thereby forming a patterned substrate. In one aspect of this embodiment, the solvent contact time can be varied, for example, from 1 second to 10,000 seconds. In another aspect of this embodiment, solvent exposure can be performed at a temperature ranging from 20°C to the standard boiling point of the solvent. In a further aspect of this embodiment, the one or more solvents include one or more of THF, cyclohexanone, propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), anisole, 2-heptanone, and 4-methyl-2-pentanol. In one aspect, such formulations are free of aromatic solvents.

[0062] One embodiment of the dry development method involves contacting a film with a vapor phase or gaseous reactant that selectively etches a portion of the film, thereby forming a patterned substrate. In one aspect of this embodiment, the reactant contact time can be varied, for example, from 1 second to 10,000 seconds. In another aspect of this embodiment, reactant exposure can be performed at a temperature ranging from about 20°C to about 350°C. In a further aspect of this embodiment, one or more reactants comprise one or more inorganic acids, such as HCl, HBr, and HI. In another embodiment, one or more reactants comprise one or more organic acids. The organic acids in this embodiment include carboxylic acids, such as formic acid, acetic acid, butyric acid, and neopentanoic acid.

[0063] In one embodiment, spin-coating deposition is used to fabricate bismuth-containing films and / or antimony-containing films. Formulations of bismuth-containing compounds and antimony-containing compounds are prepared by dissolving precursors in suitable solvents.

[0064] In another aspect, the disclosed and claimed subject matter includes formulations comprising (i) one or more of the disclosed and claimed bismuth-containing and antimony-containing compounds and (ii) one or more solvents suitable for spin coating processes. In one embodiment, the formulation comprises (i) two or more of the disclosed and claimed bismuth-containing and antimony-containing compounds and (ii) one or more solvents suitable for spin coating processes.

[0065] On the other hand, the disclosed and claimed subject matter includes the preparation of the target compound at the desired concentration in a spin-coating solvent (mixture) to avoid material separation and direct formation of spin-coating formulations.

[0066] In one embodiment, one or more solvents suitable for spin coating processes include one or more of alcohols, esters, ketones, lactones, diketones, solvents having an aromatic moiety, solvents having a carboxylic acid, amides, and mixtures thereof.

[0067] In another embodiment, one or more solvents suitable for spin coating processes include one or more of the following: propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl pentyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropionate, methyl-3-ethoxypropionate, methyl-3-methoxypropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl neopentanoate, ethyl neopentanoate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propylene glycol monomethyl ether The solvents used in the spin coating process include esters, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, toluene, 2-heptanone, 1-hexanol, 4-methyl-2-pentanol, and anisole. In a further aspect of this embodiment, one or more solvents used in the spin coating process include one or more of toluene, tetrahydrofuran (THF), cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol. In a further aspect of this embodiment, one or more solvents used in the spin-coating process include one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol. In one aspect, such formulations do not contain aromatic solvents.

[0068] In another embodiment, the bismuth-containing compound and the antimony-containing compound formulation have a concentration of about 1 mg / mL to about 1000 mg / mL. In another embodiment, the bismuth-containing compound and the antimony-containing compound can be formulated into a solution having a concentration of about 1 mg / mL to about 100 mg / mL. In another embodiment, the bismuth-containing compound and the antimony-containing compound can be formulated into a solution having a tin cluster concentration of about 1 mg / mL to about 50 mg / mL. In another embodiment, the bismuth-containing compound and the antimony-containing compound formulation can be formulated into a solution having a tin cluster concentration of about 10 mg / mL to about 50 mg / mL. In another embodiment, the bismuth-containing compound and the antimony-containing compound formulation have a tin cluster concentration of about 25 mg / mL to about 50 mg / mL. In another embodiment, the bismuth-containing compound and the antimony-containing compound formulation have a concentration of about 50 mg / mL to about 100 mg / mL.

[0069] The disclosed and claimed subject matter also includes the use of disclosed and claimed bismuth-containing and antimony-containing compound formulations in EUV and electron beam processes. Such formulations are used or can be used to pattern a radiation-sensitive coating in a method comprising the following steps: (i) forming a coating on a substrate surface with one or more of the disclosed and claimed bismuth-containing and antimony-containing compound formulations, (ii) drying the coating to produce a dried layer; and (iii) irradiating at least a portion of the dried layer to form a latent image.

[0070] In one embodiment, the substrate of step (i) comprises silicon. In another embodiment, the substrate of step (i) comprises silicon and at least one additional material layer (i.e., a material stack) deposited on top thereon.

[0071] In one embodiment, the dried layer of step (ii) has a thickness of about 1 nm to about 500 nm. In one embodiment, the dried layer of step (ii) has a thickness of about 10 nm to about 100 nm. In one embodiment, the dried layer of step (ii) has a thickness of about 15 nm to about 50 nm.

[0072] In one embodiment, the irradiation in step (iii) includes exposing at least a portion of the dried layer to ionizing radiation. In one aspect of this embodiment, the ionizing radiation has a wavelength range of about 10 nm to about 365 nm. In another aspect of this embodiment, the ionizing radiation is generated by an electron beam.

[0073] In another embodiment, the dried layer obtained from steps (i)-(iii) is developed to produce a patterned substrate. The development process includes both wet and dry methods.

[0074] One embodiment of the wet development method involves contacting a dried layer with one or more solvents that selectively dissolve a portion of the dried layer to form a patterned substrate. In one aspect of this embodiment, the solvent contact time can vary, for example, from 1 second to 10,000 seconds. In another aspect of this embodiment, solvent exposure can be performed at a temperature ranging from 20°C to the standard boiling point of the solvent. In a further aspect of this embodiment, the one or more solvents include one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol. In one aspect, such formulations do not contain aromatic solvents.

[0075] One embodiment of the dry development method involves contacting a dried layer with a vapor or gaseous reactant that selectively etches a portion of the dried layer, thereby forming a patterned substrate. In one aspect of this embodiment, the reactant contact time can be varied, for example, from 1 second to 10,000 seconds. In another aspect of this embodiment, reactant exposure can be performed at a temperature of about 20°C to about 300°C. In a further aspect of this embodiment, one or more reactants comprise one or more inorganic acids, such as HCl, HBr, and HI. In another embodiment, one or more reactants comprise one or more organic acids. The organic acids in this embodiment include carboxylic acids, such as formic acid, acetic acid, butyric acid, and neopentanoic acid.

[0076] One embodiment of material photopatterning involves spin-coating onto a substrate at 500 rpm for 5 seconds, followed by 800-5000 rpm for 15-120 seconds. The substrate is then exposed to an electron beam of 2-100 keV at 1-10,000 μC or EUV (13.5 nm) through a mask. The exposed wafer is baked at 100-200°C for 0.5-20 minutes and developed in an organic solvent (mixture) for 15-300 seconds. Solvents and mixtures thereof include, but are not limited to, 2-heptanone, cyclohexanone, PGMEA, PGME, anisole and mixtures of PGMEA, anisole and cyclohexanone, and anisole and 2-heptanone.

[0077] In one embodiment, the disclosed and claimed subject matter relates to a bismuth compound comprising, substantially, or consisting of, at least one aromatic ligand and at least one non-aromatic ligand, having different reactivity to the co-reactant used for depositing a photoresist film.

[0078] Suitable bismuth-based and antimony-based compounds that can be used or formulated for the disclosed and claimed methods include the following materials.

[0079] Class 1 compounds In one embodiment, the disclosed and claimed method and formulation utilize the formula Bi(R) a ) x (Ar) 3-x It contains at least one aromatic (“Ar”) ligand and at least one non-aromatic (“R”) ligand. a Bismuth compounds containing ligands, wherein (i) x = 1 or 2; (ii) Each R aIndependently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, alkoxy, carboxylic acid group, amino, diketo acid group, keto ester group, amidoyl group, guanidinyl group, and amidine group; and (iii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle.

[0080] In some implementations, R a It has the structure described in Table 1:

[0081] Table 1 In some implementations, R a It has the structure described in Table 2:

[0082] Table 2 In some implementations, R a It has the structure described in Table 3:

[0083] Table 3 In some implementations, R a It has the structure described in Table 4:

[0084] Table 4 In some implementations, R a It has the structure described in Table 5:

[0085] Table 5 In some implementations, R a It has the structure described in Table 6:

[0086] Table 6 In some implementations, R a It has the structure described in Table 7:

[0087] Table 7 In some implementations, R a It has the structure described in Table 8:

[0088] Table 8 In some implementations, Ar has the structure shown in Table 9:

[0089] Table 9 Specific examples of this implementation include, but are not limited to, the examples shown in Table 10:

[0090] Table 10 Class 2 compounds In another embodiment, the disclosed and claimed subject matter methods and formulations utilize a bismuth compound comprising, substantially comprising, or consisting of: at least one alkyl group and at least one other ligand having different reactivity with the co-reactant used for depositing a photoresist film. More specifically, the disclosed and claimed subject matter relates to the formula Bi(R a ) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is independently one of alkoxy, carboxylic acid, amino, diketo acid, keto ester, amidoyl, amidoyl and guanidine.

[0091] In some implementations, L has the structure described in Table 11:

[0092] Table 11 In some implementations, L has the structure described in Table 12:

[0093] Table 12 In some implementations, L has the structure described in Table 13:

[0094] Table 13 In some implementations, L has the structure described in Table 14:

[0095] Table 14 In some implementations, L has the structure described in Table 15:

[0096] Table 15 In some implementations, L has the structure described in Table 16:

[0097] Table 16 In some implementations, L has the structure described in Table 17:

[0098] Table 17 Class 3 compounds In another embodiment, the disclosed and claimed methods and formulations utilize formula (R a )2Bi-Bi(R b Bismuth compounds of 2, wherein each R a and R b Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic group, amino-substituted C3-C8 aromatic group, 5-membered heterocycle, and 6-membered heterocycle.

[0099] Examples include, but are not limited to, the compounds listed in Table 18:

[0100] Table 18 Class 4 compounds In another embodiment, the disclosed and claimed method and formulation tablet use the formula M(R) a ) x (R b ) 3-x or (R) a )2M-M(R b Compounds of )2, in which (i) M is independently Sb or Bi; (ii) X = 0, 1, or 2; and (iii) Each R a and R b Independently, it can be an unsubstituted straight-chain C1-C6 alkyl group, one or more halogen-substituted straight-chain C1-C6 alkyl groups, an amino-substituted straight-chain C1-C6 alkyl group, an alkoxy-substituted straight-chain C3-C6 alkyl group, an unsubstituted branched C3-C6 alkyl group, one or more halogen-substituted branched C3-C6 alkyl groups, an amino-substituted branched C3-C6 alkyl group, an alkoxy-substituted branched C3-C6 alkyl group, an unsubstituted amine, a substituted amine, -Si(CH3)3, or an unsubstituted cyclic C3-C6 alkyl group. Alkyl group, one or more halogen-substituted cyclic C3-C6 alkyl groups, amino-substituted cyclic C3-C6 alkyl groups, unsubstituted C3-C8 aromatic groups, one or more halogen-substituted C3-C8 aromatic groups, amino-substituted C3-C8 aromatic groups, 5-membered heterocycles, 6-membered heterocycles, trialkyltinalkyl groups wherein the alkyl group is a straight-chain C1-C6 alkyl group, trialkyltinalkyl groups wherein the alkyl group is a branched C3-C6 alkyl group, and trialkyltinalkyl groups wherein the alkyl group is a cyclic C3-C6 alkyl group.

[0101] Examples include, but are not limited to, the compounds listed in Table 19:

[0102] Table 19 Class 5 compounds In another embodiment, the disclosed and claimed subject matter method and formulation utilize formula (R a )2Sb-Sb(R b Antimony compounds or cyclotetrastane: (The following text:) ) Each R a and R bIndependently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic group, amino-substituted C3-C8 aromatic group, 5-membered heterocycle, and 6-membered heterocycle.

[0103] Examples include, but are not limited to, the compounds listed in Table 20:

[0104] Table 20 Class 6 compounds In another embodiment, the disclosed and claimed subject matter method and formulation utilize formula M(R) a ) x (R b ) 3-x or (R) a )2M-M(R b Compounds of )2, in which (i) M is independently Sb or Bi; (ii) X = 0, 1, or 2; and (iii) Each R a and R b Independently, it is one of the following: a straight-chain C1-C6 alkyl group, one or more halogen-substituted unsaturated straight-chain C1-C6 alkyl groups, an amino-substituted unsaturated straight-chain C1-C6 alkyl group, an unsaturated branched C3-C6 alkyl group, one or more halogen-substituted unsaturated branched C3-C6 alkyl groups, an amino-substituted unsaturated branched C3-C6 alkyl group, an unsubstituted amine, a substituted amine, -Si(CH3)3, an unsubstituted cyclic C3-C6 alkyl group, one or more halogen-substituted unsaturated cyclic C3-C6 alkyl groups, an amino-substituted unsaturated cyclic C3-C6 alkyl group, a 6-membered aromatic ring, an aromatic ring having a C2-C6 unsaturated alkyl group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iv) The compound contains at least one unsaturated group.

[0105] Examples include, but are not limited to, the compounds listed in Table 21:

[0106] Table 21 The disclosed and claimed subjects also include the use of bismuth- and antimony-containing compositions having unsaturated alkyl ligands or imide / imide functional groups (exhibiting sufficient vapor pressure and thermal stability) for depositing thin films, but forming polymers upon decomposition. Polymer formation can be triggered by pyrolysis or exposure to EUV light, as well as other process conditions. These compositions may include neutral compounds having polymerizable ligands (for crosslinking); or they may be self-initiating photocatalysts.

[0107] Another embodiment is a method using compounds that react with a co-agent in a liquid or gas phase to form polymers or nanoclusters. An example of this embodiment is a pre-formed soluble nanocluster that can be dispersed in a uniform film. Another embodiment is a pre-formed nanocluster dispersed in an inert liquid, with or without a dispersing agent (such as a surfactant).

[0108] Among other methods, hydrolysis and sol-gel reactions are used to prepare metal oxide nanoclusters, preferably with a diameter of <10 nm, more preferably <5 nm, and most preferably <2 nm. The nanoclusters can be of various shapes, including spherical, square, hexagonal, and irregular shapes. The surface of the nanoclusters can be functionalized with groups suitable for dissolution and / or linking reaction chemistry to link the nanoclusters into 2-D or 3-D networks. Examples of linking reaction chemistry include, but are not limited to, polymerization, crosslinking, homolytic and heterolytic coupling reactions, and condensation reactions. Polymerization reactions can be promoted by chemical catalysts, pyrolysis, plasma treatment, and light exposure, as well as other conditions. Chemical catalysts may include the monomer units themselves or added polymerization catalysts.

[0109] Bismuth-containing clusters can begin to form from bismuth compounds such as bismuth nitrate, bismuth chloride, other bismuth salts, and triphenylbismuth. Antimony-containing clusters can begin to form from antimony compounds such as antimony nitrate, antimony chloride, other antimony salts, and triphenylantimony.

[0110] The resulting nanoclusters can be further functionalized through subsequent reactions to attach additional groups to their surface. These groups can contain reactive moieties, such as unsaturated functional groups, functional groups undergoing reduction or oxidation, photoreactive functional groups, and functional groups activated by pyrolysis to react with other functional groups.

[0111] Many reactions can be used to attach functional groups, including but not limited to polymerization, crosslinking, homolytic and heterolytic coupling, and condensation.

[0112] One implementation of this reaction for attaching functional groups to nanoclusters is acid-catalyzed coupling. Examples of the synthesis and acid-catalyzed coupling of nanoclusters with unsaturated groups (such as arylsulfonic acids and vinylsulfonic acids) are shown in [reference needed]. Figure 1The addition of such unsaturated functional groups can be used in subsequent processing steps to promote crosslinking or other methods to form solid bismuth-containing films, such as... Figure 2 As shown.

[0113] Figure 3 The use of functionalized nanoclusters in a patterning process is illustrated, wherein cross-functionalized nanoclusters on a substrate are exposed using a patterned mask. The functionalized nanoclusters exposed to light are cross-linked. In a second step, the unexposed nanoclusters are removed from the substrate.

[0114] Figure 4 The use of functionalized nanoclusters in a patterning process is illustrated, wherein cross-linked functionalized nanoclusters on a substrate are exposed using a patterned mask. The cross-linked functionalized nanoclusters exposed to light are uncross-linked. In a second step, the exposed nanoclusters are removed from the substrate.

[0115] Suitable methods for dispersing pre-formed clusters onto a substrate include spin coating, spraying, and atomization.

[0116] The disclosed and claimed subject matter also includes the formation of heterobimonas compounds by selectively replacing aryl ligands on heterobimonas alkyl / aryl compounds to produce heterobimonas compositions that can be used as metal-organic photoresists. The aryl ligands can be replaced by ligands such as alkoxide groups, carboxylic acid groups, diketo acid groups, keto ester groups, amidoyl groups, and amidine groups.

[0117] Although it is well known in the art that alkyl groups on bismuth are more reactive to certain reagents (e.g., oxidizing agents) than aryl groups, we were surprised to find very high selectivity for replacing aryl groups with oxygen-containing ligands, starting with hetero-bismuth organometallic compounds. The reaction of triphenylbismuth with acetic acid leads to the formation of bismuth triacetate, similar to the literature reports on the reaction of triphenylbismuth with other carboxylic acids: Conversely, the reaction of heterocyclic bismuth organometallic compounds, di(neopentyl)phenylbismuth, with acetic acid under the same conditions results in the selective substitution of only the phenyl ligand to form [Bi(neopentyl)2(OAc)]. n : Figure 5 The [Bi(neopentyl)₂(OAc)] assay is shown by single-crystal X-ray diffraction. n Molecular structure of coordination polymers.

[0118] In a similar manner, under the same conditions, the substitution of the phenyl ligand of methyldiphenylbismuth with acetic acid resulted in an unusually selective R reaction to produce [Bi(methyl)(OAc)2]n: Figure 6a shows the [Bi(methyl)(OAc)2] chromatogram determined by single-crystal X-ray diffraction. n [Bi(isopropyl)(OAc)2] n and [Bi(neopentyl)(OAc)2] n The asymmetric molecular structure of the coordination polymer. Examination of structural parameters revealed that molecular packing (packaging groups, symmetry, crystal density) is influenced by the R groups bound to bismuth.

[0119] Figure 6b shows the [Bi(methyl)(OAc)2] chromatogram determined by single-crystal X-ray diffraction. n Extended structure of coordination polymers (A-axis).

[0120] Attempts to react the trialkylbismuth compound with acetic acid under forced conditions (150 °C) resulted in no reaction. Tris(neopentyl)bismuth was heated to 150 °C in the presence of glacial acetic acid. NMR analysis showed no reaction under these conditions. Therefore, the selective reaction of aryl ligands relative to alkyl ligands can be used in reactions to generate hetero bismuth complexes that can be used in metal-organic photoresists.

[0121] Formulations containing specific compounds derived from the selective reaction of aryl ligands with alkyl ligands can be used in metal-organic photoresist processes. The formulation may comprise portions of a film coating on a substrate to be patterned.

[0122] Figure 7 The patterned film (which is manufactured by spin-coating methyl bismuth diacetate to form a thin film) was selectively exposed to electron beam radiation and developed as described in Example 23.

[0123] The disclosed and claimed subjects also include the following new bismuth-containing compounds.

[0124] Group 1 In one embodiment, the disclosed and claimed subject matter includes the formula Bi(R) a ) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each R aIndependently, it is an unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is a carboxylic acid group; and (iv) Exclude x=1 and R a It is a compound with -CH3 and each L being an acetic acid group.

[0125] As those skilled in the art will understand, the bismuth compounds of the disclosed and claimed embodiments exclude the following compounds: .

[0126] In one aspect of this embodiment, x=1. In another aspect of this embodiment, x=2.

[0127] In another aspect of this embodiment, each L is independently one of an acetate group, a formic acid group, a neopentanoic acid group, a methacrylate group, and a salicylic acid group. In one aspect of this embodiment, each L is independently one of a formic acid group, a neopentanoic acid group, a methacrylate group, and a salicylic acid group. In another aspect of this embodiment, each L is an acetate group. In another aspect of this embodiment, each L is a formic acid group. In another aspect of this embodiment, each L is a neopentanoic acid group. In another aspect of this embodiment, each L is a methacrylate group. In another aspect of this embodiment, each L is a salicylic acid group. In another aspect of this embodiment, when x=1, each L is the same. In another aspect of this embodiment, when x=1, each L is different from each other.

[0128] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0129] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0130] In one aspect of this implementation, formula Bi(R)a ) x (L) 3-X The bismuth compounds are: .

[0131] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0132] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0133] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0134] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0135] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0136] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0137] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0138] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-XThe bismuth compounds are: .

[0139] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0140] In one aspect of this implementation, formula Bi(R) a ) x (L) 3-X The bismuth compounds are: .

[0141] Group 2 In another embodiment, the disclosed and claimed subject matter includes formula Bi(R) a ) x (L) 3-X Bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is an unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is an amido, formamidin, or guanidine.

[0142] In one aspect of this embodiment, x=1. In another aspect of this embodiment, x=2.

[0143] In another aspect of this embodiment, each L is an amidine group. In another aspect of this embodiment, each L is a formamidinium group. In another aspect of this embodiment, each L is a guanidine group.

[0144] Group 3 In another embodiment, the disclosed and claimed subject matter includes formula Bi(Ar). x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iii) Each L is an amido, formamidin, or guanidine.

[0145] In one aspect of this embodiment, x=1. In another aspect of this embodiment, x=2.

[0146] In another aspect of this embodiment, each L is an amidine. In another aspect of this embodiment, each L is a methylmidine. In another aspect of this embodiment, each L is a guanidine. In another aspect of this embodiment, each L is independently one of 1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidinyl, N,N′-diisopropyl-N″,N″-dimethylguanidine, and N,N′-diisopropylacetamidine. In another aspect of this embodiment, each L is 1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidinyl. In another aspect of this embodiment, each L is N,N'-diisopropyl-N”,N”-dimethylguanidine. In another aspect of this embodiment, each L is N,N'-diisopropylacetamidine. In another aspect of this embodiment, when x=1, each L is the same. In another aspect of this implementation, when x=1, each L is different from the others.

[0147] In one aspect of this implementation, formula Bi(Ar) x (L) 3-x The bismuth compounds are: .

[0148] In one aspect of this implementation, formula Bi(Ar) x (L) 3-x The bismuth compounds are: .

[0149] In one aspect of this implementation, formula Bi(Ar) x (L) 3-x The bismuth compounds are: .

[0150] Group 4 In another embodiment, the disclosed and claimed subject matter includes formula Bi(Ar). x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iii) Each L is an alkoxide group.

[0151] In one aspect of this embodiment, x=1. In another aspect of this embodiment, x=2.

[0152] In one aspect of this implementation, formula Bi(Ar) x (L) 3-x The bismuth compounds are: .

[0153] Example Reference will now be made to more specific embodiments of this disclosure and experimental results supporting these embodiments. The embodiments are given to illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0154] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter (including the description provided by the following embodiments) is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0155] Materials and methods: All reactions and operations described in the examples were performed under a nitrogen atmosphere using an inert atmosphere glove box or standard Schlenk technique. Unless otherwise stated, all reagents were purchased from Millipore Sigma and used “as is” without further purification. For single-crystal X-ray diffraction experiments, suitable crystals were selected and mounted on a Bruker APEX-IICCD diffractometer. The crystals were kept at ~100 K during data collection. Olex2 [Dolomanov, OV, etc.] was used. J. Appl Cryst. , 42, 339-341 (2009)], structure using SHELXT [Sheldrick, GM, Acta Cryst. [A71, 3-8 (2015)] The structure resolution procedure uses intrinsic phasing for resolution and uses XL [Sheldrick, GM, Acta Cryst. [A64, 112-122 (2008)] The refinement package is optimized using least squares minimization.

[0156] In the vapor deposition process, the bismuth precursor is delivered to the reaction chamber via a stainless steel container filled with ~50-100 sccm of argon gas. The temperature of the bismuth precursor container is varied between approximately 110-120°C to achieve sufficient vapor pressure for the precursor. The wafer temperature varies between approximately 130-200°C. The reaction chamber pressure varies between approximately 5-25 Torr. The deposition time varies between approximately 20 seconds and 20 minutes to obtain films of different thicknesses.

[0157] Bismuth-containing films were grown on silicon substrates using a CN-1 nozzle reactor.

[0158] Film thickness was measured using X-ray fluorescence (XRF), elliptic polarization method, and scanning electron microscopy (SEM). Specific Implementation Example 1: Synthesis of dineopentylbismuth acetate / Bi(neopentyl)2(OAc). A 1:1 stoichiometric mixture of di(neopentyl)phenylbismuth and glacial acetic acid in d8-toluene was placed in an NMR tube. NMR analysis showed no reaction after 2 hours at room temperature. The tube was heated to 90°C for 4 hours and then cooled to room temperature over 4 hours, resulting in colorless crystals. NMR analysis of the supernatant showed only trace amounts of unreacted di(neopentyl)phenylbismuth. The molecular structure is shown in... Figure 5 C 12 H 25 BiO2 ( M Crystal data for (410.30 g / mol): orthorhombic, space group Pbca (no. 61). a = 14.6494(17) Å, b = 10.4636(13) Å, c = 21.400(3) Å, V = 3280.3(7) Å 3 , Z = 8, T = 100.15K, μ(CuKα)=20.974 mm -1 , Dcalc =1.662g / cm 3 25,306 reflections were measured (8.262° ≤ 2Θ ≤ 138.124°), and 3,040 unique reflections were measured. R int =0.0475, R sigma =0.0282), which is used in all calculations. Finally R 1 is 0.0350 (I>2α(I)), and wR 2 is 0.0778 (all data).

[0160] Example 2: Synthesis of methylbismuth diacetate / Bi(methyl)(OAc)2. A 1:2 stoichiometric mixture of methylbismuth diacetate and glacial acetic acid in d8-toluene was placed in an NMR tube. NMR analysis showed no reaction after 2 hours at room temperature. The tube was heated to 90°C for 4 hours and then cooled to room temperature over 4 hours, resulting in colorless crystals. NMR analysis of the supernatant showed only trace amounts of unreacted methylbismuth diacetate. The asymmetric crystal structure is shown in Figure 6a (left). The extended crystal structure (A-axis) is shown in Figure 6b. C5H9BiO4 ( M Crystal data for (342.10 g / mol): Tetragonal system, space group P4 / nnc. a = b = 16.3676(10) Å, c = 15.5112(10) Å, V = 4155.4(6) Å 3 , Z = 16, T = 100.15 K, Dcalc =2.187 g / cm 3 21,823 reflections were measured, including 2,139 unique reflections, which were used in all calculations.

[0161] Example 3: Synthesis of Bi(OAc)3. A stoichiometric mixture of triphenylbismuth and glacial acetic acid in d8-toluene (approximately 1:2) was placed in an NMR tube. NMR analysis showed no reaction after 2 hours at room temperature. The tube was heated to 90°C for 4 hours and then cooled to room temperature over the same period, resulting in the formation of colorless crystals. NMR analysis of the supernatant revealed Bi(OAc)3 and trace amounts that may correspond to BI(phenyl)3. x (OAc) y Other compounds. Acetic acid is completely consumed during the reaction. Crystal data for C6H9BiO6 (MW = 386.11 g / mol): monoclinic system, space group P21 / c (no. 14). a = 12.0052(4) Å, b =10.8168(4) Å, c = 7.2433(3) Å, β = 106.612(2), V = 901.34(6) Å 3 , Z = 4, T = 100.15 K, μ(CuKα) = 38.462 mm -1 , Dcalc = 2.845 g / cm 39819 reflections were measured (7.684° ≤ 2Θ ≤ 139.482°), and 1379 unique reflections were observed. R int = 0.0409, R sigma = 0.0263), which is used in all calculations. Finally... R 1 is 0.0223 (I>2σ(I)) and wR 2 is 0.0575 (all data).

[0162] Example 4: Synthesis of neopentylbismuth diacetate. Bismuth diphenylchloride (10 g, 25.1 mmol) and 150 cc of toluene were added to a 200 mL Schlenk flask. The white suspension was cooled to -78°C with stirring. A solution of neopentylmagnesium chloride (2,2-dimethylpropylmagnesium chloride, 1 M in diethyl ether, 25 cc, 25 mmol) was added dropwise at -78°C with stirring. After addition, the flask was warmed to room temperature. The resulting light gray suspension was stirred overnight and filtered to obtain a light yellow solution. A portion (~1 g) of the crude neopentylbismuth diphenylchloride was dissolved in 10 cc of toluene. Glacial acetic acid (0.5 g) was added with stirring. The resulting colorless solution was allowed to stand overnight at room temperature to form colorless crystals. The crystals were washed with toluene (2 × 2 cc) and pentane (2 cc) and dried under vacuum. 1 ¹H NMR (d⁸-THF): 2.2 (s, 2H), 1.82 (s, 6H), 1.15 (s, 9H). X-ray diffraction was performed on the selected crystal to characterize the crystal structure of neopentylbismuth diacetate. The asymmetric crystal structure is shown in Figure 6a (right). C₁₈H₂O 17 Crystal data for BiO4 (MW = 398.2 g / mol): Tetragonal crystal system, space group I4 1 / a , a = b = 23.0989(7) Å, c = 9.6411(4) Å, V = 5144.1(4) Å 3 , Z = 16, T = 100 K, collected 44685 reflections, 2637 unique reflections, which are used in all calculations.

[0163] Example 5: Synthesis of neopentylbismuth dipentanoate. Neopentyldiphenylbismuth (~1 g) was dissolved in 10 cc of toluene. Neopentanoic acid (0.5 g) was added with stirring. The resulting colorless solution was allowed to stand overnight at room temperature to form colorless crystals. The crystals were washed with toluene (2 × 2 cc) and dried under vacuum. 1¹H NMR (d8-toluene): 2.31 (s, 2H), 1.18 (s, 18H), 1.09 (s, 9H).

[0164] Example 6: Synthesis of methylbismuth dicarboxylate. Methyldiphenylbismuth (5 g, 13.2 mmol) in 50 cc toluene was added to a 100 mL flask. Formic acid (1.38 g, 30 mmol) was added dropwise with stirring. A white precipitate was observed 2–3 minutes after addition. After standing overnight at room temperature, the white suspension was partially liquefied with shaking and filtered. Hexane (3 × 10 mL) was added to wash the substance from the flask and toluene was washed away from the bright white solid. The solid was dried under vacuum at room temperature. The bright white amorphous solid (3.6 g) was analyzed by TGA and DSC.

[0165] Example 7: Synthesis of methylbismuth dinepentanoate. Methyldiphenylbismuth (5 g, 13.2 mmol) in 25 cc toluene was added to a 100 cc Schlenk flask. Neopentanoic acid (3.06 g; 30 mmol) was added dropwise to the colorless solution with stirring. The solution was heated to 100°C for 4 hours under slight nitrogen pressure (~2 psig). The resulting colorless solution was slowly cooled to room temperature. After standing overnight, a large amount of colorless fine crystals formed in the flask. The colorless supernatant was removed by pipette. The crystals were washed with hexane (2 × 2 cc), and the washings were added to the supernatant. The crystals were dried under vacuum at room temperature for 1 hour. 1 H NMR (d8-THF): 1.33 (s, 3H), 1.15 (s, 18H).

[0166] Example 8: Synthesis of dimethylbismuth acetate. Phenylated bismuth dibromide (73 mmol) was suspended in toluene (150 cc) and cooled to -78°C. Methyllithium (1.6 M, 160 mmol, 100 cc in diethyl ether) was added dropwise with stirring. The resulting suspension was warmed to room temperature and stirred overnight. The gray precipitate was filtered, and the resulting colorless solution was concentrated under vacuum, resulting in an additional solid precipitate. This solid was filtered, and the resulting light brown solution was distilled at 50°C and 200 mTorr to give a colorless liquid. A portion of the dimethylphenylbismuth (5 g, 15.8 mmol) was dissolved in 10 cc of toluene. Glacial acetic acid (1.2 g, 20 mmol) was added with stirring. The resulting colorless solution was allowed to stand at room temperature for 2 days. Large colorless crystals formed. The crystals were washed with toluene (2 × 2 cc) and pentane (2 cc) and dried under vacuum. 1 H NMR (d8-THF): 1.8 (s, 6H), 1.36 (s, 3H).

[0167] Example 9: Synthesis of diisopropylphenylbismuth. Triphenylbismuth (39.6 g, 0.09 mol) was slowly added to a solution of bismuth tribromide (89.8 g, 0.2 mol) in 400 cc diethyl ether. A yellow precipitate formed upon the addition of solid triphenylbismuth to the stirred solution. After stirring overnight at room temperature, the bright yellow suspension was cooled to -78°C. Under stirring, 2 M isopropylMgCl (300 cc, 0.6 mol) in THF was added to the cold suspension over 1 hour. The resulting suspension was warmed to room temperature over several hours. The suspension was filtered, and the solid was washed with pentane (100 cc). The combined solutions were concentrated under vacuum, precipitating a separate gray solid. The solid was filtered to give a pale yellow liquid (72.1 g). A portion of this liquid was distilled under vacuum (200 mTorr) at 95°C to produce a colorless viscous liquid.

[0168] Example 10: Synthesis of diisopropylbismuth acetate / bismuth diisopropylacetate. Diisopropylphenylbismuth (3.7 g, 10 mmol) was dissolved in 10 cc of toluene. Glacial acetic acid (1.2 g, 20 mmol) was added with stirring. The resulting colorless solution was allowed to stand at room temperature for 2 days, and colorless crystals formed. The crystals were washed with toluene (2 × 2 cc) and pentane (2 cc) and dried under vacuum. X-ray diffraction of the selected crystals showed a structure of bismuth diisopropylacetate. This compound may have been formed in situ via the disproportionation of bismuth diisopropylacetate to bismuth diisopropylacetate and triisopropylbismuth. The asymmetric crystal structure is shown in Figure 6a (middle). C7H 13 Crystal data for BO4 (MW = 370.15 g / mol): Trigonal crystal system, space group R-3. a = b = 15.3049(15) Å, c =22.174(3) Å, V = 4498.2(11) Å 3 , Z = 18, T = 100 K, collect 16140 reflections, 2054 unique reflections, and use them in all calculations.

[0169] Example 11: Synthesis of dineopentylbismuth formate. Diisopropylphenylbismuth (3.7 g, 10 mmol) and 10 cc of toluene were placed in a 50 cc round-bottom flask. Formic acid (0.5 g, 11 mmol) was added to the colorless solution with stirring. The resulting colorless solution was allowed to stand overnight at room temperature. During this time, a fluffy colorless solid formed. The toluene solution was decanted, and 5 cc of fresh toluene was added while mixing. The toluene solution was filtered to obtain a colorless solid, which was dried under vacuum.

[0170] Example 12: Synthesis of di-neopentylbismuth neopentanoate. Di-neopentylphenylbismuth (10 g, 23.4 mmol) and 10 cc toluene were placed in a 100 cc Schlenk flask. An excess of neopentanoic acid (5.7 g, 55.9 mmol) was added to the pale yellow solution with stirring. The resulting bright yellow solution was heated to 100 °C for 6 hours. During this time, a small amount of black solid precipitated, and the solution color turned yellowish-green. The flask was cooled to room temperature and allowed to stand overnight. During this time, colorless crystals formed at the bottom of the flask. NMR (d8-THF): 1.09 (brs, 6.9H), 2.22 (brs, 1H). If the tBu protons overlapped with the methyl protons from the neopentyl group (27 methyl protons vs. four methylene protons; 4 / 27 = 6.75:1), this matched the expected structure. TGA analysis showed complete evaporation with approximately 0.5% by weight of non-volatile residue. However, the vapor pressure was low, with a T½ of 187 °C. DSC analysis showed no significant exothermic reaction, but endothermic reactions occurred at 75 °C (very low) and 235 °C (high).

[0171] Example 13: Synthesis of methylbismuth dimethacrylate. Methyldiphenylbismuth (3.8 g, 10 mmol) and 10 cc of toluene were placed in a 100 cc round-bottom flask. Methacrylic acid (1.9 g, 22 mmol) was added to the colorless solution with stirring. The resulting colorless solution was allowed to stand overnight at room temperature. No solid formed during this period. The solution was heated to 90°C for 2 hours. After cooling, a small amount of colorless solid was formed. Toluene was removed under vacuum to give a white solid. The solid was washed with pentane (10 cc) and dried under vacuum. 1 ¹H NMR (d3-acetonitrile): 1.53 (s, 3H), 1.91 (s, 6H), 5.51 (brs, 2H), 6.0 (brs, 2H).

[0172] Example 14: Synthesis of diphenylbismuth Hhpp (Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidinyl). A solution of sodium Hhpp (2.5 g, 15.5 mmol) in 50 cc THF was prepared. Diphenylbismuth chloride (6 g, 15 mmol) was added to this light orange solution with stirring. The resulting suspension was stirred overnight, turning light gray. THF was removed under vacuum, and the resulting viscous gray solid was extracted with pentane (50 cc). After evaporation of pentane under vacuum, a bright white precipitate was formed. After drying, it was... 1 H NMR determination of crude solids. 11H NMR (d8-toluene): 1.62 (m, 4H), 2.68 (t, 4H), 3.29 (t, 4H), 7.09 (m, 2H), 7.17 (m, 4H), 7.67 (m, 4H).

[0173] Example 15: Synthesis of diphenylbismuth iPrDMGD (iPrDMGD = N,N′-diisopropyl-N″,N″-dimethylguanidine). In a 100 cc round-bottom flask, diphenylbismuth chloride (330 mg, 0.83 mmol) and 10 cc toluene were mixed with stirring. Lithium iPrDMGD (180 mg, ~1 mmol) was added to the suspension. With the addition of Li iPrDMGD, the white solid diphenylbismuth chloride was rapidly consumed to give a turbid, pale yellow solution. The solution was stirred overnight. Toluene was removed under vacuum with gentle heating to give a light brown oil. The oil was extracted with pentane and filtered. Pentane was removed under vacuum. The resulting off-white solid was dissolved in d8-toluene and analyzed. 1 ¹H NMR (d8-toluene): 1.30 (d, 12H), 2.49 (s, 6H), 3.60 (m, 2H), 7.08 (m, 2H), 7.15 (m, 4H), 7.67 (m, 4H) ppm.

[0174] Example 16: Synthesis of diphenylbismuth iPrAMD (iPrAMD = N,N'-diisopropylacetamide). A solution of triphenylbismuth (10 g, 23 mmol) was prepared in 100 cc of toluene. A 4 M hydrogen chloride solution (6.25 cc, 25 mmol) in dioxane was added to this solution. A white solid precipitated upon addition of hydrogen chloride solution. The resulting suspension was stirred at room temperature for 1 hour. Li(iPrAMD) (3.7 g, 25 mmol) was slowly added to the suspension with stirring. Upon addition, the suspension turned yellow. After stirring overnight at room temperature, the solid was filtered and washed with pentane. The solution was concentrated under vacuum to give a viscous white solid. This solid was dissolved in a minimal amount of THF and added dropwise to pentane to precipitate the solid. The solvent was slowly removed by evaporation to give a colorless crystalline solid, which was then analyzed. 1 ¹H NMR (d8-toluene): 1.01 (d, 12H), 1.25 (s, 3H), 4.22 (m, 2H), 7.10 (m, 2H), 7.15 (m, 4H), 7.67 (m, 4H) ppm.

[0175] Example 17: Synthesis of isopropenyl diphenylbismuth. Bismuth diphenylchloride (4 g, 10 mmol) in toluene (30 cc) was stirred to form a white suspension. An isopropenyl MgBr solution (0.5 M in THF, 30 cc, 15 mmol) was added dropwise to this suspension with stirring at room temperature. The solution rapidly darkened, and the white solid dissolved. The resulting dark gray solution was stirred overnight at room temperature. The solution was evaporated to dryness to form a dark gray viscous solid. This solid was extracted with pentane (20 cc). Evaporation of the pentane solution yielded a mixture of needle-like crystals and liquid. The liquid was separated by filtration to give a colorless viscous liquid (2.7 g) and needle-like crystals. The needle-like crystals... 1 1H NMR analysis revealed that the crystals were triphenylbismuth (compared to the real sample). The liquid product was a mixture of triisopropenylbismuth (signal compared to literature data) and two other compounds (whose NMR signals were consistent with isopropenyldiphenylbismuth and diisopropenylphenylbismuth). The NMR data clearly showed that the disproportionation of the isopropenyl and phenyl ligands occurred at room temperature.

[0176] Example 18: Synthesis of Bi(methyl)(OSal)2. Methyldiphenylbismuth (1 g, 2.64 mmol) was dissolved in toluene (5 mL), and 2-hydroxybenzoic acid (HOSal, 0.8 g, 5.82 mmol, 2.2 equivalents) was added dropwise at room temperature. The turbid solution was stirred in the dark for 2 hours. The solid was filtered and washed twice with 2 mL of hexane. 1 H NMR (THF-d8): δ11.1 (s(br),Ph-O H , 2H), 7.8 (dd, Ph- H , 2H), 7.4 (m, Ph- H , 2H), 6.9 (m, 2Ph- H , 4H), 1.7 (s,Bi-CH3, 3H) ppm.

[0177] Example 19: BiPh2(O t Synthesis of bismuth diphenyl bromide (Bb). Bismuth diphenyl bromide (1 g, 2.26 mmol) was dissolved in THF (10 ml), and potassium tert-butoxide (K₂O₃) was slowly added at room temperature. t Bu (0.25 g, 2.26 mmol, 1 equivalent). The mixture was stirred for 16 hours, filtered, and the solvent was removed under vacuum. The pale yellow solid was sublimated at 70 °C and 0.02 mbar to give a colorless solid. NMR showed the target compound as the main component and small amounts of BiPh3 and Bi(O)2. t Bu)3 and BiPh(O t Bu)2. 1H NMR (THF-d8): δ 8.0 (m, Ph- H , 4H), 7.4 (m, Ph- H , 4H), 7.2 (m, Ph- H , 2H), 1.2 (s, OC(C H 3)3- H ,9H)ppm.

[0178] Example 20: Synthesis of BiPh2 (MODMP). Bismuth diphenyl bromide (500 mg, 1.13 mmol) was suspended in toluene (10 mL) and cooled to -78 °C. A 0.4 M solution of 3-methoxy-1,1-dimethylpropyl magnesium chloride (MODMP-MgCl, 3 mL, 1.13 mmol, 1 equivalent) was added dropwise. The solution turned black, and the mixture was stirred for 16 hours while being warmed to room temperature. The solvent was then removed, and the residue was extracted with pentane (20 mL). The mixture was filtered, and the solvent was removed to give a yellow oil. 1 H NMR (500 MHz, THF-d8): δ 7.8 (m, Ph-H, 4H), 7.3 (m, Ph-H, 4H), 7.2 (m, Ph-H, 2H), 3.5 (t, CH2-OCH3, 2H), 3.3 (s, OCH3, 3H), 2.3 (t, CH2-CH2-OCH3, 2H), 1.9 (t, Sn-C-(CH3)2, 6H) ppm.

[0179] Example 21: Deposition of bismuth-containing films using methylbismuth diacetate. Bismuth-containing films were deposited on silicon wafers using the process conditions shown in Table 22. The process sequence cycle consisted of pulses of bismuth precursor / purge / co-reactant / purge (pulse times in seconds). Film thicknesses measured by elliptic polarization and XRF for the same film samples are shown. The results indicate that both ozone and water are used as co-reactants for bismuth-containing film deposition. Using ozone, a combination of higher substrate temperature and chamber pressure produces thicker films. Using ozone as a co-reactant and increasing the ampoule temperature results in even thicker films. Using water as a co-reactant, bismuth-containing films were grown under various process conditions.

[0180] Table 22 Further experiments were conducted using molecular oxygen as a co-reactant. The resulting membrane characterization showed that no membrane formed with oxygen under thermal conditions (without plasma), however, a membrane was deposited using oxygen plasma (Table 23).

[0181] Table 23 Example 22: Etching of bismuth-containing films with acetic acid. Bismuth-containing films were deposited using methyldiphenyl bismuth and ozone. These films were primarily bismuth oxide with a low carbon content (<5 atomic%). When these films were exposed to acetic acid at a substrate temperature of 200 °C, acetic acid was observed to etch the bismuth oxide films at an etching rate of 0.25 Å / cycle (acetic acid / Ar; 1s / 2s; 2T; 50 sccm acetic acid). Additional films were prepared using methylbismuth diacetate and water under the conditions described in Example 21. These films were etched with acetic acid at 200 °C, as shown in Table 24.

[0182] Table 24 Example 23: Spin-coating and electron beam exposure experiments. A solution of methylbismuth diacetate (20 g / L concentration) was prepared in cyclohexanone. The formulation was spin-coated onto silicon wafers pre-treated with oxygen plasma (400 W, 10 min) at 800–4000 rpm. After baking at 60 °C for 120 sec, the wafers were exposed to dose levels ranging from 10 to 5000 μC / cm². 2 Electron beam irradiation (30 keV) was applied. After exposure, the wafer was heated at 60°C for 120 seconds. The wafer was then developed with 2-heptanone at room temperature for 120 seconds. The wafer was then rinsed with water and dried under nitrogen. The unexposed film had a thickness of ~30 nm, which was determined by profilometry. The developed structure was also determined by profilometry. The peak height vs. dose was converted into a fitted dose-level curve, D... 50 Values ​​range from 500 to 5000 μC / cm 2 Between. Profilometry demonstrates that the developed wafers exhibit sensitivity to electron beam radiation ( ). Figure 7 Each line was exposed to the following dose [from top (darkest spot, thickest membrane) to bottom (brightest spot, thinnest membrane)], at μC / cm. 2 The numbers are: 5000, 4000, 3000, 2500, 2000, 1500, 1250, 1000, 950, 900, 850, 800, 750, 700, 600, 550, and 500.

[0183] Comparative Example 1: An attempt to react tris(neopentyl)bismuth with glacial acetic acid. A stoichiometric mixture of approximately 1:3 tris(neopentyl)bismuth and glacial acetic acid in d8-toluene was placed in a high-pressure NMR tube. NMR analysis showed no reaction after 2 hours at room temperature. The tube was then heated to 90°C for 4 hours and analyzed by NMR, showing only unreacted tris(neopentyl)bismuth and glacial acetic acid. The tube was then heated to 150°C for 4 hours and analyzed by NMR again, showing only unreacted tris(neopentyl)bismuth and glacial acetic acid.

[0184] Comparative Example 2: Film Deposition Experiments Using Di-Neopentylphenylbismuth. Bismuth-containing films were deposited on silicon oxide and zirconium oxide wafers using the cycling process conditions shown in Table 25. The pulse sequence cycle consisted of pulses of bismuth precursor / purge / co-reactant / purge (pulse duration in seconds). Film thicknesses measured by XRF are shown. The results indicate that no bismuth-containing films were deposited using water with di-neopentylphenylbismuth, which differs from the deposition results observed for methylbismuth diacetate (where bismuth-containing films were deposited using water as a co-reactant under similar process conditions). The absence of film formation in the case of acetic acid as a co-reactant may indicate simultaneous deposition and etching.

[0185] Table 25 Although the disclosed and claimed subject matter has been described and illustrated with a degree of specificity, it should be understood that this disclosure is by way of example only, and many changes in conditions and sequence of steps may be made by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, comprising the following steps: (a) Providing the substrate to the reactor; (b) Contact the substrate with one or more bismuth-containing compounds or antimony-containing compounds and one or more co-reactants; and (c) A bismuth-containing film or an antimony-containing film is formed on the substrate.

2. A method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, comprising the following steps: (a) Providing the substrate to the reactor; (b) Perform pretreatment to remove contaminants from the surface of the substrate; (c) Contacting the substrate with one or more bismuth-containing compounds or antimony-containing compounds and one or more co-reactants; and (d) Forming a bismuth-containing film or an antimony-containing film on the substrate.

3. A method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, comprising the following steps: (a) Providing the substrate to the reactor; (b) Contact the substrate with one or more bismuth-containing compounds or antimony-containing compounds and one or more co-reactants; and (c) Exposing the substrate, the one or more bismuth-containing compounds or antimony-containing compounds, and the one or more co-reactants to plasma; and (d) Forming a bismuth-containing film or an antimony-containing film on the substrate.

4. A method for depositing a bismuth-containing film or an antimony-containing film on a substrate in a reactor, comprising the following steps: (a) Providing the substrate to the reactor; (b) Contact the substrate with one or more bismuth-containing compounds or antimony-containing compounds and one or more co-reactants; (c) Forming a bismuth-containing film or an antimony-containing film on the substrate; (d) Expose a portion of the membrane to extreme ultraviolet (EUV) light. (e) Remove a portion of the membrane.

5. A formulation comprising one or more bismuth-containing compounds or antimony-containing compounds.

6. A formulation comprising (i) one or more bismuth-containing compounds or antimony-containing compounds and (ii) at least one solvent.

7. A deposition method comprising exposing a film formed of one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof to extreme ultraviolet light (EUV).

8. A deposition method comprising exposing a film formed of one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof to extreme ultraviolet light (EUV), wherein the film is deposited on a substrate by a spin-coating process.

9. A deposition method comprising exposing a film formed of one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof to extreme ultraviolet light (EUV), wherein the film is deposited on a substrate by a vapor deposition process.

10. A deposition method comprising exposing a film formed of one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof to extreme ultraviolet light (EUV), wherein the film is deposited on a substrate by a vapor deposition process selected from CVD, CCVD and ALD.

11. A radiation film obtained by exposing a film formed of one or more bismuth-containing compounds or antimony-containing compounds or their preparations to extreme ultraviolet light (EUV).

12. A method for forming a polymer or nanocluster, comprising reacting one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof with one or more co-reactants.

13. A polymer formed by reacting one or more bismuth-containing compounds or antimony-containing compounds or their preparations with one or more co-reactants.

14. A nanocluster formed by reacting one or more bismuth-containing compounds or antimony-containing compounds or their preparations with one or more co-reactants.

15. A method for forming functionalized nanoclusters, comprising (i) reacting one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof with one or more co-reactants to form nonfunctionalized nanoclusters, and (ii) functionalizing the nonfunctionalized nanoclusters.

16. A functionalized nanocluster formed from one or more bismuth-containing compounds or antimony-containing compounds or their preparations.

17. A method for forming functionalized nanoclusters, comprising (i) reacting one or more bismuth- or antimony-containing compounds or preparations thereof with one or more co-reactants to form nonfunctionalized nanoclusters, and (ii) functionalizing the nonfunctionalized nanoclusters.

18. A method for forming functionalized nanoclusters, comprising (i) reacting one or more bismuth-containing compounds or antimony-containing compounds or preparations thereof with one or more co-reactants to form unfunctionalized nanoclusters, and (ii) functionalizing the unfunctionalized nanoclusters with at least one group comprising at least one unsaturated bond.

19. The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula Bi(R) a ) x (Ar) 3-x Bismuth compounds, basically of the formula Bi(R) a ) x (Ar) 3-x Bismuth compounds are composed of or derived from the formula Bi(R) a ) x (Ar) 3-x The composition of bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, alkoxy, carboxylic acid group, amino, diketo acid group, keto ester group, amidoyl group, and amidine group; and (iii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle.

20. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein X=1.

21. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein X = 2.

22. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 23. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 24. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 25. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 26. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 27. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 28. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 29. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 30. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each R a Independently one of the following: 。 31. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein each Ar is independently one of the following: 。 32. The method, formulation, membrane, polymer, nanocluster, or process of claim 19, wherein said compound is one of the following: 。 33. The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula Bi(R) a ) x (L) 3-x Bismuth compounds, basically of the formula Bi(R) a ) x (L) 3-x Bismuth compounds are composed of or derived from the formula Bi(R) a ) x (L) 3-x The composition of bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is independently one of an alkoxy group, a carboxylic acid group, an amino group, a diketo acid group, a keto ester group, and an amidation group.

34. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein X=1.

35. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein X=2.

36. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 37. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 38. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 39. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 40. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 41. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 42. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 43. The method, formulation, membrane, polymer, nanocluster, or process of claim 33, wherein each L is independently one of the following: 。 44. The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula (R a )2Bi-Bi(R b Bismuth compounds of formula (R) are essentially composed of bismuth compounds of formula (R) a )2Bi-Bi(R b Bismuth compounds of formula (R)2 or composed of formula (R) a )2Bi-Bi(R b The composition of bismuth compounds is 2, wherein each R a and R b Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic group, amino-substituted C3-C8 aromatic group, 5-membered heterocycle, and 6-membered heterocycle.

45. The method, formulation, membrane, polymer, nanocluster, or process of claim 44, wherein the compound is one of the following: 。 46. ​​The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula M(R a ) x (R b ) 3-x or (R) a )2M-M(R b Compounds of formula M(R) are essentially composed of the following: a ) x (R b ) 3-x or (R) a )2M-M(R b The compound composition of )2 or is composed of formula M(R) a ) x (R b ) 3-x or (R) a )2M-M(R b The compound composition of )2, in which (iii) M is independently Sb or Bi; (iv) X = 0, 1, or 2; and (iii) Each R a and R b Independently, it can be an unsubstituted straight-chain C1-C6 alkyl group, one or more halogen-substituted straight-chain C1-C6 alkyl groups, an amino-substituted straight-chain C1-C6 alkyl group, an alkoxy-substituted straight-chain C3-C6 alkyl group, an unsubstituted branched C3-C6 alkyl group, one or more halogen-substituted branched C3-C6 alkyl groups, an amino-substituted branched C3-C6 alkyl group, an alkoxy-substituted branched C3-C6 alkyl group, an unsubstituted amine, a substituted amine, -Si(CH3)3, or an unsubstituted cyclic C3-C6 alkyl group. Alkyl group, one or more halogen-substituted cyclic C3-C6 alkyl groups, amino-substituted cyclic C3-C6 alkyl groups, unsubstituted C3-C8 aromatic groups, one or more halogen-substituted C3-C8 aromatic groups, amino-substituted C3-C8 aromatic groups, 5-membered heterocycles, 6-membered heterocycles, trialkyltinalkyl groups wherein the alkyl group is a straight-chain C1-C6 alkyl group, trialkyltinalkyl groups wherein the alkyl group is a branched C3-C6 alkyl group, and trialkyltinalkyl groups wherein the alkyl group is a cyclic C3-C6 alkyl group.

47. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein M is Sb.

48. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein M is Bi.

49. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein X = 0.

50. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein X=1.

51. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein X=2.

52. The method, formulation, membrane, polymer, nanocluster, or process of claim 46, wherein said compound is one of the following: 。 53. The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula (R a )2Sb-Sb(R b )2 or cyclotetrastimane (" Antimony compounds, essentially composed of or consisting of, wherein each R a and R b Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, unsubstituted amine, substituted amine, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, amino-substituted cyclic C3-C6 alkyl, unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic group, amino-substituted C3-C8 aromatic group, 5-membered heterocycle, and 6-membered heterocycle.

54. The method, formulation, membrane, polymer, nanocluster, or process of claim 53, wherein said compound is one of the following: 。 55. The method, formulation, membrane, polymer, nanocluster, or process according to any one of claims 1-18, comprising the formula M(R a ) x (R b ) 3-x or (R) a )2M-M(R b Compounds of )2, essentially composed of or composed of, wherein (i) M is independently Sb or Bi; (ii) X = 0, 1, or 2; (iii) Each R a and R b Independently, it is one of the following: a straight-chain C1-C6 alkyl group, one or more halogen-substituted unsaturated straight-chain C1-C6 alkyl groups, an amino-substituted unsaturated straight-chain C1-C6 alkyl group, an unsaturated branched C3-C6 alkyl group, one or more halogen-substituted unsaturated branched C3-C6 alkyl groups, an amino-substituted unsaturated branched C3-C6 alkyl group, an unsubstituted amine, a substituted amine, -Si(CH3)3, an unsaturated cyclic C3-C6 alkyl group, one or more halogen-substituted unsaturated cyclic C3-C6 alkyl groups, an amino-substituted unsaturated cyclic C3-C6 alkyl group, a 6-membered aromatic ring, an aromatic ring having a C2-C6 unsaturated alkyl group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iv) The compound comprises at least one unsaturated group.

56. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein M is Sb.

57. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein M is Bi.

58. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein X = 0.

59. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein X=1.

60. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein X=2.

61. The method, formulation, membrane, polymer, nanocluster, or process of claim 55, wherein said compound is one of the following: 。 62. Equation Bi(R) a ) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is a carboxylic acid group; and (iv) Exclude x=1 and R a It is a compound with -CH3 and each L being an acetic acid group.

63. The compound of claim 62, wherein x = 1.

64. The compound of claim 62, wherein x = 2.

65. The compound of claim 62, wherein each L is independently one of an acetate group, a formic acid group, a neopentanoic acid group, a methacrylate group, and a salicylic acid group.

66. The compound of claim 62, wherein each L is independently one of formic acid group, neopentanoic acid group, methacrylate group and salicylic acid group.

67. The compound of claim 62, wherein each L is an acetic acid group.

68. The compound of claim 62, wherein each L is a formic acid group.

69. The compound of claim 62, wherein each L is a neopentanoic acid group.

70. The compound of claim 62, wherein each L is a methacrylate group.

71. The compound of claim 62, wherein each L is a salicylic acid group.

72. The compound of claim 62, wherein each L is identical.

73. The compound of claim 62, wherein each L is different from one another.

74. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 75. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 76. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is 。 77. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 78. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 79. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 80. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 81. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 82. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 83. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 84. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 85. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 86. The compound of claim 62, wherein the formula Bi(R) a ) x (L) 3-x The compound is: 。 87. Formula Bi(R) a ) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each R a Independently, it is one of the following: unsubstituted straight-chain C1-C6 alkyl, one or more halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, alkoxy-substituted straight-chain C3-C6 alkyl, unsubstituted branched C3-C6 alkyl, one or more halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, alkoxy-substituted branched C3-C6 alkyl, -Si(CH3)3, unsubstituted cyclic C3-C6 alkyl, one or more halogen-substituted cyclic C3-C6 alkyl, and amino-substituted cyclic C3-C6 alkyl; and (iii) Each L is an amido, formamidin, or guanidine.

88. The compound of claim 87, wherein x = 1.

89. The compound of claim 87, wherein x = 2. 90.Formula Bi(Ar) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iii) Each L is an amido, formamidin, or guanidine.

91. The compound of claim 90, wherein x = 1.

92. The compound of claim 90, wherein x = 2.

93. The compound of claim 90, wherein each L is an amidine group.

94. The compound of claim 90, wherein each L is a formamidinyl group.

95. The compound of claim 90, wherein each L is a guanidine group.

96. The compound of claim 90, wherein each L is independently one of 1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidinyl, N,N′-diisopropyl-N″,N″-dimethylguanidine, and N,N′-diisopropylacetamidine.

97. The compound of claim 90, wherein each L is 1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidinyl.

98. The compound of claim 90, wherein each L is N,N'-diisopropyl-N”,N”-dimethylguanidine.

99. The compound of claim 90, wherein each L is N,N'-diisopropylacetamidine.

100. The compound of claim 90, wherein each L is identical.

101. The compound of claim 90, wherein each L is different from one another.

102. The compound of claim 90, wherein the formula Bi(Ar) x (L) 3-x The compound is: 。 103. The compound of claim 90, wherein the formula Bi(Ar) x (L) 3-x The compound is: 。 104. The compound of claim 90, wherein the formula Bi(Ar) x (L) 3-x The compound is: 。 105.Formula Bi(Ar) x (L) 3-x Bismuth compounds, in which (i) x = 1 or 2; (ii) Each Ar is independently one of an unsubstituted C3-C8 aromatic group, one or more halogen-substituted C3-C8 aromatic groups, an amino-substituted C3-C8 aromatic group, a 5-membered heterocycle, and a 6-membered heterocycle; and (iii) Each L is an alkoxide group.

106. The compound of claim 105, wherein x = 1.

107. The compound of claim 105, wherein x = 2.

108. The compound of claim 105, wherein the formula Bi(Ar) x (L) 3-x The compound is: 。 109. The method, formulation, membrane, polymer, nanocluster, or process of any one of claims 1-18, comprising a bismuth compound of any one of claims 62-108, substantially consisting of a bismuth compound of any one of claims 62-108, or consisting of a bismuth compound of any one of claims 62-108.

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