Organotin photoresist composition having a fluoride-forming compound, fluorinated organotin coating and patterning

Abstract

Organotin patterning compositions may incorporate Sn-F bonds to improve patterning performance. A precursor solution for a radiation patterning composition may comprise a blend of an organic solvent, an organotin composition represented by the formula RSnL3, and a compound capable of generating Sn-F bonds, where R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and Sn-C bonds, and L is a hydrolyzable ligand. The fluoride source may be ammonium fluoride. The patterning structure on the substrate surface generally contains RSnF bonds within an oxo-hydroxo network. n It has a part.

Description

TECHNICAL FIELD

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to co-pending U.S. Provisional Patent Application No. 63 / 537,977 filed September 12, 2023 by Cardineau et al., entitled "Organotin Photoresist Compositions Having Fluoride Generator Compounds", which is incorporated herein by reference in its entirety.

[0002] The present invention relates to organotin radiation patterning compositions having a fluoride source capable of introducing tin-fluoride bonds. The present invention further relates to organotin patterning compositions that are effective for high-resolution EUV patterning and have lower dose requirements to achieve desirable patterning results.

BACKGROUND ART

[0003] Extreme ultraviolet lithography (EUV) is currently used in high-volume semiconductor manufacturing, and metal-organic resists (MOR) have been shown to be high-performance photoresists for use in EUV lithography. EUV lithography generally involves complex processes and expensive machinery, and it is generally desirable to improve MOR photoresist performance, such as by reducing patterning dose requirements, to maximize wafer throughput and thereby lower the cost of EUV lithography.

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEMS

[0004] One aspect of the present invention relates to an organotin photoresist solution composition having a compound capable of generating Sn-F bonds upon exposure to radiation.

[0005] Another aspect of the present invention relates to an organotin photoresist solution composition comprising ammonium fluoride represented by the formula NR'4F, wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0006] In a further aspect, the present invention relates to a precursor solution for a radiation patterning composition, comprising a blend of an organic solvent, an organotin composition represented by the formula RSnL3, and a compound capable of forming a Sn-F bond, wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and a Sn-C bond, and L is a hydrolyzable ligand.

[0007] In some aspects, the present invention relates to a precursor solution for a radiation patterning composition, comprising a blend of an organic solvent, an organotin composition represented by the formula RSnL3, and a compound capable of generating fluoride ions during exposure to EUV radiation or post-exposure baking.

[0008] In a further aspect, the present invention relates to one or more organotin compounds represented by the formula RSnL3, wherein R is a saturated or unsaturated linear, branched, cyclic, aromatic hydrocarbyl group having 1 to 31 carbon atoms optionally substituted with a heteroatom, and L is a hydrolyzable ligand, and a compound of the formula NR a R b R c R d F, wherein R a , R b , R c and R d are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or a mixture thereof, to a photoresist precursor composition comprising a mixture with an ionic fluoride compound represented by the formula.

[0009] In another aspect, the present invention is a method of forming a photoresist solution having a Sn-F bond, the method comprising an organotin precursor represented by the formula RSnL3, and a compound of the formula NR a R b R c Rd F (wherein R a , R b , R c and R d are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or a mixture thereof) and a fluoride source compound represented by the formula are mixed in an organic solvent to form a photoresist solution having an Sn-F bond, wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond, and L is a hydrolyzable ligand.

[0010] In a further aspect, the present invention relates to a structure comprising a substrate and a patterning material on the surface of the substrate, wherein the patterning material comprises RSnF n moiety (wherein 0 < n ≤ 1, and R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond).

[0011] Furthermore, the present invention relates to a method of patterning an organotin material having Sn-F bonds, the method comprising the step of irradiating the organotin material with a dose of patterning EUV radiation that is at least 8% lower than the corresponding dose of a comparable non-fluorinated organotin patterning material to provide a patterned material having a comparable critical dimension at the same coating thickness. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] [Figure 1] 19F NMR spectrum of a concentrated solution prepared by mixing tert-butyltin tris(pentan-3-yloxide), ammonium fluoride and 1-propanol. [Figure 2] 119Sn NMR spectrum of the concentrated solution of Figure 1. [Figure 3] 19F NMR spectrum of a concentrated solution prepared by mixing isopropyltin tris(sec-butoxide), ammonium fluoride and 4-methyl-2-pentanol. [Figure 4]The following are sets of ESI-MS spectra of photoresist solutions P1-P4, prepared by mixing tert-butylsutris (pentane-3-yloxide) and ammonium fluoride in different molar ratios using a solvent containing a controlled amount of water. [Figure 5] This is a series of contrast curves for coated wafers prepared from either a precursor solution containing ammonium fluoride or / or a control precursor solution. [Figure 6] These are a series of 15 CD-SEM images of a silicon substrate having an organotin resist patterned by EUV lithography to form a 28 nm pitch line. Each image is taken from the field closest to the average line CD of 14 nm. The top five SEM images correspond to a post-exposure bake (PEB) temperature of 170°C, the second five SEM images correspond to processing at a PEB temperature of 180°C, and the bottom five SEM images correspond to processing at a PEB temperature of 190°C. The five images in each row correspond to resist films prepared using precursor solutions with NH4F additive (A), tetramethylammonium fluoride additive (B), tetrabutylammonium fluoride additive (C), or no fluoride additive (Control 1 and Control 2). [Figure 7] Figure 6 shows bar graphs of the EUV dose for each image. [Modes for carrying out the invention]

[0013] The radiosensitivity of organotin photoresists can be improved by the presence of a fluoride generator in the precursor solution, which is then present in the organometallic matrix obtained after solvent removal. The fluoride generator is a fluoride anion (F - ) can be generated, which can function as a tin ligand in organometallic compositions. In some embodiments, several F -The species can bind to tin species in the precursor solution. In some embodiments, fluoride-generating agent-reactive fluorides can be generated in the matrix during exposure of the organometallic matrix to radiation and / or heating, thereby forming tin-fluoride bonds. In further embodiments, F - Ligands can associate with tin atoms at various points during processing, and the exact mechanism and degree of ligand formation may depend on the specific species and processing. Organometallic patterning compositions generally have an RSn moiety, where R is an organic ligand that can be radiosensitive. Patterning compositions formed on a substrate surface form an oxo-hydroxo network where the presence of organic ligands limits complete condensation to the metal oxide. Cracking of organic ligands by radiation yields high-contrast irradiated materials with virtual images. The presence of fluoride ligands, introduced by using fluoride-producing species, such as ammonium fluoride, has been found to reduce the radiation required for patterning without significantly reducing contrast. While not wanting to be limited by theory, the presence of tin-fluoride bonds in an organotin matrix can lower the activation energy of tin-carbon bonds in the matrix, thus improving the radiosensitivity of the material.

[0014] To reduce manufacturing costs and improve the yield of semiconductor device manufacturing, it is desirable to improve photoresist performance. Organometallic materials, particularly those based on organotin compositions, have been shown to be high-performance photoresists that enable high-resolution and high-fidelity patterning. Organotin photoresists are extensively described in U.S. Patent No. 9,310,684, entitled “Organometallic Solution Based High Resolution Patterning Compositions,” U.S. Patent No. 10,642,15, entitled “Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods,” and U.S. Patent No. 10,228,618, entitled “Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning,” all of which are incorporated herein by reference. The process time can be shortened to a degree that reduces radiation levels without compromising patterning performance, because the dose is effectively correlated with the irradiation time. Therefore, as the dose decreases, throughput increases and the efficiency of capital equipment utilization improves.

[0015] Generally, these organotin photoresist materials are deposited as a coating formed from a precursor, and the Sn atoms in the coating associate within the oxo-hydroxo network via Sn-OH and Sn-O-Sn bonds, along with intact Sn-C bonds that associate with organic ligands. The intact Sn-C bonds prevent the formation of an expanded, dense network, and therefore, the deposited material is generally soluble in suitable organic solvents and developers. When the organotin coating is exposed to a suitable radiation source, such as extreme ultraviolet (EUV), ultraviolet (UV), or an electron beam, the Sn-C bonds cleavage occurs, allowing for further densification of the exposed areas, decreasing solubility, and thereby increasing the solubility contrast between the exposed and unexposed areas. In this way, a physical pattern can be realized after development.

[0016] High contrast against radiation exposure results in high-resolution lines and low linewidth roughness. While we do not wish to be limited by theory, the presence of fluoride generators can reduce the activation energy required to cleave Sn-C bonds, thereby improving the radiosensitivity of organotin materials. The presence of Sn-C bonds in organotin materials during deposition generally results in hydrophobic organotin films, and upon exposure to radiation, generally yields more hydrophilic materials. The presence of fluoride ligands significantly improves the processing for latent image formation. One or more precise mechanisms remain unclear, and it is likely that multiple effects influence the results. The results suggest that the presence of fluoride ligands improves radiosensitivity while roughly maintaining or improving thermal stability. The improvement in radiosensitivity can be obtained from one or more mechanisms, which can be investigated in future studies. In any case, the results allow for a reduction in the effective dose for patterning, while simultaneously maintaining high contrast and obtaining good resolution and pattern characteristics.

[0017] The mechanism and timing of Sn-F ligand formation are not fully understood and appear to be determined by the specific chemical species and conditions involved. In particular, specific fluoride generators, designated organotin, solvents, and process conditions can all influence the structure in solution. Furthermore, even after depositing the precursor solution and removing the solvent, the structure of the resulting material may still be affected by the chemical species and process conditions. In some embodiments, Sn-F bonds can be formed in solution. In some embodiments, which may not be mutually exclusive, exposure of organotin materials containing fluoride generators to radiation and / or heating can induce tin-carbon bond cleavage and the formation of Sn-F bonds and Sn-O-Sn and / or Sn-OH bonds, thereby obtaining materials with higher polarity and greater hydrophilicity, and improving the chemical contrast between irradiated and unirradiated materials. Following radiolysis, radiation-induced thermal decomposition, or thermal decomposition of C-Sn bonds, CF bonds may also be formed, which may stabilize the cleaved organic portion and / or facilitate its removal from the material. F on the bond structure - Regardless of the mechanism and timing of placement, these effects can be highly desirable and impressive. The difference in hydrophilicity / polarity between the irradiated and unirradiated regions of the organotin film allows for both positive-type processing, where the irradiated material is removed during development, and negative-type processing, where the unirradiated material is removed during development. Generally, the desired type can be achieved by the appropriate selection of a developer, for example, a developer having an organic solvent in the case of negative-type processing and an aqueous solvent in the case of positive-type processing. The following example shows the case of negative-type patterning.

[0018] The presence of a fluoride generator in organotin materials allows for the formation of tin-fluoride bonds, which promotes the cleavage of tin-carbon bonds within the irradiated area of ​​the material, thereby reducing the radiation dose required for patterning the material. This effect is demonstrated in the examples. Tin-fluoride bonds are also desirable due to their high hydrolysis and thermal stability, which reduces susceptibility to post-exposure effects such as reactions at ambient humidity, delayed treatment, and decomposition in post-exposure bake (PEB) processes. Furthermore, fluorides are known to have higher EUV absorbance than C, H, and O, and therefore can increase the EUV radiation absorbance of photoresist films.

[0019] The presence of tin-fluoride bonds can also improve the thermal decomposition behavior induced by radiolysis of organotin photoresist compositions. Generally, after irradiation, Sn-C bonds in the irradiated region of the material cleave. It has been found that the thermal stability of hydrocarbyl compounds remaining in the material after irradiation decreases significantly, and their thermal stability decreases with decreasing Sn-C concentration. In other words, as the concentration of Sn-C bonds in the irradiated material decreases, the thermal stability of the Sn-C bonds remaining in the irradiated material also decreases. When Sn-F bonds are formed from the fluoride generating agent compositions described herein, the stability of the Sn-C bonds is further reduced, thereby strengthening the chemical contrast between the irradiated and unirradiated regions of the film. After exposure to radiation, if an initial amount of Sn-C bonds are cleaved and Sn-F bonds are present and / or formed, subsequent baking can promote further cleavage of Sn-C bonds through thermal decomposition in a phenomenon called radiolysis-induced thermal decomposition.

[0020] Fluoride generators are generally stable compounds that can be mixed into the organotin photoresist matrix during the deposition of a precursor solution for forming a photoresist film. Fluoride anions are then obtained from the fluoride source, and reactions in solution and / or with the organotin matrix can occur to form tin-fluoride bonds. Generally, fluoride generators can be thermally stable compounds capable of generating fluoride anions due to solvent interactions that may favor the nucleophilicity of the fluoride anions.

[0021] In some embodiments, the fluoride generator is an ionic compound, for example, formula NR a R b R c R d F (where R a , R b , R c and R d The compounds may include ammonium fluoride, alkylammonium fluoride, and quaternary ammonium fluoride compounds, where R' is independently represented by hydrogen or an alkyl group having 1 to 6 carbon atoms. Generally, all of these are referred to herein as ammonium fluoride. One subgenus of these ammonium fluoride compounds is NR'4F, where R' is hydrogen or an alkyl group having 1 to 6 carbon atoms, e.g., R = methyl, ethyl, propyl, butyl, pentyl, hexyl, and their respective isomers, e.g., isopropyl, tert-butyl. The examples focus on inorganic ammonium fluoride, NH4F, tetramethylammonium fluoride, and tetrabutylammonium fluoride. Fluoride-generating compounds yield fluoride anions that are not bonded to metals, which are referred to in the art as "naked fluorides." These fluoride anions are then available for bonding to tin. In an alcoholic solvent, ammonium fluoride can be useful for supplying fluoride anions for nucleophilic substitution. These ammonium fluoride compounds are used to introduce fluoride substituents into organic compounds by nucleophilic substitution. In solution, fluoride anions can reach equilibrium in various bonding configurations depending on the specific solvent, concentration, and especially other factors.

[0022] The results of the examples showed that the reactant cation was NH4 + In this case, at least some F in the solution - This suggests that it binds to tin. The fluoride bond to tin at the free hexagonal binding site is the alkoxide group: RSnFOOH - or RSnOF+ - It is currently unknown whether OR' and other compounds are substituted in any particular ratio or combination thereof. Binding at the free binding site causes the formula NH4 + [RSnL3F] - Fluorinated salt complexes can be formed as shown by . The results in the examples suggest that some of each type of bond can occur. Details of the reaction and mechanism are not particularly important at present, other than the fact that Sn-F bonds can be formed. In principle, fluoride ligands can bridge between tin atoms. SnF4 has an unusual crystal structure with octahedral coordinated tin having four bridging planar fluorine atoms and two opposing vertex non-bridging fluorine atoms. Thus, in principle, fluoride ligands can provide a variety of bonding options for tin materials, and potentially all of them can be utilized in patterning materials.

[0023] Tin-fluoride bonds can lead to the formation of fluorinated organotin oxide hydroxide networks. While we do not wish to be limited by theory, fluorine atoms are generally considered more likely to form terminal Sn-F bonds than bridging between tin atoms, which can reduce the formation of defects such as microbridges. By using non-bridging Sn-F bonds instead of bridging Sn-OH-Sn bonds, the formation of the extended oxide hydroxide network can be inhibited, thereby improving the solubility of unexposed and lightly exposed materials, and thus helping to reduce defects such as microbridges and scum. Due to their tendency to form terminal Sn-F bonds, the addition of fluorides can reduce the average domain size in photoresist coatings. After exposure to radiation to develop the pattern, the smaller domain size obtained by the presence of tin-fluoride bonds allows for the formation of finer features with less roughness, enabling more finely controlled removal of the material.

[0024] During coating, the solvent is removed, and fluoride ions from the fluoride source may or may not bind to tin. Although we do not wish to limit the theory to the extent that they still do not bind to tin, radiation exposure and / or heating of organotin compositions having a fluoride generator, e.g., ammonium fluoride, can generally cause the decomposition of ammonium fluoride compounds and the promotion of Sn-F bond formation by the following reactions: [ka]

[0025] In reactions 1 and 2, R and R' are defined as described above. Several ammonium fluoride compounds have been shown to decompose at the temperatures used for processing organotin coatings. It is unknown whether they disperse by the coating material and still decompose thermally, but this decomposition may be favorable for the formation of the tin-fluoride bonds described above. In this case as well, at present, the exact mechanism and timing of fluoride-tin bond formation are not important as long as the desired degree of fluoride-tin bond formation is achieved during patterning.

[0026] Various methods can be used to form the precursor solution, and the resulting composition may or may not be independent of the order of the processes. In some embodiments, the fluoride generator can be added to the photoresist solution by dissolving an appropriate mass of the compound in the photoresist solution composition. These solutions can be formed at a certain initial concentration and then diluted to achieve the desired concentration for deposition. The fluoride generator and solvent can be appropriately selected to achieve the desired solubility for the tin precursor concentration. In some embodiments, the fluoride generator compound can first be dissolved in a suitable solvent to form a fluoride generator solution, which can then be added to the photoresist solution composition. In this case as well, these solutions can be formed at a certain initial concentration and then diluted. The realization of dissolved ammonium fluoride can be carried out over a long period of time, and the dissolution process can be completed by appropriately stirring the initial mixture for a sufficient amount of time, such as several minutes, several hours, overnight, or longer.

[0027] The concentration of the fluoride generator can be expressed as the number of moles of fluoride relative to Sn. Based on the selected concentration of tin in the precursor solution, the concentration of the fluoride generator can be determined from the tin concentration and molar ratio. In some embodiments, the fluoride generator compound can be present in the solution at a molar ratio of 0.001 to about 1 mole of fluoride per mole of tin, in further embodiments about 0.0015 to about 0.75, in some embodiments about 0.002 to about 0.6, in further embodiments about 0.002 to about 0.5, in further embodiments about 0.0035 to about 0.45, in further embodiments about 0.005 to about 0.4, and in some embodiments about 0.0075 to about 0.3 moles of fluoride relative to tin. These molar ratios can also be expressed as the ratio of tin to a fluoride generator, such as ammonium fluoride, for example, from about 20:1 to about 1.5:1, which is equivalent to a molar ratio of about 0.05 to about 0.667 of fluoride generator to tin. Those skilled in the art will understand that a further range of molar ratios of fluoride ions to tin can be considered and fall within the scope of this disclosure.

[0028] Where used herein and in accordance with general use in the art, the terms “organotin,” “hydrocarbyltin,” and “alkyltin” may be used synonymously, and similarly, “monoalkyl” may be used synonymously with “monoorgano” or “monohydrocarbyl.” The “alkyl” (i.e., “organo”) ligand suggests bonding to tin with the Sn-C bond broken, and the carbon is generally sp 3 or sp 2 It is a hybrid and generally forms bonds that are not hydrolyzable upon contact with water. The "alkyl" group may optionally have an internally unsaturated bond and a heteroatom, i.e., an atom other than carbon and hydrogen that is not included in the bond with tin. In the art, chemical groups that bond to a metal atom are generally called ligands. References to "hydrolyzable ligands" generally refer to ligands that bond to Sn by a hydrolyzable bond, such as alkoxide ligands that bond to the oxygen atom by an organo substituent on oxygen (e.g., -OR') or an organo substituent on nitrogen (e.g., -NR'). 1 R 2This refers to an amide ligand that is bonded to the nitrogen atom by ). Synthetic methods have been developed to obtain monoalkyltin trialkoxides in high yield and with low levels of (non-tin) metal and polyalkyltin (i.e., polyhydrocarbyl, e.g., dialkyltin, trialkyltin) contaminants after direct purification.

[0029] Organotin photoresist precursor compositions generally have the overall formula R n SnL 4-n (wherein the formula, n = 0.5 to 3 (or in further embodiments, n = 0.75 to 2.0, where n is the average of the species present), L is one or more hydrolysis-sensitive organotin species represented by ligands that form a hydrolyzable bond with Sn, e.g., dialkylamide (-NR'2), alkoxide (-OR'), acetylide (-CCR'), carboxylate (-COOR'), and / or similar). Generally, photoresist compositions containing a monoalkyltin composition (n=1) are of particular interest and correspond to currently commercially available organotin photoresists. Generally, R is an organo group having 1 to 31 carbon atoms that forms a C-Sn bond, and R' is an organo group having 1 to 10 carbon atoms. In some embodiments, R may contain ≤10 carbon atoms and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, t-amyl, propenyl, butenyl, pentenyl, or isomers thereof. The R group can be a linear, branched (i.e., a secondary or tertiary carbon atom bonded to a metal) or cyclic hydrocarbyl group. Each R group individually and generally has 1 to 31 carbon atoms, 3 to 31 carbon atoms in the case of a group with a secondary carbon atom, and 4 to 31 carbon atoms in the case of a group with a tertiary carbon atom, and optionally has unsaturated or aromatic carbon bonds. Groups with unsaturated carbon bonds and no heteroatoms have a total stoichiometry of C n H 2(n-1)+3It can be represented as a branched or linear group (n=1~31). In particular, branched alkyl (unsaturated) ligands may be desirable in some patterning compositions. The formation of the oxo-hydroxo coating material may involve the deposition of one or more tin compositions having hydrolyzable bonds, e.g., RSnL3 (wherein L is a hydrolyzable ligand, e.g., an alkoxide, dialkylamine, acetylide, or another suitable hydrolyzable ligand). With hydrolyzable ligands, the formation of an oxo-hydroxo network by hydrolysis may occur during and / or after the coating deposition (i.e., hydrolysis is completed after deposition). As further described in Edson et al.'s published U.S. Patent Application Publication No. 2022 / 00064192, entitled "Methods to Produce Organotin Compositions With Convenient Ligand Providing Reactants" (incorporated herein by reference), the applicant has developed a method for efficiently and effectively forming a wide range of patterning compositions having different R groups, optionally having various heteroatoms, and having C-Sn bonds.

[0030] In general, the exact structure of chemical species that may be transient in solution is unknown, but gelation is controlled to facilitate the maintenance of processability and avoid instability of the precursor solution. As further described below, controlling the amount of water in the precursor solution has been found to be desirable to homogenize the process without excessively sacrificing shelf life. In some cases, organotin photoresists have multiple RSn moieties linked via Sn-O-Sn, Sn-OH-Sn, or Sn-COO-Sn bonds, e.g., dodecamer "football-shaped" clusters [(RSn) 12 O 14 (OH)6] 2+The following may be included: and cluster compositions such as hexameric "drum-type" clusters [RSnOOCR']6. These organotin compositions generally dissolve in a suitable solvent to form an organotin photoresist solution. The use of tin dodecamer clusters for patterning is described in U.S. Patent No. 11,392,028, entitled "Tin Dodecamers and Radiation Patternable Coatings With Strong EUV Absorption" (incorporated herein by reference). The fluoride-generating compounds described herein can generally be dissolved in these organotin photoresist solutions. In some embodiments, the fluoride-generating compounds may be added to and / or dissolved in the organotin photoresist composition. In another embodiment, the fluoride-generating compound may be added to a solvent and dissolved to form a fluoride-generating compound solution, which can then be incorporated into the organotin photoresist solution. The solvent used to dissolve the fluoride-generating agent may be the same as the solvent in the precursor solution, or may be selected to be soluble or miscible with the solvent in the precursor solution.

[0031] While a range of organotin compositions can be effective radiation patterning materials, organotin compounds with a single carbon-tin bond have been found to yield desirable treatments for patterning in commercial settings, and the following discussion focuses on these monoorganotin compositions. For example, organotin precursor compositions, upon complete hydrolysis, yield the compound RSnO (1.5-(x / 2)) (OH) xcan comprise a group of compositions (RSnL₃) that can be hydrolyzed with water or another suitable reagent under conditions suitable to form a monohydrocarbyltin oxo-hydroxo patterning composition that can be represented by (wherein 0<x≦3). In general, R is a hydrocarbyl ligand substituted or unsubstituted with a heteroatom, and L is a hydrolyzable ligand further described below. It may be advantageous to perform the hydrolysis such that the oxo-hydroxo composition is formed in situ, such as during deposition and / or after formation of the initial coating. In particular, triamides (L=amide) and trialkoxides (L=alkoxide) can be desirable ligands for use under hydrolysis conditions to form radiation-sensitive coatings for patterning. It should be noted that while the terms follow the convention for hydrolyzable ligands, these may optionally contain organo substituents of various substitutions with unsaturated bonds or heteroatom substitutions. Various precursor compounds having hydrolyzable ligands are generally synthesized with this perspective by delivering the R-ligand to tin via pre-irradiation treatment. Examples of the hydrolyzable ligand include alkoxide (hydrocarbyloxide), acetylide, or amide moieties. Suitable alkoxide ligands include, for example, tert-butoxide, sec-butoxide, pentane-3-rioxide (i.e., alkoxide of pentan-3-ol), or tert-amyloxide. The organotin precursor compositions can generally be synthesized, for example, as described in U.S. Patent No. 10,787,466 issued to Edson et al. entitled "Monoalkyl Tin Compounds with Low Polyalkyl Contamination, Their Compositions and Methods" and U.S. Patent Application Publication No. 2022 / 0064192 to Edson et al. entitled "Methods to Produce Organotin Compositions with Convenient Ligand Providing Reactants", both of which are incorporated herein by reference.

[0032] By mixing a fluoride-generating compound with a precursor in a solvent, a precursor solution of the organotin patterning composition for delivery to the substrate is formed. The solvent for the organotin precursor can generally be suitable for dissolving the fluoride-generating compound, or can be selected accordingly.

[0033] The precursor solution generally comprises an organometallic precursor composition, a fluoride generating agent compound, and an organic solvent. The resist precursor composition can be conveniently defined based on the molar concentration of tin ions. Generally, the resist precursor solution contains about 0.0025 M to about 1 M of tin cations, about 0.004 M to about 0.9 M in some embodiments, about 0.005 M to about 0.75 M in further embodiments, and about 0.01 M to about 1 M in some embodiments, and about 0.01 M to about 0.5 M in further embodiments. With respect to the fluoride generating agent compound, these can be defined as a molar ratio or molar concentration relative to tin. The fluoride-generating compound can be present in the solution at a molar ratio of 0.001 to about 1 mole of fluoride to tin per mole of tin, in a further embodiment, about 0.0015 to about 0.75, in some embodiments, about 0.002 to about 0.6, in further embodiments, about 0.002 to about 0.5, in further embodiments, about 0.0035 to about 0.45, in further embodiments, about 0.005 to about 0.4, and in some embodiments, about 0.0075 to about 0.3 moles of fluoride to tin. Similarly, the precursor solution may contain the fluoride-generating compound at a concentration of about 0.000025 M to about 0.75 M, in some embodiments, about 0.00005 M to about 0.4 M, in further embodiments, about 0.000075 M to about 0.35 M, and in further embodiments, about 0.0001 M to about 0.2 M. In some embodiments, multiple fluoride-generating compounds may be present, and the sum of the concentrations of all fluoride-generating compounds will be within the aforementioned range. Those skilled in the art will recognize that further concentration ranges and values ​​within the explicitly stated range will be considered and fall within the scope of this disclosure.

[0034] Suitable organic solvents include, for example, alcohols or blends thereof. Generally, the solvent is at least 50 weight percent alcohol, and the remaining organic solvent liquid is soluble in alcohol, such as alkanes (pentane or hexane, etc.), aromatic hydrocarbons (toluene, etc.), ethers (diethyl ether C2H5OC2H5, etc.), or mixtures thereof. In some embodiments, the solvent is at least 90 weight percent alcohol, and the solvent may be substantially alcohol and only have trace amounts of other compounds as impurities. Suitable alcohols are generally monomeric alcohols with a melting point of about 10°C or less, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, their branched forms, and mixtures thereof. It has been found that a homogeneous and stable precursor solution can be obtained by controlling the amount of water. In particular, the amount of water can generally be adjusted by adding small amounts of water to the solvent to achieve a target amount of water, generally about 10,000 ppm by weight or less, in a further embodiment about 300 ppm by weight to about 2,500 ppm by weight, in a further embodiment from about 200 ppm by weight, and in a further embodiment about 250 ppm to about 1,000 ppm by weight. Those skilled in the art will recognize that further ranges within the explicitly stated range above are considered and fall within the scope of this disclosure. The use of water content adjustment is further discussed in U.S. Patent No. 11,300,876 (hereinafter referred to as '876') granted to Jiang et al., entitled "Stable Solutions of Monoalkyl Tin Alkoxides and Their Hydrolysis and Condensation Products" (incorporated herein by reference).

[0035] As described above, a photoresist precursor solution containing an organotin composition and a fluoride generator can be used to form a radiation-patternable organotin oxohydroxo material containing a Sn-F moiety pre-formed from the fluoride generator and / or solution, and such a coating can be formed using any suitable deposition method known in the art. Spin coating may be particularly desirable for coating using a photoresist precursor solution containing a fluoride generator. In a typical spin coating process, a certain volume of photoresist solution is introduced onto the surface of a substrate, and the substrate is rotated at high speed to promote rapid evaporation and a hydrolysis process, generally using atmospheric water, thereby forming a radiation-patternable coating. In some embodiments, the substrate may be rotated at speeds (i.e., spin speeds) of about 500 rpm to about 10,000 rpm, in further embodiments about 1,000 rpm to about 7,500 rpm, and in even further embodiments about 2,000 rpm to about 6,000 rpm. The spin speed may be adjusted to obtain a desired coating thickness for a particular precursor solution and a particular substrate size. Spin coating can be performed for approximately 5 seconds to 5 minutes, and in further embodiments, approximately 15 seconds to 2 minutes. An initial low-speed rotation of, for example, 50 rpm to 250 rpm can be used to initially spread the majority of the composition across the entire substrate. To remove any edge beads, a backside rinse, edge bead removal step, etc., can be performed using water or another suitable solvent. See, for example, U.S. Patent No. 10,627,719, entitled “Methods of Reducing Metal Residue in Edge Bead Region From Metal-Containing Resists” (incorporated herein by reference). Those skilled in the art will recognize that further ranges of spin coating parameters within the explicitly stated range above can be considered and fall within the scope of this disclosure.

[0036] A substrate generally provides a surface on which a coating material can be deposited, and the substrate may comprise multiple layers, with its surface relating to the top layer. The substrate surface may be treated to prepare the surface for adhesion of the coating material. Before surface preparation, the surface may be cleaned and / or smoothed as necessary. A suitable substrate surface may comprise any reasonable material. Some substrates subject to this application include, for example, silicon wafers, silica substrates, other inorganic materials, polymer substrates, for example, organic polymers, composites thereof, and combinations thereof, throughout the entire surface of the substrate and / or within the layers of the substrate. In some embodiments, the substrate may comprise a patterned structure as described by Stowers et al. in U.S. Patent No. 10,649,328, entitled “Pre-Patterned Lithography Templates, Process Based on Radiation Patterning Using The Templates And Processes To Form The Templates” (incorporated herein by reference).

[0037] The thickness of the coating can generally be a function of the concentration, viscosity, and spin velocity of the precursor solution. In other coating processes, the thickness can also generally be adjusted by selecting coating parameters. In some embodiments, it may be desirable to use a thin coating to facilitate the formation of small, high-resolution features in subsequent patterning. For example, the dried coating material may have an average thickness of more than about 250 nanometers (nm), with further embodiments having an average thickness of about 1 nm to about 50 nm, another embodiment about 2 nm to about 40 nm, and yet another embodiment about 3 nm to about 25 nm. Those skilled in the art will recognize that further ranges of thickness within the explicitly stated range above are considered and fall within the scope of this disclosure. The thickness can be evaluated using non-contact methods of X-ray reflectivity and / or polarization analysis based on the optical properties of the film. Generally, the coating is relatively uniform to facilitate processing. In some embodiments, the uniformity or flatness of a coating, such as a highly uniform coating on a reasonably sized substrate, can be evaluated using, for example, a 1-centimeter edge exclusion, i.e., the uniformity of the coating is not evaluated in the coated portion within a 1-centimeter edge, but another appropriate edge exclusion can be selected.

[0038] While heating may not be necessary for the deposition process to proceed without problems, it may be desirable to heat the coated substrate before irradiation to densify the coating material in order to accelerate the process, remove residual solvent, improve process reproducibility, and / or promote the evaporation of hydrolysis by-products, such as alcohols and / or amines. In embodiments in which the coated substrate is heated before irradiation, the coated substrate may be heated to a temperature of about 45°C to about 250°C, and in further embodiments, about 55°C to about 225°C. Heating can generally be performed for at least about 0.1 minutes, in further embodiments, about 0.5 minutes to about 30 minutes, and in further embodiments, about 0.75 minutes to about 10 minutes. Those skilled in the art will recognize that further ranges of heating temperatures and times within the explicitly stated ranges above are considered and fall within the scope of this disclosure.

[0039] Generally, photoresist coatings can be patterned using radiation. Suitable radiation sources include extreme ultraviolet (EUV), ultraviolet (UV), or electron beam (EB) radiation. When manufacturing semiconductor devices, EUV radiation is preferred over UV radiation due to its higher resolution and higher throughput than electron beam (EB) based processing. The radiation can generally be directed onto the substrate material through a mask, or a latent image can be formed within the resist coating by controllingly scanning the radiation beam across the entire substrate. In the case of EUV "masking," a pattern is formed using mirrors that reflect and direct light from a plasma source.

[0040] According to the international standard ISO 21348 (2007) (incorporated herein by reference), ultraviolet light extends to wavelengths between 100 nm and less than 400 nm. Krypton fluoride lasers can be used as 248 nm ultraviolet light sources. The ultraviolet range can be further divided in several ways under approved standards, for example, into extreme ultraviolet (EUV) from 10 nm to less than 121 nm and far ultraviolet (FUV) from 122 nm to less than 200 nm. The 193 nm line from an argon fluoride laser can be used as an FUV radiation source. EUV light is used in 13.5 nm lithography and can be generated from Xe or Sn plasma sources excited using high-energy lasers or discharge pulses. A commercially available EUV photon source is a scanner manufactured by ASML Holding NVN Ethernet. Soft X-rays can be defined as 0.1 nm to less than 10 nm.

[0041] The amount of electromagnetic radiation can be characterized by the fluence or dose obtained by integrating the radiation flux over the exposure time. In embodiments where EUV radiation is used, a suitable radiation dose is about 1 mJ / cm². 2 ~Approx. 150mJ / cm 2 In further embodiments, approximately 2 mJ / cm² 2 ~about 100mJ / cm 2 In further embodiments, approximately 3 mJ / cm² 2 ~about 50mJ / cm 2 In some embodiments, the load is approximately 10 mJ / cm². 2 ~about 60mJ / cm 2 This is possible. A person skilled in the art will recognize that a further range of radiation fluence within the explicitly stated range above will be considered and fall within the scope of this disclosure.

[0042] The coating material for development is RSnF nIt is thought to contain fluoride, but the range of possible values ​​for "n" in the coating at various processing stages of development has not been determined. The amount of fluoride initially added is known, but the quantification of the amount that ultimately binds to tin is not clear. In the irradiated area, the organic component is reduced, which is further reduced by post-exposure baking as described below. The coating still contains an oxo-hydroxo network, which is modified to some extent by the fluoride ligands without sacrificing much contrast between the irradiated and unirradiated areas based on the patterning results.

[0043] After exposure to radiation to form a latent image, a post-exposure bake (PEB) is typically performed. In some embodiments, the PEB can be performed at temperatures of about 45°C to about 250°C, in further embodiments about 50°C to about 190°C, and in even further embodiments about 90°C to about 185°C. The post-exposure heating can generally be performed for at least about 0.1 minutes, in further embodiments about 0.5 minutes to about 30 minutes, and in even further embodiments about 0.75 minutes to about 10 minutes. Further ranges of PEB temperatures and times within the explicitly stated ranges above will be considered and will be recognized as being within the scope of this disclosure by those skilled in the art. The PEB can be planned to further solidify the exposed area without decomposing the unexposed area into a metal oxide.

[0044] The applicant has found that PEB can significantly contribute to radiation-induced thermal decomposition. In other words, radiolysis may initially proceed in the irradiated structure, inducing the cleavage of hydrocarbyl ligands, removing the material of the formed product species, and forming cleaved ligands. However, it has been found that PEB can result in a further reduction of organic matter from the irradiated material, which can be called radiation-induced thermal decomposition, because neither treatment alone causes a similar reduction in organic species from the material. The reduction of organic matter from the material can be measured using infrared spectroscopy tuned to organic frequencies. It has been found that the presence of Sn-F bonds in the organotin matrix can improve radiosensitivity, which suggests an improvement in the effect of radiation-induced thermal decomposition. Furthermore, it has been found that increasing the PEB temperature also improves radiation-induced thermal decomposition. In particular, in one example involving the presence of a Sn-F bond, increasing the PEB temperature to 190°C reduced the dose required to achieve a critical line / space pattern of approximately 14 nanometers (nm) without significantly altering the linewidth roughness.

[0045] After performing PEB, image development involves either bringing a patterned coating material containing a latent image into contact with a developer composition to remove the unirradiated coating material to form a negative image, or removing the irradiated coating to form a positive image. The irradiated area of ​​an organotin hydroxide coating is generally hydrophilic and therefore soluble in aqueous bases and insoluble in organic solvents, while the unirradiated area is generally hydrophobic and therefore soluble in organic solvents and insoluble in aqueous bases. In the case of negative image formation, the developer may be an organic solvent, for example, a solvent used to form a precursor solution.

[0046] In particular, for positive image formation, a suitable developer can generally be an aqueous base. In some embodiments, aqueous bases can be used to form sharper images. To reduce contamination from the developer, it may be desirable to use a developer that does not contain metal atoms. Therefore, quaternary ammonium hydroxide compositions, such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or combinations thereof, are desirable positive developers. Generally, quaternary ammonium hydroxides of particular interest may be represented by the formula R4NOH, where R = methyl, ethyl, propyl, butyl, or combinations thereof. The coating materials described herein can generally be developed using the same developers currently commonly used for polymer resists, particularly tetramethylammonium hydroxide (TMAH). Commercially available TMAH is available in 2.38 weight percent. Furthermore, mixed quaternary tetraalkyl-ammonium hydroxides can be used. Generally, the developer may contain about 0.5 to about 30 weight percent, in a further embodiment about 1 to about 25 weight percent, and in another embodiment about 1.25 to about 20 weight percent of tetraalkylammonium hydroxide or similar quaternary ammonium hydroxide. Those skilled in the art will recognize that further ranges of developer concentrations within the explicitly stated range above are considered and fall within the scope of this disclosure. In the case of positive-type developers, it may be desirable to dissolve the densified material with a relatively high dose of radiation, assuming that the unirradiated material is not removed very well. This further broadens the process window.

[0047] In negative image formation, the developer may be an organic solvent, such as the solvent used to form the precursor solution. Generally, the choice of developer may be influenced by the solubility parameters of both irradiated and unirradiated coating materials, as well as the developer's volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials. Suitable developers include, for example, aromatic compounds (e.g., benzene, xylene, toluene), esters (e.g., propylene glycol monomethyl acetate (PGMEA), ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, methanol), ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 2-octanone), and ethers (e.g., tetrahydrofuran, dioxane, anisole). The improved developer compositions are described in Jiang et al.'s published U.S. Patent Application Publication No. 2020 / 0326627, entitled "Organometallic Photoresist Developer Compositions and Processing Methods" (incorporated herein by reference). The improved developer solutions generally comprise a reference organic solvent composition and an additive composition with higher polarity and / or hydrogen bonding properties than the reference solvent composition. In one example, the improved developer composition may comprise PGMEA and acetic acid. Development can be carried out for about 5 seconds to about 30 minutes, in a further embodiment about 8 seconds to about 15 minutes, and in a further embodiment about 10 seconds to about 10 minutes. Those skilled in the art will recognize that further ranges within the explicitly stated range are considered to be within the scope of this disclosure.

[0048] In the case of negative-type development, the choice of developer can be substantially influenced by the solubility parameters of both irradiated and unirradiated coating materials, as well as the developer's volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials. Several useful developer compositions for these organotin oxide photoresists are described in Jiang et al.'s published U.S. Patent Application Publication 2020 / 0326627, entitled "Organometallic Photoresist Developer Compositions and Processing Methods" (incorporated herein by reference). In particular, the developer may have different amounts of components with higher or lower polarity, which can be more precisely defined using solubility parameters. In some embodiments, the solvent blends each independently have a total Hansen solubility parameter δH + δP of about 16 (J / cm²). 3 ) 1 / 2 One or more solvents in an amount of at least 55% by volume, each independently having a Hansen solubility parameter δH + δP sum of at least approximately 16 (J / cm³). 3 ) 1 / 2 It may contain at least two solvents, one or more solvents in an amount of approximately 0.25% to approximately 45% by volume.

[0049] We also discovered that solvent-free development, also known as dry development, can be used for organotin materials. Dry development may include, for example, the selective removal of irradiated or unirradiated areas of a photoresist by exposing the material to a suitable plasma or a suitable flowing gas. Dry development of organotin resists is described in the PCT published international publication 2020 / 132281A1 by Volosskiy et al. entitled "Dry Development of Resists" and the published U.S. Patent Application Publication 2023 / 0100995 by Cardineau et al. entitled "High Resolution Latent Image Processing and Thermal Development" (both incorporated herein by reference). In such dry development processes, development can be achieved by performing a plasma or thermal process on an irradiated substrate while flowing a gas containing small molecule reactants that facilitate the removal of irradiated or unirradiated areas. If it is desirable to further remove unwanted material from the pattern after development, a rinsing step may be performed, and such a method is described in Kocsis et al.'s published U.S. Patent Application Publication 2020 / 0124970, entitled "Patterned Organometallic Photoresists and Methods of Patterning" (incorporated herein by reference).

[0050] To remove residual developer and other debris, a rinse using an inert liquid, such as deionized water, may be used. After the development step is complete, the coating material may be heat-treated to further densify the material and to further dehydrate, concentrate, or remove residual developer or rinse from the material. This heat treatment may be particularly desirable in embodiments where the oxide coating material is incorporated into the final device, but may also be desirable in some embodiments where the coating material is used as a resist for pattern transfer and is eventually removed, if stabilization of the coating material is desired to facilitate further patterning. In particular, the baking of the patterned coating material may be carried out under conditions in which the patterned coating material exhibits a desired level of etching selectivity. To distinguish this heating step, it may be called a hard bake. In some embodiments, the patterned coating material may be heated to temperatures of about 100°C to about 600°C, in further embodiments about 175°C to about 500°C, and in even further embodiments about 200°C to about 400°C. Heating can be carried out for at least about 1 minute, in another embodiment about 2 minutes to about 1 hour, and in a further embodiment about 2.5 minutes to about 25 minutes. Heating can be carried out in air, in a vacuum, or in an inert gas atmosphere, such as Ar or N2. Further ranges of temperatures and times for heat treatment within the explicitly stated range above will be considered and will be recognized as being within the scope of this disclosure by those skilled in the art. Similarly, non-heat treatments such as blanket UV exposure or exposure to an oxidizing plasma such as O2 can also be used for similar purposes.

[0051] Patterned structures can be evaluated using automated imaging devices, and scanning electron microscope (CD-SEM) imaging devices are commonly used. For example, certain commercially available CD-SEM instruments can measure the limit line dimensions (line width) and can also evaluate defects such as microbridging. To evaluate photoresist performance, CD-SEM instruments are generally used to analyze and measure patterns formed across multiple fields on multiple wafers. Coated wafers can be exposed to different doses of radiation within each wafer, resulting in an array of patterns with different doses across the wafer (e.g., fields), each of which can then be analyzed by CD-SEM. In this way, dose-versus-size values ​​or a set of processing conditions for a target pattern with a particular resist formulation can be collected.

[0052] Generally, improved radiosensitivity allows for lower doses to achieve the same pattern resolution under specific processing conditions. In some embodiments, comparable non-fluorinated organotin patterning materials can be patterned by irradiating the organotin material with patterning EUV radiation at a dose corresponding to at least about 8%, and in further embodiments at least about 10%, a dose corresponding to the corresponding dose for obtaining comparable limiting dimensions using the same selected developer, under the same coating thickness, same PAB and PEB conditions. The dose reduction can be rephrased as a reduction in irradiation time and, correspondingly, an increase in throughput. [Examples]

[0053] Example 1: Preparation and analysis of organotin precursor solution containing fluoride additives This example describes the preparation of an organotin precursor solution by mixing a non-fluorinated organotin precursor composition, an ammonium fluoride compound, and a solvent. NMR analysis was used to confirm the presence of Sn-F species in the prepared precursor solution.

[0054] Appropriate amounts of tert-butylsutris (pentan-3-yl oxide) and ammonium fluoride (NH4F) were mixed, and then an appropriate volume of 1-propanol was added to prepare a concentrated solution having a concentration of 1 M Sn and an initial concentration of 0.2 M NH4F. This mixture was stirred overnight to obtain a clear concentrated stock solution FA1. A second concentrated stock solution FA2 was prepared in a similar manner by mixing isopropylsutris (sec-butoxide), ammonium fluoride, and 4-methyl-2-pentanol to obtain a clear concentrated solution having a concentration of 1 M Sn and an initial concentration of 0.2 M NH4F.

[0055] NMR analysis was performed on solutions FA1 and FA2. Aliquots of each solution were taken without further interpretation and analyzed using a 500 MHz Bruker NMR spectrometer. 19 F and 119 Sn NMR analysis was performed. Figure 1 shows the results of solution FA1. 19 The 1F NMR spectrum is shown. Two covalent fluoride peaks are observed around -51 ppm and -56.3 ppm, the latter having two Sn satellite peaks (indicated by arrows). 1 J( 119 Sn- 19 F) ≈ 320 Hz, indicating the presence of a Sn-F bond. Figure 2 shows the solution FA1. 119 The Sn NMR spectrum is shown. A broad peak is observed around -406 ppm. This peak is associated with Sn alkoxide species. A sharp peak is also observed around -472.5 ppm. This sharp peak is associated with the presence of fluorinated Sn species. Similarly, Figure 3 shows the spectrum of solution FA2. 19 The F NMR spectrum is shown, and inset A shows a magnified view of the indicated region. The spectrum shows a peak with a Sn satellite peak at -59.1 ppm. 1 J( 119 Sn- 19 F) ≈ 520 Hz, which is consistent with the presence of a (covalent) Sn-F bond. Further peaks in the range of approximately -110 ppm to -180 ppm are consistent with the presence of anionic F species.

[0056] The results suggest that a reaction occurs between ammonium fluoride and organotin trialkoxide to form a fluorinated organotin precursor solution containing a Sn-F bond. In particular, the results are for formula NH4 + [tBuSn(pentan-3-yloxide)3F] - (In the case of solution FA1) or formula NH4 + [i-PrSn(sec-butoxide)3F] - This suggests the formation of a complex salt containing ammonium ions and tin / fluorine-containing ions, as represented by (in the case of solution FA2).

[0057] Example 2: ESI-MS analysis of fluorinated organotin resist precursor solution This example further demonstrates the presence of fluorinated organotin oxo-hydroxo species in an organotin photoresist precursor solution prepared with a fluoride additive.

[0058] First, a series of concentrated stock solutions were prepared by mixing tert-butylsutris(pentane-3-yloxide) and ammonium fluoride in molar ratios of 10:1, 5:1, 2:1, or 1:1. Next, each mixture was dissolved in a solvent blend of 32 wt% 1-propanol / 68 wt% 1-pentanol containing 2000 ppm H2O. The mixtures were stirred overnight to form stock solutions S1, S2, S3, and S4, as summarized in Table 1.

[0059] [Table 1]

[0060] After forming the stock solutions, each stock solution was diluted 10-fold with a 32% / 68% 1-propanol / 1-pentanol solvent blend containing 2000 ppm H2O to obtain a photoresist solution with a [Sn] concentration of 0.065 M, thereby preparing photoresist solutions P1, P2, P3, and P4 from aliquots of S1, S2, S3, and S4, respectively. After dilution, the photoresist solutions were filtered through a 0.62 μm syringe filter before ESI-MS analysis.

[0061] From a precursor composition based on t-butyltin, the general formula [(tBuSn) 12 O 14 The dodecamer Sn represented by (OH)6][OH]2 12 To promote the formation of organotin oxoclusters such as seeds, 2000 ppm H2O was added to the solvent blend. According to a previous study by Dakternieks et al. (J. Organomet. Chem. 476 (1994) 33-40), the dodecimer n-BuSn 12 Species are generally identified by ESI-MS analysis as biionized species [(nBuSn)] 12 O 14 (OH)6] 2+ It has been shown that it can be easily detected as such. In this study, similar deprotonated single-ionized dodecamers are detected at an m / z value of 2434. Therefore, the presence of fluorinated dodecamer species was tested by comparing the m / z value of the dodecamer species confirmed in each sample with the reference value of 2434.

[0062] Figure 4 shows the ESI-MS spectra of photoresist solutions P1, P2, P3, and P4. Each photoresist solution contains the dodecamer t-BuSn 12The species showed an average m / z value greater than the reference value of 2434. Furthermore, it was confirmed that the average m / z value generally increased with increasing relative amounts of F to Sn used in the preparation of the corresponding stock solution, as summarized in Table 4. P1 had an average m / z of 2436, and P3 and P4 had an average m / z of 2440. In other words, it was confirmed that the maximum m / z value of the peak corresponding to the dodecamer species generally shifted to a larger m / z value with increasing fluoride concentration, suggesting that the hydrolysis / condensation pathway leading to the formation of organotin oxo / hydroxo species can proceed similarly in the presence of fluoride, and that the Sn-OH bond can be substituted with a Sn-F bond. Dodecamer t-BuSn 12 It was also confirmed that the peak shifts to an n+2 larger m / z value when the amount of ammonium fluoride increases between P1 and P2 and between P2 and P3. This result indicates that OH - F by (m / z=17) - This is consistent with the increase in substitution at (m / z=19). The equation shown in Table 2 is consistent with the observed fluorinated dodecamer peak.

[0063] [Table 2]

[0064] As shown in Table 4, the photoresist solution P4 formed a precipitate during the experiment, which was observed to be t-BuSn 12This likely explains why the m / z value of 2440 did not follow the increasing trend in m / z. Further experiments were conducted using photoresist solutions prepared in the same way as P4, except that a lower water content (300 ppm) solvent was used. These lower water content photoresist solutions were observed to not form precipitates and not to form dodecamer species detectable by ESI-MS analysis. The ESI-MS results for the low-water solutions showed species with Sn and F atoms, which could reasonably be considered to have Sn-F bonds, but the exact structure could not be easily evaluated with the contrast of dodecamers. This result suggests that the precipitation of photoresist solution P4 is due to the formation of insoluble hydrolysis / condensation products due to the higher water content. Nevertheless, the inclusion of fluoride in the organotin oxo species formed in photoresist solution P4 was evident from the average m / z value of 2440.

[0065] Example 1 demonstrates the formation of a fluorinated organotin precursor solution having Sn-F bonds by mixing an organotin trialkoxide with ammonium fluoride. This example shows that fluorinated organotin oxo-hydroxo clusters are formed by contacting an alkoxide fluoride complex with water. The relatively high water content of the photoresist solution used in this example serves as a model for hydrolysis / condensation products formed during the deposition of the photoresist solution to form a photoresist film. Therefore, films formed from such fluorinated organotin precursor solutions are expected to contain a fluorinated organotin oxo-hydroxo network incorporating Sn-F bonds.

[0066] Example 3: Fluorinated organotin film and contrast curve This example demonstrates that the patterning dose of organotin photoresist films prepared using an organotin precursor solution to which ammonium fluoride has been added decreases.

[0067] Organotin precursor solutions F1, F2 and C having Sn and F concentrations and Sn:F molar ratios as shown in Table 3 were prepared. First, a concentrated stock solution was prepared by mixing appropriate masses of ammonium fluoride with a 20 mol% / 80 mol% blend of methyltin tris(tert-butoxide) and tert-butyltin tris(pentan-3-yloxide), which are organotin trialkoxides, respectively. Each mixture was dissolved in a solvent blend of 32 wt% 1-propanol / 68 wt% 1-pentanol containing 350 ppm H₂O. The mixture was stirred overnight to form a concentrated fluorinated organotin precursor solution with a total [Sn] concentration of 0.62 M. After mixing, the concentrated stock solution was diluted 10-fold with a 32 wt% / 68 wt% 1-propanol / 1-pentanol solvent blend containing 350 ppm H₂O to obtain photoresist solutions (F1 and F2) with a [Sn] concentration of 0.065 M. A control solution was also prepared by dissolving an appropriate mass of the organotin precursor in a 32 wt% / 68 wt% 1-propanol / 1-pentanol solvent blend containing 350 ppm H₂O.

[0068] [Table 3]

[0069] The precursor solution was spin-coated onto a 300 mm circular Si wafer having an approximately 10 nm layer of spin-on-glass (SOG) to form a photoresist coating. The coated wafer was then subjected to a post-application bake (PAB) at 130°C for 60 seconds. The film thickness of each coated wafer was measured by ellipsometry to be approximately 28 nm.

[0070] After PAB, each coated wafer was then exposed on an ASML TwinScan NXE3400 EUV exposure tool to form an exposure area contrast array (i.e., pads) across each wafer, and each exposure area was about 1 mJ / cm 2 ~90 mJ / cm 2The wafers were exposed to different doses of radiation. After EUV exposure, the films were then subjected to post-exposure baking (PEB) at 180°C for 60 seconds. Next, each wafer was developed using 5 wt% acetic acid in a PGMEA solution. Finally, the wafers were subjected to hard baking at 250°C for 60 seconds. After hard baking, contrast curves were created for each wafer by measuring the thickness of each exposed region to form a thickness-versus-radiation plot for each wafer. The thickness of the SOG layer (8.8 nm) was subtracted from the measured thickness of the resist. For clarity, the thickness was normalized to the maximum thickness observed in each curve (i.e., maximum thickness = 1).

[0071] Figure 5 shows the contrast curves of coated wafers prepared from F1, F2, and the control (precursor solution C). The results, plotted on a logarithmic scale, show a significant decrease in the patterning dose as the amount of ammonium fluoride in the precursor solution increases. Coated wafers prepared from precursor solutions F1 and F2 showed lower patterning doses than those prepared from the control precursor solution. The results indicate that the addition of ammonium fluoride to the precursor solution results in the presence of fluoride within the film, thereby reducing the dose required for patterning. Coated wafers prepared from precursor solution F1, with a [Sn]:[F] ratio of 10:1, required a lower dose for gelation than coated wafers prepared from the control (which did not contain fluoride). Coated wafers prepared from precursor solution F2, with twice the ammonium fluoride concentration of precursor solution F1, required an even lower dose for gelation. This is particularly true for the apparent contrast of the film, indicated by the sharpness of the thickness transition. This indicates that adding fluoride to the resist precursor solution can improve the radiosensitivity of the resist film while significantly maintaining high contrast between unexposed and exposed areas.

[0072] These results indicate that the addition of ammonium fluoride to the organotin photoresist precursor solution can improve the dose sensitivity of the photoresist film without significantly reducing contrast.

[0073] Example 4: EUV patterning of fluorinated organotin oxo-hydroxo films This example demonstrates an improvement in EUV patterning of films produced from an organotin photoresist precursor solution containing an ammonium fluoride additive.

[0074] A photoresist precursor solution was prepared by mixing tert-butylsutris (tert-butoxide), an ammonium fluoride compound, and a solvent according to Table 4.

[0075] The ammonium fluoride compounds used in this study were inorganic ammonium fluoride ("HNF"), tetramethylammonium fluoride ("MNF"), and tetrabutylammonium fluoride ("BNF"). As shown in Table 5, the components selected for each precursor solution were combined and mixed.

[0076] [Table 4]

[0077] [Table 5]

[0078] The precursor solution SA containing HNF was mixed via the concentrated solution route and then diluted with the solvent blends described in Examples 1-3, as shown in Table 5 as the mixing method "Conc.". Precursor solutions SB and SC were prepared by dissolving an appropriate mass of BNF or MNF, respectively, in a mixture of tert-butylsutris (tert-butoxide) and a solvent having the described final concentration of Sn. No secondary dilution was performed in this "standard" mixing method ("Std."). For each precursor solution, an amount of fluoride compound was used to obtain the described percentage fluoride relative to Sn. Control precursor solutions (CS-1 and CS-2) without the addition of a fluoride compound were also prepared using solvents Z1 and Z2, respectively.

[0079] A photoresist coating was formed on a circular 300 mm Si wafer with a spin-on glass (SOG) layer of approximately 10 nm by spin-coating a precursor solution. Next, the coated wafer was subjected to PAB at 100°C for 60 seconds. The obtained resist films are summarized in Table 6. The film thickness was measured by polarization analysis.

[0080] [Table 6]

[0081] After PAB, each coated wafer was then exposed on an ASML NXE3400 TwinScan EUV lithography tool using a dose meander exposure scheme to form an array of line-space patterns with a nominal dimension of 14 nm (14p28) on a 28 nm space, with each array portion printed at a different location on the wafer with a different dose. The exposed wafers were then subjected to PEB at 170°C, 180°C, or 190°C for 60 seconds, followed by development with 5 wt% acetic acid in PGMEA. Finally, each wafer was hard baked at 250°C for 60 seconds.

[0082] Next, CD-SEM images were collected and analyzed using a commercially available CD-SEM instrument to determine the dose, limiting dimensions (CD, average diameter of holes), and linewidth roughness (LWR) values ​​for each collected image. Figure 6 shows the CD-SEM images and PEB conditions for each sample in the case of a 14p28 line space pattern. Each image corresponds to the EUV dose (unit: mJ / cm²). 2 The values ​​shown are CD (in nm) and LWR (in nm). Figure 7 shows bar graphs of EUV dose versus PEB conditions for each sample.

[0083] Sample (A) prepared from a precursor solution containing HNF showed lower doses under all PEB conditions, which is consistent with the contrast curve shown in Example 3 (Figure 5). Samples prepared from precursor solutions using HNF or MNF as additives allowed for lower patterning doses while simultaneously maintaining a photoresist resolution of at least 14p28 and exhibiting LWR performance equivalent to samples prepared without fluoride additives (Control 1 and Control 2). In the case of sample (B) prepared from a precursor solution containing BNF, a higher patterning dose was observed under the lowest PEB conditions than the control samples, but a lower LWR was also observed. When the PEB temperature increased from 170°C to 180°C and then to 190°C, there was a significant decrease in dose, to 70.3 mJ / cm², respectively. 2 From 57.5 mJ / cm² 2 Up to 45.9 mJ / cm² 2 The following changes were observed with each temperature increase. The dose decrease for sample B, as a function of PEB temperature, was greater than that for sample A or sample C. This result suggests that BNF has a much higher thermal effect than HNF or MNF. Similarly, the patterning dose of the MNF sample decreased more rapidly with PEB temperature than that of the HNF sample and control.

[0084] These results demonstrate that adding ammonium fluoride to an organotin photoresist precursor solution can improve the patterning performance of the photoresist by reducing the patterning dose without increasing the LWR of the pattern. The results also suggest that further improvements in patterning performance, such as reduced patterning dose and improved LWR, may be possible by preparing precursor solutions containing a blend of ammonium fluoride compounds.

[0085] The embodiments described above are descriptive and not limiting. Further embodiments are within the scope of the claims. Furthermore, although the invention has been described with reference to specific embodiments, those skilled in the art will recognize that modifications in form and detail are possible without departing from the intent and scope of the invention. Any referential use of the above-mentioned documents is limited so as not to refer to subject matter contrary to the express disclosure herein. Unless otherwise specifically stated, the disclosure herein extends to embodiments that essentially consist of specific components, elements, components or other sections, including specific embodiments, specific components, elements, components or other sections, and may include further features that do not alter the fundamental nature of the subject matter as suggested in the embodiments and discussion. The use of the term “about” herein means an expected uncertainty in the relevant value as understood by those skilled in the art in the particular context.

Claims

1. Organic solvent and formula RSnL ３ A precursor solution for a radiation patterning composition, comprising a blend of an organotin composition represented by and a compound capable of generating an Sn-F bond, wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond, and L is a hydrolyzable ligand.

2. The precursor solution according to claim 1, wherein the organic solvent comprises one or more alcohols.

3. The precursor solution according to claim 1, wherein the organic solvent comprises 1-propanol, 1-pentanol, 4-methyl-2-pentanol, or a combination thereof.

4. A precursor solution according to any one of claims 1 to 3, comprising a controlled amount of water.

5. A precursor solution according to any one of claims 1 to 4, comprising approximately 200 ppm by weight to approximately 10,000 ppm by weight of water.

6. A precursor solution according to any one of claims 1 to 4, comprising approximately 250 ppm by weight to approximately 1,000 ppm by weight of water.

7. The precursor solution according to any one of claims 1 to 6, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, an unbranched alkyl group, a branched alkyl group, or a combination thereof.

8. The precursor solution according to any one of claims 1 to 6, wherein R comprises a t-butyl group, an isopropyl group, or a combination thereof.

9. The precursor solution according to any one of claims 1 to 6, wherein R comprises an alkyl group substituted with an I, F, or O atom.

10. The precursor solution according to any one of claims 1 to 9, wherein the Sn-C bond is radiosensitive.

11. The precursor solution according to any one of claims 1 to 10, wherein L is an alkoxide, a dialkylamide, an alkylacetylide, an alkylsilylamide, or a combination thereof.

12. The precursor solution according to any one of claims 1 to 10, wherein L is tert-butoxide, sec-butoxide, pentane-3-yloxide, or tert-amyloxide.

13. The compound has the formula NR ａ R ｂ R ｃ R ｄ F (wherein R ａ , R ｂ , R ｃ and R ｄ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or a mixture thereof), the precursor solution according to any one of claims 1 to 12, comprising an ammonium fluoride compound represented by the formula.

14. The compound is of formula NR' ４ A precursor solution according to any one of claims 1 to 12, comprising an ammonium fluoride compound represented by F (wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms).

15. The aforementioned compound is NH ４ F, N (CH ３ ) ４ F, N (C ４ H ９ ) ４ A precursor solution according to any one of claims 1 to 12, comprising F or a mixture thereof.

16. The precursor solution according to any one of claims 1 to 15, wherein the molar ratio of Sn to F is about 100:1 to about 1:

1.

17. A precursor solution according to any one of claims 1 to 16, comprising a fluorinated organotin oxo-hydroxo species.

18. A precursor solution according to any one of claims 1 to 17, comprising a Sn-F bond.

19. A precursor solution according to any one of claims 1 to 18, comprising fluoride ions.

20. A precursor solution according to any one of claims 1 to 19, comprising a dissolved fluorinated salt complex.

21. The dissolved fluorinated salt complex is of formula NH ４ ＋ [RSnL ３ F] － The precursor solution according to claim 20, represented by [the specified figure].

22. The precursor solution according to any one of claims 1 to 21, wherein the compound capable of generating Sn-F bonds can generate Sn-F bonds in solution and / or after solvent removal.

23. The precursor solution according to claim 22, wherein the formation of the Sn-F bond after solvent removal is accompanied by a thermal or radiative propulsion force.

24. A precursor solution according to any one of claims 1 to 23, having a tin concentration of approximately 0.0025 M to approximately 1 M.

25. Organic solvent and formula RSnL ３ A precursor solution for a radiation patterning composition comprising a blend of an organotin composition represented by and a compound capable of generating fluoride ions during exposure to EUV radiation or post-exposure baking.

26. The precursor solution according to claim 25, further comprising a compound capable of generating an Sn-F bond.

27. The precursor solution according to claim 26, wherein the compound capable of generating fluoride ions and the compound capable of generating Sn-F bonds are the same.

28. The precursor solution according to any one of claims 25 to 27, wherein the organic solvent comprises one or more alcohols.

29. The precursor solution according to any one of claims 25 to 27, wherein the organic solvent comprises 1-propanol, 1-pentanol, 4-methyl-2-pentanol, or a combination thereof.

30. A precursor solution according to any one of claims 25 to 29, comprising a controlled amount of water.

31. A precursor solution according to any one of claims 25 to 30, comprising approximately 200 ppm by weight to approximately 10,000 ppm by weight of water.

32. A precursor solution according to any one of claims 25 to 30, comprising approximately 250 ppm by weight to approximately 1,000 ppm by weight of water.

33. The precursor solution according to any one of claims 25 to 32, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, a non-branched alkyl group, a branched alkyl group, or a combination thereof.

34. The precursor solution according to any one of claims 25 to 32, wherein R comprises a t-butyl group, an isopropyl group, or a combination thereof.

35. The precursor solution according to any one of claims 25 to 32, wherein R comprises an alkyl group substituted with an I, F, or O atom.

36. The precursor solution according to any one of claims 25 to 35, wherein the Sn-C bond is radiosensitive.

37. The precursor solution according to any one of claims 25 to 36, wherein L is an alkoxide, a dialkylamide, an alkylacetylide, an alkylsilylamide, or a combination thereof.

38. The precursor solution according to any one of claims 25 to 36, wherein L is tert-butoxide, sec-butoxide, pentane-3-yl oxide, or tert-amyl oxide.

39. The aforementioned compound is of formula NR ａ R ｂ R ｃ R ｄ F (wherein, R ａ , R ｂ , R ｃ and R ｄ The precursor solution according to any one of claims 25 to 38, comprising an ammonium fluoride compound (which is independently represented by hydrogen or an alkyl group having 1 to 6 carbon atoms or a mixture thereof).

40. The compound is of formula NR' ４ A precursor solution according to any one of claims 25 to 38, comprising an ammonium fluoride compound represented by F (wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms).

41. The aforementioned compound is NH ４ F, N (CH ３ ) ４ F, N (C ４ H ９ ) ４ A precursor solution according to any one of claims 25 to 38, comprising F or a mixture thereof.

42. The precursor solution according to any one of claims 25 to 41, wherein the molar ratio of Sn to F is about 100:1 to about 1:

1.

43. A precursor solution according to any one of claims 25 to 42, comprising a fluorinated organotin species.

44. A precursor solution according to any one of claims 25 to 43, comprising a Sn-F bond.

45. A precursor solution according to any one of claims 25 to 44, comprising fluoride ions.

46. A precursor solution according to any one of claims 25 to 45, comprising a dissolved fluorinated salt complex.

47. The dissolved fluorinated salt complex is of formula NH ４ ＋ [RSnL ３ F] － The precursor solution according to claim 46, represented by [the specified method].

48. A precursor solution according to any one of claims 25 to 47, having a tin concentration of approximately 0.0025 M to approximately 1 M.

49. Exposure to EUV radiation is approximately 100 mJ / cm². ２ The precursor solution according to any one of claims 25 to 48, administered at the following doses.

50. The precursor solution according to any one of claims 25 to 49, wherein the post-exposure baking is performed at a temperature of about 50°C to about 250°C.

51. Organic solvent and formula RSnL ３ One or more organotin compounds represented by formula NR (wherein R is a saturated or unsaturated linear, branched, cyclic, or aromatic hydrocarbyl group having 1 to 31 carbon atoms optionally substituted with heteroatoms, and L is a hydrolyzable ligand), and formula NR ａ R ｂ R ｃ R ｄ F (wherein, R ａ , R ｂ , R ｃ and R ｄ A photoresist precursor composition comprising a mixture with an ionic fluoride compound (which is independently represented by hydrogen or an alkyl group having 1 to 6 carbon atoms, or a mixture thereof).

52. The precursor solution according to claim 51, wherein the organic solvent comprises one or more alcohols.

53. The precursor solution according to claim 51, wherein the organic solvent comprises 1-propanol, 1-pentanol, 4-methyl-2-pentanol, or a combination thereof.

54. A precursor solution according to any one of claims 51 to 53, comprising a controlled amount of water.

55. The aforementioned ionic fluoride compound is of formula NR' ４ A precursor solution according to any one of claims 51 to 54, comprising an ammonium fluoride compound represented by F (wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms).

56. The aforementioned ionic fluoride compound is NH ４ F, N (CH ３ ) ４ F, N (C ４ H ９ ) ４ A precursor solution according to any one of claims 51 to 54, comprising F or a mixture thereof.

57. The precursor solution according to any one of claims 51 to 56, wherein the molar ratio of Sn to F is about 100:1 to about 1:

1.

58. The precursor solution according to any one of claims 51 to 56, wherein the molar ratio of Sn to F is about 10:1 to about 1.5:

1.

59. The precursor solution according to any one of claims 51 to 58, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, a non-branched alkyl group, a branched alkyl group, or a combination thereof.

60. The precursor solution according to any one of claims 51 to 58, wherein R comprises a t-butyl group, an isopropyl group, or a combination thereof.

61. The precursor solution according to any one of claims 51 to 58, wherein R comprises an alkyl group substituted with an I, F, or O atom.

62. The precursor solution according to any one of claims 51 to 61, wherein the Sn-C bond is radiosensitive.

63. The precursor solution according to any one of claims 51 to 62, wherein L is an alkoxide, a dialkylamide, an alkylacetylide, an alkylsilylamide, or a combination thereof.

64. The precursor solution according to any one of claims 51 to 62, wherein L is tert-butoxide, sec-butoxide, pentane-3-yl oxide, or tert-amyl oxide.

65. A radiation-patternable film formed by depositing a photoresist composition according to any one of claims 51 to 64.

66. A method for forming a photoresist solution having an Sn-F bond, wherein the formula is RSnL ３ The organotin precursor represented by formula NR ａ R ｂ R ｃ R ｄ F (wherein, R ａ , R ｂ , R ｃ and R ｄ A method comprising mixing a fluoride source compound (which is independently represented by hydrogen or an alkyl group having 1 to 6 carbon atoms or a mixture thereof) in an organic solvent to form the photoresist solution having an Sn-F bond, wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond, and L is a hydrolyzable ligand.

67. The method according to claim 66, wherein the organic solvent comprises one or more alcohols.

68. The method according to claim 66, wherein the organic solvent comprises 1-propanol, 1-pentanol, 4-methyl-2-pentanol, or a combination thereof.

69. The method according to any one of claims 66 to 68, wherein the organic solvent is provided as a solvent blend comprising the organic solvent and a controlled amount of water.

70. The method according to claim 69, wherein the solvent blend contains about 200 ppm by weight to about 10,000 ppm by weight of water.

71. The method according to claim 69, wherein the solvent blend contains about 250 ppm by weight to about 1,000 ppm by weight of water.

72. The method according to any one of claims 66 to 71, further comprising adding a controlled amount of water to the photoresist solution.

73. The method according to any one of claims 66 to 72, wherein the mixing comprises mixing the fluoride source compound with the organotin precursor to form an initial mixture, and mixing the initial mixture with the organic solvent to form the photoresist solution.

74. The method according to any one of claims 66 to 72, wherein the mixing comprises mixing the fluoride source compound with the organotin precursor to form an initial mixture; mixing the initial mixture with a first portion of the organic solvent to form a concentrated solution; and mixing the concentrated solution with the remaining portion of the organic solvent to form the photoresist solution.

75. The method according to claim 74, wherein the concentrated solution has a tin concentration of about 0.25 M to about 2 M.

76. The method according to any one of claims 66 to 72, wherein the mixing comprises adding the fluoride source compound to the solution of the organotin precursor in the organic solvent.

77. The method according to any one of claims 66 to 72, wherein the fluoride source compound is first dissolved in a first solvent to form a first solution, and the organotin precursor is dissolved in a second solvent to form a second solution, and the mixing comprises combining the first solution and the second solution, wherein the organic solvent is a combination of the first solvent and the second solvent.

78. The method according to any one of claims 66 to 77, wherein the organotin precursor and the fluoride source compound are mixed in a molar ratio of about 100:1 to about 1:

1.

79. The method according to any one of claims 66 to 77, wherein the organotin precursor and the fluoride source compound are mixed in a molar ratio of about 20:1 to about 1.5:

1.

80. The method according to any one of claims 66 to 79, wherein the photoresist solution has a tin concentration of about 0.0025 M to about 1 M.

81. The method according to any one of claims 66 to 80, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, an unbranched alkyl group, a branched alkyl group, or a combination thereof.

82. The method according to any one of claims 66 to 81, wherein L is an alkoxide, a dialkylamide, an alkylacetylide, an alkylsilylamide, or a combination thereof.

83. The fluoride source compound is of formula NR' ４ The method according to any one of claims 66 to 82, comprising an ammonium fluoride compound represented by F (wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms).

84. The fluoride source compound is NH ４ F, N (CH ３ ) ４ F, N (C ４ H ９ ) ４ The method according to any one of claims 66 to 82, comprising F or a mixture thereof.

85. The fluoride source compound is of formula NR ａ R ｂ R ｃ R ｄ F (wherein, R ａ , R ｂ , R ｃ and R ｄ The method according to any one of claims 66 to 82, comprising an ammonium fluoride compound represented independently by hydrogen or an alkyl group having 1 to 6 carbon atoms or a mixture thereof.

86. A structure comprising a substrate and a patterning material on the surface of the substrate, wherein the patterning material is RSnF ｎ A structure comprising a portion (wherein 0 < n ≤ 1, and R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and Sn-C bonds).

87. The patterning material has the structure according to claim 86, wherein the patterning material has an oxo-hydroxo network.

88. The structure according to claim 86 or 87, wherein R has a Sn-C bond.

89. The structure according to any one of claims 86 to 88, wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond.

90. The method according to any one of claims 86 to 89, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, an unbranched alkyl group, a branched alkyl group, or a combination thereof.

91. The method according to any one of claims 86 to 89, wherein R comprises a t-butyl group, an isopropyl group, or a combination thereof.

92. The method according to any one of claims 86 to 89, wherein R comprises an alkyl group substituted with an I, F, or O atom.

93. The method according to any one of claims 86 to 92, wherein the Sn-C bond is radiosensitive.

94. The method according to any one of claims 86 to 93, wherein the patterning material has an average thickness of about 2 nm to about 40 nm on the surface.

95. The method according to any one of claims 86 to 93, wherein the patterning irradiation of the patterning material forms an irradiated region and a non-irradiated region, and the irradiated region has a reduced organic concentration.

96. The method according to claim 95, wherein the patterning material in the irradiated area is soluble in aqueous base.

97. The method according to claim 95, wherein the patterning material in the non-irradiated region is soluble in an organic solvent.

98. The method according to any one of claims 86 to 97, wherein the patterning material comprises an ammonium cation.

99. The patterning material is NH ４ ＋ , N(CH ３ ) ４ ＋ , N(C ４ H ９ ) ４ ＋ or a mixture thereof, the method according to any one of claims 86 to 97.

100. The method according to any one of claims 86 to 99, wherein the substrate includes a silicon wafer.

101. The method according to claim 100, wherein the un-irradiated portion of the patterning material is substantially removed to form a negative pattern, or the irradiated portion of the patterning material is substantially removed to form a positive pattern.

102. A method for patterning an organotin material having Sn-F bonds, comprising irradiating the organotin material with patterning EUV radiation at a dose corresponding to at least 8% lower than the corresponding dose for an equivalent non-fluorinated organotin patterning material, thereby providing a patterned material having the same coating thickness and equivalent limiting dimensions.

103. The method according to claim 102, wherein the organotin patterning material comprises an RSn moiety (wherein R is a substituted or unsubstituted hydrocarbyl ligand having 1 to 31 carbon atoms and an Sn-C bond).

104. The method according to claim 103, wherein the organotin patterning material comprises an oxo-hydroxo network.

105. The method according to claim 103 or 104, wherein R comprises a cyclic alkyl group, an aromatic group, a fluorinated group, an unbranched alkyl group, a branched alkyl group, or a combination thereof.

106. The method according to claim 103 or 104, wherein R comprises a t-butyl group, an isopropyl group, or a combination thereof.

107. The method according to any one of claims 103 to 106, wherein the Sn-C bond is radiosensitive.

108. The method according to any one of claims 102 to 107, wherein the ratio of Sn to F atoms is about 1:0.01 to about 1:0.

75.

109. The method according to any one of claims 102 to 108, wherein the patterning material has an average thickness of about 2 nm to about 40 nm on its surface.

110. The method according to any one of claims 102 to 109, wherein the patterning irradiation of the patterning material forms an irradiated region and a non-irradiated region, and the irradiated region has a reduced organic concentration.

111. The aforementioned dose is approximately 10 mJ / cm². ２ ~Approx. 60mJ / cm ２ The method according to any one of claims 102 to 110.

Images