Organotin alkoxides as precursors for patterning compositions having fluorine substituents and carbon-carbon double bonds.

Abstract

Organotin compositions suitable for radiation-based patterning have ligands that provide a fluorinated group and an unsaturated carbon-carbon bond, such as a C=C bond. The fluorinated group and the unsaturated carbon-carbon bond may or may not be located on the same ligand. Blends of precursors with different ligands provide additional flexibility in precursor design. Fluorinated organometallic compounds are given by formula R UF It can be expressed by Sn(OR')3, where R UF R' is an organic group consisting of 1 to 31 carbon atoms, having at least one C=C bond and at least one fluorine atom bonded to carbon, and this organic group forms a C-Sn bond, while R' is an organic group consisting of 1 to 10 carbon atoms. The precursor is suitable for liquid-phase or gas-phase deposition.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to the pending U.S. Provisional Patent Application No. 63 / 521,158, titled "Selective Synthesis of Organotin Alkoxides," which is incorporated herein by reference.

[0002] The present invention relates to organometallic tin-based photopatternable materials having organic ligands with fluorine-carbon bonds and intercarbon double bonds, and hydrolyzable ligands. The fluorine-carbon bonds and intercarbon double bonds may or may not be present in the same ligand, and in some embodiments, one or more carbon atoms having double bonds may be fluorinated. The present invention further relates to solutions for coating these compositions, and coatings formed from these compositions, generally following hydrolysis of the hydrolyzable ligand. [Background technology]

[0003] Organometallic compounds suitable for radiation-based patterning can provide metal ions in solution or in vapor form for thin film deposition. Organotin compounds can provide high extreme ultraviolet (EUV) absorption and radiation-sensitive tin-ligand bonds, and can be used to pattern thin films by lithography. The fabrication of semiconductor devices at conventional shrinkage dimensions using EUV radiation requires novel materials with wide process margins to achieve the required patterning resolution and low defect density. [Overview of the Initiative] [Means for solving the problem]

[0004] In the first embodiment, the present invention is R 1 SnL 1 3 and R 2 SnL 2 Regarding compositions including a blend with 3, R1 and R 2 are each independently an organic group having 1 to 31 carbon atoms, collectively including at least one carbon atom having at least one unsaturated carbon-carbon bond and at least one carbon atom having a C-F bond, and each organic group forms a C-Sn bond, and R 1 SnL 1 3 and R 1 SnL 1 3 each contain at least about 1% of the total Sn atoms in the composition, and L 1 and L[[ID=十四]] 2 are each independently a hydrolyzable ligand selected. The photoresist composition may contain an organic solvent, and the composition contains a blend of R 1 SnL 1 3 and R 2 SnL 2 3.

[0005] at 0000180 In a further aspect, the present invention relates to a fluorinated organometallic compound represented by the formula R UF Sn(OR’)3, where R UF is an organic group having 1 to 31 carbon atoms, having at least one C=C bond and at least one fluorine atom bonded to carbon, and the organic group forms a C-Sn bond, and R’ is an organic group having 1 to 10 carbon atoms. The photoresist composition contains an organic solvent and a fluorinated organometallic compound.

[0006] In another aspect, the present invention relates to a method for synthesizing a fluorinated organometallic compound represented by the formula R UF Sn(OR’)3, where R UF is an organic group having 1 to 31 carbon atoms, having an unsaturated C-C bond and at least one fluorine atom bonded to carbon, R UF forms a C-Sn bond, and R’ is an organic group having 1 to 10 carbon atoms. This method involves reacting R UF [[ID=四十三]]X (where X is Cl, Br or I) with Sn2(OR’)4 or MSn(OR’)3 under visible light or ultraviolet light.

[0007] Furthermore, the present invention relates to R B SnO(3 / 2-x / 2) (OH) x With respect to a composition containing, in the formula, 0 <x<3であり、R B represents a blend of organic groups or ligands, each being an organic group, each independently having 1 to 31 carbon atoms, and collectively the organic group having at least one carbon atom with a C=C bond and at least one carbon atom with a CF bond, each organic group forming a C-Sn bond, and the composition containing an oxo-hydroxo network structure. The coated substrate is a substrate having a surface, and the surface of the substrate has R B SnO (3 / 2-x / 2) (OH) x A composition containing and may contain

[0008] Furthermore, the present invention relates to a method for forming a patterning composition on a substrate surface, comprising coating the substrate surface with a solution and removing a solvent to form the coating. The solution comprises a solvent and R 1 SnL 1 3 and dR 2 SnL 2 May include 3 blends, R 1 and R 2 These are organic groups of 1 to 31 carbon atoms, each independently containing at least one unsaturated carbon-carbon bond and at least one fluorine atom bonded to a carbon atom, where the organic groups form C-Sn bonds, and R 1 SnL 1 3 and R 1 SnL 2 Each of the three components contains at least about 1% of the total Sn atoms in the composition, and L 1 and L 2 is an independently selected hydrolyzable ligand. The resulting coating is R B SnO (3 / 2-x / 2) (OH) x It may include, in the formula, 0 <x<3であり、R B is R 1 Ligand and R 2 It is a blend with a ligand.

[0009] In some embodiments, the present invention relates to a method for forming a radiation-patternable coating on a substrate surface, comprising reacting an organotin precursor with a corresponding reactant simultaneously or sequentially to form a patternable organometallic composition on the substrate surface, wherein the organotin precursor and the corresponding reactant are supplied as vapors. Generally, the organotin precursor vapor is R 1 SnL 1 3 and R 2 SnL 2 Includes 3, R 1 and R 2 These are organic groups of carbon atoms 1 to 31, each independently containing at least one unsaturated carbon-carbon bond and at least one fluorine atom bonded to a carbon atom, and the organic groups form a C-Sn bond, R 1 SnL 1 3 and R 1 SnL 2 Each of the three components contains at least about 1% of the total Sn atoms in the composition, and L 1 and L 2 is an independently selected hydrolyzable ligand. The corresponding reactants may include water, oxygen molecules, and / or other oxygen-donating compounds; the method comprises forming a radiation-patternable coating on the surface of a substrate, wherein the radiation-patternable coating is R B SnO (3 / 2-x / 2) (OH) x Including, in the formula, 0 <x<3であり、R B is R 1 Ligand and R 2 It is a blend with a ligand.

[0010] In other embodiments, the present invention is R 1 SnL 1 3 and R 2 SnL 2 Regarding compositions including a blend with 3, R 1 and R 2 These are independent organic groups containing 1 to 31 carbon atoms, each distinct from the others, and each contains at least one fluorinated group and a C=C bond, forming a C-Sn bond, and R F SnL1 3 contains at least about 1% of the total Sn atoms in the composition, L 1 and L 2 is an independently selected hydrolyzable ligand. The photoresist composition may contain an organic solvent, and the composition is R 1 SnL 1 3 and R 2 SnL 2 Includes blends with 3.

[0011] In a further embodiment, the present invention relates to formula R UF Regarding fluorinated organometallic compounds represented by SnL3, in the formula, R UF R is an organic group having 1 to 31 carbon atoms, with at least one carbon atom forming both a C=C bond and a CF bond. UF L forms a C-Sn bond, and L is a hydrolyzable ligand.

[0012] Furthermore, the present invention is R UF Regarding fluorinated organotin compositions containing -Sn bonds, UF R is an organic group having 1 to 31 carbon atoms, with at least one carbon atom forming both a C=C bond and a CF bond. UF -Sn bonds include C-Sn bonds. [Brief explanation of the drawing]

[0013] [Figure 1] The normalized FTIR peak area as a function of bake temperature for fluorinated and non-fluorinated organotin resists is plotted. [Modes for carrying out the invention]

[0014] Novel synthetic routes for organotin trialkoxide compositions provide effective synthetic routes for organotin compositions with organic ligands that are difficult to achieve compared to synthetic routes with good yield and efficient processing for the purposes of actual commercial materials. The ability to effectively form a wider range of compositions suitable for industrialization provides the ability to form blends of organotin patterning materials that can provide desirable specifications for coating patterning materials. In particular, ligands with a fluorine atom can provide improved absorption of radiation used for patterning, thereby improving the patterning results. At the same time, the fluorine atom can stabilize the carbon-tin bond, increasing the thermal stability of the ligand. Ligands with an intercarbon double bond may also exhibit greater radiation absorption. Particularly desirable ligands have both unsaturated intercarbon bonds with a fluorine atom in the same ligand, optionally containing the same carbon atom, and the synthesis of such compositions is exemplified. An effective synthetic method allows for the direct synthesis of trialkoxides, which are convenient precursors for coating formation. Alkoxide ligands are generally hydrolyzed during the formation of patterning materials on a substrate. In compositions formed from a blend of organic ligands, the material formed after solvent removal forms an integrated oxo-hydroxonetic network structure, where the distribution of tin atoms has corresponding organic ligands. Thus, patternable coatings can be designed to impart desired properties based on a selected blend of ligands. The availability of improved synthetic routes allows for the formation of materials having ligand mixtures that provide an overall desired balance of properties through the practical formation of desirable ligands that may be included in the blend accordingly.

[0015] Regarding precursor blends, fluorine atoms can be effective in providing thermal stability. CF bonds generally have stronger bond energies than CH bonds and can provide improved thermal stability compared to non-fluorinated precursors. Furthermore, fluorine generally exhibits increased EUV absorption with respect to the hydrogen atoms they substitute for. For example, intercarbon double bonds in alkenes and their derivatives can provide increased reactivity of ligands, leading to thermal instability. Therefore, the presence of CF bonds can improve the thermal stability of alkene-containing ligands. In organometallic materials formed following solvent removal, the collective effect of ligand properties becomes more complex because the material contains an interconnected oxo-hydroxonetic network structure.

[0016] The terms “organotin,” “hydrocarbyltin,” and “alkyltin,” as used herein and in accordance with their general use in the art, may be used interchangeably, and similarly, “monoalkyl” may be used interchangeably with “monoorganic” or “monohydrocarbyl.” “Alkyl” (i.e., “organic”) ligands suggest bonding to tin via a Sn-C bond, where the carbon is generally sp 3 or sp 2The hybrids form bonds that are generally not hydrolyzable upon contact with water. The "alkyl" group may optionally have internally unsaturated bonds, as well as heteroatoms that do not participate in the bonding with tin, i.e., atoms other than carbon and hydrogen. Chemical groups bonded to a metal atom are generally called ligands in the art. References to "hydrolyzable ligands" generally mean ligands bonded to Sn via hydrolyzable bonds, such as alkoxide ligands bonded to the oxygen atom with an organic substituent on oxygen, or amide ligands bonded to the nitrogen atom with one or more organic substituents on nitrogen. The synthetic methods described herein produce monoalkyltin trialkoxides and polyalkyltin (e.g., dialkyltin, trialkyltin) contaminants in high yield and low (non-tin) metal after simple purification. The synthetic approach to organometallic precursors is applicable to efficient scale-up for commercial production, the reactions are simple and straightforward, and can be carried out as one-pot synthesis.

[0017] For precursor synthesis, individual precursors are synthesized by appropriate and efficient synthesis protocols for specific organic ligands, and individual precursors can be blended if necessary. The applicant has developed several synthesis protocols that are generally effective and efficient in terms of cost, time, or other practical factors for specific ligands. Many synthesis procedures require the reactivity of halide reactants, and fluorine-containing ligands may tend to form undesirable byproducts, thus generally requiring purification of the desired product, resulting in low yields and inefficiency. The ability to form compositions with fluorine-containing ligands in an efficient process with reasonable yields has corresponding commercial importance.

[0018] Regarding fluorine-containing organic ligands, a synthetic protocol has been developed based on oxidative stannylation starting from Sn(II) alkoxides, and this method provides high selectivity and efficiency. The novel synthetic method involves the reaction of a Sn(II) alkoxide with a potassium alkoxide to form an intermediate bimetallic potassium tin(II) alkoxide composition or other similar alkali tin trialkoxide, followed by the reaction of the intermediate bimetallic composition with an alkyl halide to form a monoalkyltin trialkoxide composition. The method described herein can provide high selectivity and high yield and enables the preparation of monoalkyltin trialkoxide compositions without the need to carry out ligand exchange or conversion reactions, such as the conversion of monoalkyltin triamides to monoalkyltin trialkoxides. The reactions described herein can be useful for the preparation of monoalkyltin trialkoxides having primary or secondary Sn-C bonds. Further, the reactions described herein can be useful for the preparation of organotin compounds having fluorinated organic ligands, such as R F SnL3 compounds (where R F is an alkyl ligand substituted with one or more fluorine atoms). Due to the presence of fluorine within the alkyl ligand, the R F SnL3 compounds can be prepared by visible or ultraviolet light-induced reactions without using a metal-tin composition while still achieving high specificity for the monoalkyltin product.

[0019] Organotin compounds, particularly monoalkyltin trialkoxides and triamide compounds, have found applications as high-performance photoresists in EUV lithography. The use of alkyltin compounds in high-performance radiation-based patterning compositions is described, for example, in U.S. Patent No. 9,310,684, entitled "Organometallic Solution Based High Resolution Patterning Compositions" by Meyers et al., which is incorporated herein by reference. Improvements to these organometallic compositions for patterning are described in U.S. Patent No. 10,642,153, entitled "Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods" by Meyers et al., and in U.S. Patent No. 10,228,618, entitled "Organometallic Oxide Hydroxide Patterning Compositions, Precursors, and Patterning" by Meyers et al., both of which are incorporated herein by reference.

[0020] The compositions synthesized herein may be effective precursors for forming alkyltin oxo-hydroxo compositions, which are advantageous for high-resolution patterning in, for example, extreme ultraviolet (EUV), ultraviolet (UV), and electron beam lithography. The alkyltin precursor composition is a ligand that can be hydrolyzed with water or other suitable reagents under appropriate conditions to form a monoalkyltin oxo-hydroxo patterning composition, and when completely hydrolyzed, it is a ligand of the formula RSnO (1.5-(x / 2)) (OH) xIt contains a ligand represented by (0 < x ≦ 3). For example, it may be convenient to perform in situ hydrolysis to form an oxo-hydroxo composition, such as during deposition and / or after the formation of the first coating. For example, the alkyltin triamides and alkyltin triacetylides described in the '618 patent referenced above can be used under hydrolysis conditions for the formation of a radiation-sensitive coating for patterning, and it is desirable to use an alkyltin trialkoxide as part of the thin film forming composition. The direct synthesis of alkyltin trialkoxides is described herein.

[0021] Monoalkyltin compositions can generally be represented by the formula RSnL3, where R is an organic group (i.e., a ligand) and L is a hydrolyzable ligand. With respect to the process of forming a radiation-patternable coating, L is generally hydrolyzed before, during, or immediately after deposition (e.g., in situ), resulting in a coating containing a polymeric organotin oxo-hydroxo composition on the substrate, and the Sn-R bond remains substantially intact. As a result, a radiation-patternable coating having radiation-sensitive Sn-R bonds can be realized. When hydrolysis is completed on the substrate surface, the composition can be regarded as an integrated material, and the tin atoms are distributed within an oxo-hydroxo network structure that connects the materials. To form a radiation-patternable coating from a blend of different monoalkyltin compositions, a similar oxo-hydroxo network structure is realized, and tin atoms with different R groups are distributed throughout the oxo-hydroxo network structure, forming an integrated material. In this context, the reorganization free energy and other collective effects can influence the individual reactivity.

[0022] The synthesis described herein offers a broad selection of R groups having heteroatoms (one or more) that can confer improved thermal stability and / or photosensitivity compared to R groups having unsubstituted alkyl groups, and is advantageous for the efficient formation of R-Sn bonds. Although not bound by theory, the presence of R ligands is generally considered to give the as-deposited film solubility by preventing the formation of an expanded network structure and the condensation of the organotin film. Irradiation of the material may result in the cleavage of Sn-C bonds and the release of stabilizing R ligands, thereby enabling the formation of a network structure and condensation of the irradiated area, and subsequent processing may further condense and / or densify the film. These synthesis techniques are further described in the pending U.S. Patent Application 18 / 525,244 (hereinafter referred to as the '244 application) by Jilek et al., titled "Direct Synthesis of OrganoTin Alkoxides," which is incorporated herein by reference.

[0023] At the stage of radiation patterning, hydrolyzable ligands are generally substantially removed from the precursor composition to form the final patterning composition. Generally, the formula RzSnO( 2-z / 2-x / 2 )(OH) x(Where 0 < x < 3, 0 < z ≤ 2, x + z ≤ 4, and R is a hydrocarbyl or organic ligand that forms a carbon bond with a tin atom), an organometallic radiation-sensitive resist based on an organotin composition such as an alkyltin oxide hydroxide has been developed. A particularly effective form of these compositions is mono-organotin oxide hydroxide, where z = 1 or approximately = 1 in the above formula, and the mono-organotin composition is the focus herein. In particular, R can be an alkyl ligand having 1 to 31 carbon atoms, and one or more carbon atoms are optionally substituted with one or more heteroatom functional groups, such as O, N, Si, Ge, Sn, Te, and / or halogen atoms, or a cycloalkyl further functionalized with an alkyl, or phenyl, or cyano group. In some embodiments, R can contain 10 or fewer carbon atoms and can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, t-amyl, propenyl, butenyl, pentenyl, or an isomer thereof. The R group can be a linear, branched (i.e., secondary or tertiary at the metal-bonded carbon atom), or cyclic hydrocarbyl group. Each R group is independently and generally has 1 to 31 carbon atoms, 3 to 31 carbon atoms for a group having a secondary-bonded carbon atom, and 4 to 31 carbon atoms for a group having a tertiary-bonded carbon atom, and optionally has an unsaturated or aromatic carbon bond. A group having an unsaturated carbon bond and no heteroatoms is C n H 2(n-1)+3The total stoichiometry of branched or linear groups (wherein n=1 to 31) can be described. In particular, branched alkyl (unsaturated) ligands are desirable for some patterning compositions. The formation of the oxo-hydroxo coating material may involve the deposition of one or more tin compositions having hydrolyzable bonds, such as RSnL3 (wherein L is a hydrolyzable ligand, alkoxide, dialkylamine, acetylide, or other suitable hydrolyzable ligand). During and / or in the coating deposition, the hydrolyzable ligand may be hydrolyzed to form an oxo-hydroxo network structure, i.e., hydrolysis is completed after deposition. The applicant has developed a methodology for efficiently and curably forming a wide range of turning compositions having different R groups, which optionally have various heteroatoms along with C-Sn bonds, as further described in U.S. Patent Application Publication No. 2022 / 00064192 by Edson et al., entitled "Methods to Produce Organotin Compositions With Conveninent Ligand Providing Reactants," which is incorporated herein by reference.

[0024] The processing of organotin compositions to obtain organotin oxo-hydroxo coatings (i.e., films) generally requires the hydrolysis of the RSnL3 composition to obtain the relevant organotin oxo-hydroxo composition. Hydrolysis is performed before the deposition process to obtain soluble organotin oxo-hydroxo species (i.e., clusters, oligomer species, etc.). These soluble organotin oxo-hydroxo species are then dissolved and / or dispersed in a suitable solvent to form an organotin photoresist solution, which can then be used to form a radiation-patternable organotin oxo-hydroxo coating. Alternatively, the organotin composition can be directly dissolved in a suitable solvent to form a photoresist solution, which can then be used to form a radiation-patternable organotin oxo-hydroxo coating. The use of precursors with hydrolyzable ligands has proven effective in obtaining solutions with excellent shelf life and desirable coating properties. The organotin composition can also be hydrolyzed in situ with water during the substrate coating process, for example, during solution deposition or vapor deposition. Various processing options are further described in the '684 and '618 patents referenced above.

[0025] With respect to organotin photoresist compositions in which organotin compounds are dissolved in a solvent for spin coating, organotin trialkoxide (RSnL3, L=OR') is preferred to use over other RSnL3 compositions (e.g., organotintriamide, L=NR'2). Some advantages of organotin trialkoxide compositions include, for example, the production of more beneficient byproducts, such as alcohols, which are relatively harmless compared to the production of gaseous products (e.g., amines) that can cause contamination, environmental, sanitation, and safety (EHS) concerns, and similar concerns within wafer tracks and / or wafer manufacturing facilities. Organotin trialkoxide also possesses a considerable vapor pressure and low melting point, making it an attractive compound for use in vapor deposition methods to produce radiation-patternable coatings. In any case, the selection of an RSnL3 compound suitable for forming a radiation-patternable coating may be given by desired processing conditions to result in the formation of a desired radiation-patternable organotin oxohydroxo coating, such that the Sn-L bond is at least substantially cleaved and the Sn-R bond is at least substantially preserved before irradiation for patterning.

[0026] The synthesis of organotin trialalkoxide compounds has been previously described in the applicant's earlier patent applications. However, these reactions, which yield monoalkyltin trialalkoxides as products, generally require the conversion of alkyltin compounds to alkyltin alkoxides rather than direct synthesis. In other words, organotin trialalkoxides are generally synthesized by ligand substitution reactions. For example, organotin trialalkoxides are synthesized by the following reaction: RSnCl3+3MOR'→RSn(OR')3+3MCl Accordingly, it can be produced from the corresponding organotin trichloride by reaction with alkali metal alkoxides, such as KOR', NaOR', etc.

[0027] Therefore, the space of potential products of organotin trialkoxides is limited by access to the corresponding organotin trichlorides and their purity. Organotin trichlorides are generally synthesized by the known Kocheskov reaction, in which tetraalkyltin, R4Sn, serves as a starting material for the synthesis of other organotin halides produced by a redistribution reaction with SnCl4. This reaction is known to be non-selective and highly sensitive to stoichiometry, and generally results in some distribution of off-target and unwanted R n SnCl 4-n products. For example, to synthesize RSnCl3, a mixture of SnCl4 and R4Sn is reacted in a 3:1 ratio to target RSnCl3 as the main product, but the reaction produces significant amounts of R2SnCl2 and R3SnCl as by-products. In semiconductor applications where high purity compounds are required for low defect processing and commercial viability, one or more purification steps may be required to further purify and / or isolate the RSnCl3 compound prior to its conversion to the trialkoxide, and the purification itself is difficult. The synthesis methods described herein reduce the need for high purity organotin trichloride starting materials in the synthesis of organotin trialkoxides.

[0028] Other methods of preparing organotin trialkoxides involve the conversion of organotin triamides to organotin trialkoxides via the following reaction: RSn(NR2’’)3 + 3HOR’ → RSn(OR’)3 + 3HNR’’2 are required. Although this reaction is relatively simple, it is limited by factors such as its exothermic nature, which can potentially lead to the decomposition of reactants and / or products, and its high cost, as it requires the initial synthesis of the corresponding organotin triamide. While the applicant has described synthetic techniques for preparing a wide range of organotin triamides, there is still a need for the development of a method for directly synthesizing organotin trialalkoxides without first obtaining organotin starting materials with the desired R ligand identity. The direct synthesis of the target organotin trialalkoxide, RSn(OR')3, is desired and described herein.

[0029] To perform high-resolution radiation-based patterning, it is generally desirable to have good radiation absorption, a resist chemistry that provides high contrast, and thermal stability that avoids the decomposition of organic ligands unrelated to irradiation. Thermal stability tends to track by requiring a large radiation dose to cleave organic ligands, but increased radiation absorption can increase the efficiency of the irradiation that needs to be compensated for.

[0030] Due to their high EUV absorption, fluorine atoms are desirable to replace H atoms in the R ligand. Furthermore, the presence of F atoms in the R ligand can increase the ligand's hydrophobicity, thus improving the development contrast between the irradiated and unirradiated regions of the film. Although patterning results are not shown in this application, organic ligands having fluorine substituents and trifluoromethyl groups are exemplified in the aforementioned '244 application.' Unsaturated alkenyl ligands generally have lower thermal stability than their corresponding saturated alkyl ligands, and the reactivity of the alkene group can lead to undesirable, non-radiation-induced changes in solubility of the unexposed regions of the film, such as ligand cleavage or other undesirable side reactions. Ligand fluorination can improve the thermal stability of organotin compounds while simultaneously improving their EUV absorbance, thus achieving improved thermal stability and dose sensitivity. Radiolysis occurs in the irradiated region, and the Sn-C bond is cleaved, resulting in a loss of stability for the formation of the expanded reticular structure. The tin oxohydroxo reticular structure within the irradiated region can further densify and compress, potentially forming insoluble exposure products. Due to the high thermal stability of the fluorinated ligand, the patterned coating is heated to high temperatures, further promoting densification of the irradiated material without simultaneously decomposing the unexposed organotin material. Thus, the contrast between the irradiated and unirradiated regions can be enhanced. Therefore, by including both fluorine-substituted ligands and ligands with alkene groups, a particularly desirable improvement in patterning properties can be obtained.

[0031] Direct synthesis of organotin trialalkoxides: Based on recently developed methods, monoalkyltin trialalkoxides can be synthesized by one of two related synthetic methods. Both methods involve reacting an organic halide, such as an alkyl halide (RX), with a tin alkoxide compound to form a Sn-R bond. The tin alkoxide may be a di-tin tetraalkoxide (Sn2(OR')4) or an alkali metal tin alkoxide, e.g., MSn(OR')3. In the first approach, a di-tin tetraalkoxide is reacted with an organic halide, generally in the presence of UV or monochromatic visible light, to form a monoalkyltin trialalkoxide, RSn(OR')3. In the second approach, an alkali metal tin trialalkoxide is reacted with an organic halide, optionally using a catalyst, to form a corresponding organic tin trialalkoxide with less tin contamination.

[0032] Di-tin tetraalkoxides (Sn2(OR')4) and alkali metal tin alkoxides (MSn(OR')3) can be prepared using known methods in the literature, for example, Veith et al. (hereinafter, Veith's paper), titled "Alkoxistannate, II Tri(rerr-butoxi)alkalistannates(II): Synthesis and Structures," Z.Naturforsch.41b,1071-1080 (1986), which is incorporated herein by reference. Veith's paper does not propose specific reactions using Sn2(OR')4 or MSn(OtBu)3 as further reactants to form alkyl tin trialalkoxides, such as RSn(OtBu)3. Veith's paper discloses the synthesis of MSn(OtBu)3 using Sn2(OtBu)4. Veith also shows its structure. As illustrated herein, MSn(OtBu)3 is formed using SnCl 2 It is synthesized from M(OtBu) in a two-step reaction. After the first step, precipitated MCl(KCl) is removed, but further purification is not necessary.

[0033] In the first approach, the synthesis of monoorganotin trialalkoxides involves the following total reactions: MSn(OR')3+RX→RSn(OR')3 Based on, In the formula, M is generally an alkali metal such as Li, K, Na, Cs, or Rb, and X is a halide ion, Cl, Br, or I. R' is generally an alkyl group having 10 or fewer carbon atoms, and OR' can generally be selected for desirable properties of the monoalkyltin trialkoxide product, RSn(OR')3, such as stability, melting point, solubility, and ease of purification. In some embodiments, OR' is t-butoxide (OtBu). In some embodiments, OR' is t-amyl oxide (OtAm). The RX compound is selected to provide the desired alkyl ligand, R, to the monoorganotin product. The broad availability of the reactants, as well as the broad reactivity of the compounds in the corresponding reactions, provides the ability to introduce a wide range of alkyl ligands to the monoalkyltin product. For the reactions described herein, primary and secondary R groups (i.e., R groups having 1 or 2 carbon atoms forming a C-Sn bond) may be particularly effective in forming the desired RSn(OR')3 composition. R ligands having unsaturated carbon bonds can also be prepared as shown in the examples herein. X is generally a halide selected from I, Br, or Cl. It is desirable that a catalyst be present during the reaction to form the monoalkyltin trialkoxide. Some suitable examples of catalysts are tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, and tetraphenylphosphonium chloride.

[0034] The alkali tin alkoxide intermediate, MSn(OR')3, and Sn(II) bimetallic alkoxide have been found to be useful reagents for the formation of organotin trialkoxides, as shown in the following reaction: Sn(OR')2+MOR'→MSn(OR')3 It can be prepared according to the following. The alkali metal M can generally be selected from Li, Na, K, Cs, or Rb. In some embodiments, M is K. In some embodiments, M is Li or Na. MSn(OR')3 compounds can be isolated, purified, and used as solid reagents in synthesis, and their preparation is included in the examples herein. These compositions based on five well-known alkali metals have been studied and characterized in the above-mentioned paper by Veith. When reacted with alkyl halides at moderate temperatures and conditions, an oxidative addition reaction may occur, where an alkyltin bond is formed along with the rapid formation of a potassium halide to form RSn(OR')3. The potassium halide salt can be removed by filtration as an alternative method, and / or the RSn(OR')3 product can be purified and recovered by distillation.

[0035] Regarding some R groups, such as fluorinated organic groups, the corresponding R F Sn(OR')3 composition reacts as follows: [Sn(OR')2]2+R F XR→ F Sn(OR')3+1 / 2 Sn2X2(OR')2 Accordingly, it has been discovered that it can be synthesized directly from Sn(OR)2 ([Sn(OR')2]2) without using alkali tin alkoxide compositions, that is, in the presence of light such as visible light or ultraviolet light.

[0036] [Sn(OR')2]2 is characterized. See Fjeldberg et al., Chemistry of bulky alkoxides of bivalent germanium and tin; structures of gaseous [Sn(OBu)2]2 and crystalline Ge(OCBu)2, Journal of the Chemical Society, Chemical Communications, Issue 14, 1985, 939-941 (hereafter, Fjeldberg), which is incorporated herein by reference. As described herein, MOR' such as KOtBu and SnCl 2A new synthetic route using the reaction is described.

[0037] In the examples herein, fluorinated alkyl tin trialalkoxide (R F = Trifluoroethyl (TFE,CF3CH2-), or R F The synthesis of 3,4,4-trifluorobuto-4-enyl (FBEN, CF2=CFCH2CH2, R'=t-butyl) is described. Although we do not wish to be constrained by theory, the reaction with fluorinated alkyl groups is thought to require a radical mechanism. The presence of fluorine substituents is thought to provide UV activation, and notably, the reaction is selective for tin monoalkylation and can be carried out under UV irradiation without the presence of bimetallic tin(II) alkoxide. This reaction yields a tin byproduct, SnX2(OR')2 as a solid, which can be removed by filtration or simple methods.

[0038] The reaction is generally carried out in anhydrous organic solvents under an oxygen-free or oxygen-deficient atmosphere, such as a nitrogen-purged atmosphere. The solvent may be selected to produce solubility for various components appropriate for the particular reaction. Due to the interaction between the solvent and metal ions, the selection of the solvent may be based at least in part on the reaction rate in the selected solvent, which is evaluated empirically. When different solvents are selected, they are generally miscible. Non-protic polar solvents such as ethers (e.g., dimethyl ether, diethyl ether), tetrahydrofuran (THF), acetone, and mixtures thereof are generally useful. For alkylation steps in which alkyl groups are bonded to tin, non-polar solvents such as alkanes (e.g., hexane, pentane) and toluene have also proven effective. The solvent should generally be selected to be inert to the reactants, intermediates, and products. When multiple solvents are used to introduce separate reactants, the solvents should generally be miscible with each other.

[0039] Halide-containing catalysts may be present in the reaction of bimetallic MSn(OR')3 compounds and alkylhalide RX compounds. These catalysts may generally include quaternary ammonium salts such as tetrabutylammonium iodide, tetrabutylammonium bromide, and / or tetrabutylammonium hexafluorophosphate, and / or tetraphenylphosphonium chloride. While the roles of these catalysts are not entirely clear, they are known to act as phase-transfer catalysts by assisting the dissolution of inorganic compounds in organic solvents. Other phase-transfer catalysts, based on their usual chemical properties, should be equally useful in this context, whether or not their function is directly utilized herein.

[0040] Reactions using MSn(OR')3 as a starting material can generally be carried out in a one-pot reaction without intermediate steps such as separation, purification, or introduction.

[0041] The reactions described herein are highly selective for the formation of monoalkyltin trialkoxide compounds, and alkylhalides can generally be present as reactants in molar excess amounts of MSn(OR')3 compositions. In some embodiments, alkylhalides may be present in amounts up to about 2 molar equivalents relative to the MSn(OR')3 compound, in other embodiments up to about 1.6 molar equivalents relative to the MSn(OR')3 compound, in yet another embodiment up to about 1.3 molar equivalents relative to the MSn(OR')3 compound, and in a further embodiment up to about 1.1 molar equivalents relative to the MSn(OR')3 compound. In some embodiments, alkylhalides and the MSn(OR')3 compound may be present in approximately theoretical amounts. Those skilled in the art will recognize that an additional range of reactant molar equivalents within the above defined ranges is intended and is within this disclosure.

[0042] In some embodiments, the reaction may be carried out at temperatures generally below about 100°C, below about 80°C in other embodiments, and below 60°C in further embodiments. In some embodiments, the reaction may be carried out at room temperature. Generally, the reaction may be carried out at temperatures of about -20 to about 100°C. In some embodiments, the reaction may be carried out under ultraviolet irradiation. In embodiments in which ultraviolet irradiation is carried out during the reaction, the reaction may or may not be heated. In some embodiments, ultraviolet irradiation may be carried out at a wavelength of 365 nm. In some embodiments, ultraviolet irradiation may be carried out at a wavelength of 254 nm, although other UV wavelengths are suitable. Generally, any reasonable light source may be selected, such as an LED (coherent or noncoherent), laser, plasma, lamp, or other suitable light source. The reaction is generally stirred for the duration of the reaction. To determine when the reaction has reached complete completion, 1 H and / or 119 The effectiveness of the reaction can be monitored by analyzing the reaction mixture using Sn NMR. In some embodiments, the reaction may be carried out for about 5 days or less, in other embodiments for about 3 days or less, in other embodiments for about 2 minutes to about 1 day, and in further embodiments for about 5 minutes to about 1 hour. Those skilled in the art will recognize that additional ranges of time and temperature within the above defined ranges are intended and within this disclosure. Desired reaction times and temperatures may generally vary depending on the identity of the alkyl halide (RX). The reactivity of alkyl halides generally follows the order of carbon atoms forming the CX bond as 1°>2°>>3° in the order X=I>Br>Cl. Appropriate reaction times and temperatures may be determined by conventional experimentation.

[0043] After the product has been formed, the organotin trialkoxide can be purified. Purification varies depending on the properties of the product, but generally requires separation of the desired product from by-products and, optionally, unreacted reagents. Purification can generally be achieved by methods known in the art. Suitable purification methods may include filtration, recrystallization, extraction, distillation, or a combination thereof. Filtration is usually performed on the crude product mixture to remove insoluble contaminants and / or by-products, such as metal halide salts like KI, from the solution containing the desired product. Recrystallization can be useful for purifying solid compounds by heating a saturated solution, which is then cooled. Extraction techniques may include, for example, liquid-liquid extraction using two miscible solvents of different concentrations, where the desired compound is separated based on its relative solubility. Purification may also include removing volatile compounds, such as solvents, from the product mixture by drying or exposure to vacuum. For products with considerable vapor pressure, purification is desirable by vacuum distillation or, if desired, by fractional distillation designed to achieve high purity. See U.S. Patent Application Publication No. 2020 / 0241413 by Clark et al., entitled "Monoalkyl Tin Trialkoxides and / or Monoalkyl Tin Triamides With Low Metal Contamination and / or Particulate Contamination and Corresponding Methods," which is incorporated herein by reference. The products may also be reacted to form derivatives such as organotin compounds having other hydrolyzable ligands (e.g., organotin triamides, organotin triacetides, organotin acetamides, or organotin carboxylates) or organotin clusters, which can be further purified by the above-described techniques or by means known in the art.

[0044] Formation of precursor compositions, coatings, and patternable materials The direct synthesis process of monoorganotin trialalkoxides is described in the following sections and may be effective in forming a range of precursor compositions. These precursors can then be used alone or in blends to form coatings useful for radiation-based patterning. Whether in a blend of precursors having different organic ligands or using a single type of precursor composition having a selected organic ligand, the precursors can provide fluorine and alkene groups. For solution coating, one or more monoorganotin trialalkoxides can be mixed in a common solvent along with a solvent for delivery to the substrate surface. For vapor delivery, the precursors can be evaporated and delivered to a deposition chamber to form a coating on the substrate; however, for blended coating compositions, it is preferable to deliver the precursors as separate vapors, as this may achieve greater control over the deposition process by using separate vapor delivery of precursors having different organic ligands or hydrolyzable ligands.

[0045] To ensure the material is stable during lithography before irradiation and development, it is generally desirable for photoresists to have high thermal stability. Thermal processes typically involve various steps during the lithography process. For example, post-application baking (PAB) is usually performed after the formation of the photoresist film to aid in solvent evaporation and stabilize the film for further processing. Similarly, post-exposure baking (PEB) is usually performed after radiation exposure of the photoresist film to accelerate the reaction in the exposed areas and increase the solubility contrast between the exposed and unexposed areas of the photoresist. Since the irradiated material is thermally responsive, the unirradiated material should be stable at the PEB temperature to avoid contrast loss if a significant amount of ligand is lost during non-radioactive processes. Therefore, it is desirable for organotin photoresists to withstand high temperatures without significant decomposition, such as unwanted destruction of Sn-C bonds.

[0046] The photosensitivity of organotin photoresists generally requires radiation-induced cleavage of Sn-C bonds. Sn-C bonds within the photoresist material generally prevent complete oxide-hydroxyl condensation of the photoresist film. Similarly, the presence of organic groups bonded to Sn atoms via Sn-C bonds generally confers hydrophobicity to unexposed organotin photoresist materials. Therefore, unexposed organotin photoresists are generally soluble in organic solvents. Exposure to radiation can cleave Sn-C bonds, reducing the hydrophobicity of the exposed material and allowing condensation of the exposed material through the formation of Sn-O-Sn and Sn-OH bonds. Thus, patterning of organotin resists can be achieved by selective decomposition of radiation-sensitive Sn-C bonds, followed by development based on differential chemistry in the irradiated and unirradiated regions.

[0047] While we do not wish to be constrained by theory, the thermal stability of Sn-C bonds may correlate with the bond dissociation energy of the Sn-C bond. For example, Sn-C bonds of organic ligands having secondary and tertiary α-carbons (i.e., carbons directly bonded to the Sn atom) generally require less energy to cleave than Sn-C bonds having primary α-carbons. In other examples, functionalized organic ligands, such as ligands containing unsaturated carbon-carbon bonds or heteroatoms, can also lower the bond dissociation energy of the Sn-C bond and improve the radiation sensitivity of organotin resists. Generally, it is desirable that the Sn-C bonds of organic ligands in organotin photoresists be easily cleaved by appropriate radiation so that high exposure levels are not required to impart changes in the solubility of the material. On the other hand, organic ligands that form Sn-C bonds with low bond dissociation energy also generally have low thermal stability, and therefore, heating during lithography can induce Sn-C cleavage in non-irradiated areas, thereby reducing contrast and decreasing patterning performance. Thus, it is desirable to increase radiation absorption by adjusting the material without reducing thermal stability. The materials and blends described herein possess improved thermal stability, and therefore, at higher processing temperatures, it may be possible to densify the irradiated area of ​​the photoresist without significantly decomposing the Sn-C bonds in the unexposed areas. In this way, the reduction in the amount of thermally induced Sn-C bond cleavage results in a lack of radiation absorption, and the increase in radiation absorption is expected to promote Sn-C bond cleavage at relatively low exposure levels. As a result of this combination of features, contrast may be improved. The blend of R ligands allows for adjustment, and these trade-offs have been found to be very useful.

[0048] Fluorination and use of alkenyl moieties within ligands of organotin resists can enhance the thermal stability and dose sensitivity of the photoresist. These include fluorine or fluorine-containing groups within the R group, such as electron-withdrawing groups like CF3. In some embodiments, fluorine functional groups bonded to olefinic carbons can also stabilize alkene C=C bonds, reducing the reactivity of the ligand in the absence of radiation. Fluorinated ligands also improve the radiation sensitivity of the photoresist compared to unfluorinated ligands because fluorinated atoms have higher absorbance of extreme ultraviolet (EUV) radiation. The combinations of fluorinated and alkenyl groups within one or more ligands described herein can exhibit improved radiation sensitivity and enhanced thermal stability. In appropriate balance, these can improve contrast.

[0049] In some embodiments, the fluorinated R ligand may contain 1 to 15 carbon atoms, 2 to 10 carbon atoms in further embodiments, and 3 to 7 carbon atoms in other embodiments, and may have one, two, or more -CF3 groups, such as the trifluoroethyl (TFE) compounds described in the examples herein. In some embodiments, the R ligand has CF bonds, for example The present invention may include a tertiary carbon having -CFR'R'' (where R' and R'' are independently organic groups having 1 to 10 hydrogen atoms or carbon atoms), or a secondary carbon having a CF bond, for example, -CF2R' (where R' is an organic group having 1 to 10 carbon atoms). In other embodiments, the alkyenyl group may be a fluorinated alkyenyl group.

[0050] In some embodiments, the fluorinated alkenyl ligand is of formula: [ka] It may contain compounds represented by, In the above formula, R1, R2, and R3 are independently H, F, or an organic group having 1 to 8 carbon atoms, for example CF3 or CH3, and at least one of R1, R2, or R3 is fluorinated, for example F or CF3, and R4 is a bond or a linear, cyclic, or branched alkyl group having 1 to 10 carbon atoms, and L is a hydrolyzable ligand. In some embodiments, R 1 , R 2 R1, R2, and R3 are all F. In some embodiments, R1, R2, and R3 are all CF3. In some embodiments, R4 is -CH2-. The hydrolyzable ligand L may be any ligand having a hydrolyzable bond to Sn, e.g., an alkoxide (OR'), an amide (NR'2), an acetylide (CCR'), or a chloride. Generally, the identity of L may be selected to facilitate the formation of the associated organotin oxide hydroxide film and to ensure proper realization of the deposition process. For example, alkoxides and amides are preferred for use in deposition methods in which rapid hydrolysis occurs during deposition, such as spin coating or vapor deposition.

[0051] Organotin compounds having a fluorinated alkenyl ligand on the same or different ligands can be blended into an organotin photoresist solution containing one or more different organotin compounds. By blending two or more different organotin compounds, a photoresist with improved stability and / or patterning performance can be formed compared to a single-component photoresist composition. Fluorinated alkenyl ligands can improve the photosensitivity of the blended composition compared to non-fluorinated alkenyl ligands, while also providing improved thermal stability. Fluorinated alkenyl ligands can also impart hydrophobicity to the unexposed photoresist material, which can aid in the development process where the unexposed material is removed by an organic solvent.

[0052] Regarding ligand blends, improved photosensitive precursor compositions include one or more organotin compositions, for example, R n SnL 4-nand may be present in the blend solution together with its hydrolysis products, where R is selected from various sites detailed herein and clearly described above. Generally, the desired ligand is a monoorganic in the above formula where n=1. The blend solution is (a 1 R 1 SnL 1 3, a 2 R 2 SnL 2 3, ...a m R m SnL m 3) It can be considered that, for the blend, m≧2, e.g., 2, 3, 4, 5 or more. Hydrolyzable ligand L mThese can be individually selected, and they are generally substantially or completely hydrolyzed before patterning so that they are identical, or they can be selected based on any other practical considerations relating to effective and efficient precursor processing. Such blended solutions can be adjusted to optimize various performance elements such as solution stability, coating uniformity, and patterning performance. In some embodiments, the improved photosensitive composition may contain at least about 1 mol% of the desired component Sn in the blended solution, at least about 5 mol% in further embodiments, at least about 10 mol% of Sn relative to the blended solution in some embodiments, and about 20 to about 50 mol% of Sn relative to the blended solution in further embodiments. In a blend of two precursors, the second precursor has a corresponding concentration in the solution, for example, 99% paired with 1% of the other composition. If three or more components are present, they can be blended in reasonable combinations based on the parameters described above, so that, for example, one precursor may be dominant with two or more minor components, but all precursors may be the same or differ by relatively small proportions, such as factor 2, in non-majority amounts, or two or more may be present in larger amounts in approximately the same order, along with minor amounts of one or more additional precursors. Sn of the specific desired component of the blended solution. Those skilled in the art will recognize that an additional range of mol% of an improved photosensitive composition within a clear range of the blended solution is intended and falls within the scope of this disclosure. The hydrolyzable ligand L can be hydrolyzed, for example, by hydrolysis with steam during or following deposition.

[0053] Naturally, in some embodiments, the entire precursor is a single ligand R having a fluorine atom and an alkene group. AF It may include. Regarding the blend, R AF1 A precursor containing a ligand is used by other R AF2 Ligand, R A Ligand, R F Ligand or R N It can be combined with a ligand, R AF2 R AF1It is a ligand containing an alkene group and a fluorine atom having a different structure from R A R is a ligand containing an alkene group. F R is a ligand containing one or more fluorine atoms. N It does not contain alkenyl or fluorine functional groups, R AF2 , R A , R F and R N Each of these can independently optionally have heteroatoms and / or aromatic groups. As described above, these organic ligands are RSnL m It is found in three forms of composition. As further described below, when these are in a dissolved state, hydrolyzable ligands may be exchanged or partially exchanged, but R ligands are generally not considered to be exchanged. For gas-phase deposition, the precursors are generally neat liquids, and the compounds are generally maintained in a purified state due to the absence of solvents. For gas-phase deposition of precursor blends, the precursors may be delivered in the same proportions as described with respect to the precursor solution. For gas-phase deposition as solution-based deposition, a final film containing a mixture of RSn species may be formed using two or more separate RSnL3 compounds having different R and / or L ligands. Generally, in the final film, any of the separate RSn species are considered to be randomly distributed throughout the film in an interconnected oxo-hydroxo-network structure, which may or may not apply to sequential gas-phase deposition. Oxygen atoms may form crosslinkable oxygen ligands upon hydrolysis. Within the aggregated network structure, separate R ligands may influence the collective behavior of the film.

[0054] Whether deposited by liquid-phase deposition or gas-phase deposition, when hydrolyzable ligands are hydrolyzed, RSnO x OH 3-2xAn oxo-hydroxo-reticulate structure can be formed represented by (where R may be one or a blend of the aforementioned organic ligands). Generally, radiation exposure and patterning are carried out on hydrolyzed coatings. It is thought that cleavage of the RSn sites allows for condensation of the material and further enables the accumulation of the oxo-hydroxo-reticulate structure.

[0055] The substrate generally refers to the surface on which the coating material is deposited, and it may include multiple layers, with the uppermost layer being the surface of the substrate. The substrate is not particularly limited and may include any suitable material such as silicon, silica, other inorganic materials, e.g., ceramics and polymer materials. The coating process and patterning will be described below.

[0056] Coatings, deposits, and related compositions: The organotin precursor compositions described herein can be effectively used in radiation patterning, particularly EUV patterning. Their greater flexibility in ligand selection allows for further improvements in patterning results and ligand design, making them particularly effective for specific applications. Generally, the precursor solution can be delivered to a substrate using any suitable coating process. Suitable coating approaches include, for example, liquid-phase deposition techniques such as spin coating, spray coating, dipping, and knife-edge coating, as well as printing techniques such as inkjet printing and screen printing. Many of the precursors are also suitable for vapor-phase deposition on substrates as considered in the above-mentioned '618 patent. For some R-ligand compositions and / or specific process considerations, vapor-phase deposition may be useful for the production of radiation-sensitive coatings.

[0057] After the preparation of the desired organotin precursor, the precursor can be dissolved in a suitable solvent to prepare a precursor solution, such as an organic solvent, e.g., alcohol, aromatic and aliphatic hydrocarbons, esters, or combinations thereof. Particularly suitable solvents include, for example, aromatic compounds (e.g., xylene, toluene), ethers (anisole, tetrahydrofuran), esters (propylene glycol acetate monomethyl ether, ethyl acetate, ethyl lactate), alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ketones (e.g., methyl ethyl ketone), and mixtures thereof. Generally, the selection of an organic solvent may be influenced by its solubility parameters, volatility, flammability, toxicity, viscosity, and potential chemical interactions with other processing materials. After the components of the solution are dissolved and combined, the properties of the species may change as a result of in-situ partial hydrolysis, hydration, and / or condensation.

[0058] An organotin precursor can be dissolved in a solvent at a concentration that yields a suitable concentration of Sn for forming a coating of a suitable thickness for processing. The concentration of the species in the precursor solution can be selected to achieve the desired physical properties of the solution, in particular, lower overall concentrations yield desirable properties of the solution for certain coating approaches such as spin coating, and enable the achievement of thinner coatings with reasonable coating parameters. It is desirable to obtain ultrafine patterning using thinner coatings and to reduce the cost of materials. Generally, the concentration can be selected to suit the coating of choice. Coating properties are described further below. Generally, the tin concentration includes about 0.005 M to about 1.4 M, about 0.02 M to about 1.2 M in further embodiments, and about 0.1 M to about 1.0 M in additional embodiments. Those skilled in the art will recognize that an additional range of tin concentrations within the above distinct ranges is intended and is within this disclosure.

[0059] In some embodiments, the improved photosensitive precursor composition is R n SnL 4-nR may be present in a blend solution having one or more organotin compositions, such as and their hydrolysis products, where R is selected from various parts detailed herein and clearly described above. Such a blend solution can be adjusted to optimize various performance characteristics, such as solution stability, coating uniformity, and patterning performance. In some embodiments, the improved photosensitive composition may contain at least 1 mol% of the desired component Sn in the blend solution, in a further embodiment at least 10 mol% of Sn relative to the blend solution, in a further embodiment at least 20 mol% of Sn relative to the blend solution, and in a further embodiment at least 50 mol% of a specific desired component Sn relative to the blend solution. Further ranges of mol% of the improved photosensitive composition within a clear range of the blend solution are intended and are contained herein.

[0060] In general, due to their high vapor pressure, the organotin compositions described herein may be useful as precursors for the formation of coatings by vapor deposition. Common vapor deposition methods include chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), and modified forms thereof. In a typical vapor deposition process, the organotin composition can be reacted with small molecule vapor-phase reagents such as H2O, O2, H2O2, O3, CH3OH, HCOOH, and CH3COOH, which serve as O and H sources for the production of radiosensitive organotin oxides and oxide-hydroxyl coatings. Water vapor may be supplied from ambient air, delivered in vapor form, or provided in a suitable liquid or vapor composition. The vapor precursor may be delivered from a separate reservoir, and upon deposition and hydrolysis, the R ligand may be distributed within the resulting oxo-hydroxo-network structure. The distribution may be uniform or non-uniform depending on the vapor deposition strategy. A specific apparatus for vapor deposition of radiation-patternable organotin coatings is described by Wu et al. in PCT application number PCT / US2019 / 031618, entitled "Methods for Making EUVP atternable Hard Masks," which is incorporated herein by reference. The formation of radiation-sensitive organotin coatings can generally be achieved by reacting a volatile organotin precursor RSnL3 with small gas-phase molecules. The reaction may involve hydrolysis / condensation of the organotin precursor, which hydrolyzes the hydrolyzable ligand while leaving the Sn-C bond substantially intact.

[0061] In a typical radiation-based patterning process, such as extreme ultraviolet (EUV) lithography, a photoresist material is deposited or coated as a thin film on a substrate, baked before exposure, exposed using a radiation pattern to form a latent image, baked after exposure, and then developed using a vapor-based process or a liquid, usually an organic solvent, to produce a developed pattern of the resist. If desired, fewer steps can be used, and additional steps can be used to remove residues and improve pattern fidelity.

[0062] The selected thickness of the radiation-patternable coating may vary depending on the desired process. For use in single-patterning EUV lithography, the coating thickness is generally selected to form a pattern with low defect and fidelity of patterning. In some embodiments, suitable coating thicknesses may be 1 nm to 100 nm, in further embodiments about 2 nm to 50 nm, and in even further embodiments about 3 nm to 25 nm. It will be understood by those skilled in the art that an additional range of coating thicknesses within the above defined ranges is intended and is contained within this disclosure.

[0063] The coating thickness of radiation-patternable coatings prepared by vapor deposition techniques can generally be controlled by the appropriate selection of reaction time or process cycle. The thickness of radiation-patternable coatings may vary depending on the desired process. For use in single-patterning EUV lithography, the coating thickness is generally selected to form a pattern with low defect and fidelity of the patterning. In some embodiments, suitable coating thicknesses may be 1 nm to 100 nm, in further embodiments about 2 nm to 50 nm, and in even further embodiments about 3 nm to 25 nm. It will be understood by those skilled in the art that an additional range of coating thicknesses within the above defined ranges is intended and is contained within this disclosure.

[0064] A substrate generally represents a surface on which a coating material is deposited, and it may comprise multiple layers, with the uppermost layer being the surface. After deposition and formation of a radiation-patternable coating, further treatment may be used before exposure to radiation. In some embodiments, the coating may be heated to 30°C to 300°C, in further embodiments to 50°C to 200°C, and in further embodiments to 80°C to 150°C. Heating may be carried out for about 10 seconds to about 10 minutes in some embodiments, about 30 seconds to about 5 minutes in further embodiments, and in further embodiments to about 45 seconds to about 2 minutes. It will be understood by those skilled in the art that an additional range of temperatures and heating durations within the above defined ranges is intended and is contained within this disclosure.

[0065] Composition patterning: Radiation can generally be directed through a mask onto a coated substrate, or the radiation beam can be controlled and scanned across the substrate. Generally, the radiation can include electromagnetic radiation, electron beams (beta rays), or other suitable radiation. Generally, electromagnetic radiation can have a desired wavelength or range of wavelengths, such as visible light, ultraviolet light, or X-rays. The achievable resolution of the radiation pattern generally depends on the radiation wavelength; generally, shorter wavelengths of radiation result in higher resolution patterns. Therefore, it is desirable to use ultraviolet light, X-rays, or electron beams, especially to obtain high-resolution patterns.

[0066] According to the international standard ISO 21348 (2007), incorporated herein by reference, ultraviolet light extends to wavelengths from 100 nm to less than 40030 nm. A krypton fluoride laser can be used as a light source for 248 nm ultraviolet light. The ultraviolet range can be further divided in several ways under recognized standards, such as extreme ultraviolet (EUV) from 10 nm to less than 121 nm, and ultraviolet (FUV) from 122 nm to less than 200 nm. The 193 nm light from an argon fluoride laser can be used as a radiation source in FUV. 13.5 nm EUV light has been used for lithography, and this light is generated from a Xe or Sn plasma source excited using a high-energy laser or discharge pulse. Soft X-rays can be defined as wavelengths from 0.1 nm to less than 10 nm.

[0067] Depending on the design of the coating material, a significant contrast in material properties may exist between the irradiated area where the coating material is condensed and the unirradiated coating material having substantially intact Sn-C bonds. In embodiments where post-irradiation heating is used, the post-irradiation heating may be carried out at temperatures of about 45 to about 250°C, in additional embodiments about 50 to about 190°C, and in further embodiments about 60 to about 175°C. Post-exposure heating may generally be carried out for at least about 0.1 minutes, in further embodiments about 0.5 to about 30 minutes, and in additional embodiments about 0.75 to about 10 minutes. It will be recognized by those skilled in the art that an additional range of post-irradiation heating temperatures and times within the above defined ranges is intended and included in this disclosure. This high contrast in material properties further helps in the formation of high-resolution lines with smooth edges after development, as described in the following sections.

[0068] For negative development, the developer may be an organic solvent, such as the solvent used to form the precursor solution. Generally, the choice of developer is 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, alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, methanol), ethyl lactate, ethers (e.g., tetrahydrofuran, dioxane, anisole), and ketones (pentanone, hexanone, 2-heptanone, octanone). Development may be carried out for about 5 seconds to about 30 minutes, about 8 seconds to about 15 minutes in further embodiments, and about 10 seconds to about 10 minutes in additional embodiments. It will be recognized by those skilled in the art that an additional range within the clearly defined above is intended and is within this disclosure. In addition to the primary developer composition, the developer may include additional compositions to facilitate the development process. Suitable additives include, for example, viscosity modifiers, solubilizers, or other processing aids. Where any additive is present, the developer may contain the additive in an amount of about 10% by weight or less, and in further embodiments, about 5% by weight or less. It will be recognized by those skilled in the art that an additional range of additive concentrations within the above defined range is contemplated and included in this disclosure. A desirable developer composition is described in U.S. Patent Application Publication No. 2020 / 0326627 to Jiang, titled "Organometallic Photoresist Developer Compositions and Processing Methods," which is incorporated herein by reference.

[0069] When using weaker developers, such as diluted organic developers or compositions that develop coatings more slowly, the process speed can be increased by using a higher temperature development process. With stronger developers, the development process temperature can be lowered to reduce the development speed and / or control the development kinetics. Generally, the development temperature can be adjusted to a suitable value that matches the volatility of the solvent. Furthermore, developers that dissolve the coating material near the developer-coating interface can be dispersed using ultrasound during development. Additionally, developers with dissolved coating material near the developer-coating interface can be dispersed by ultrasound during development. The developer can be applied to the patterned coating material using any reasonable approach. For example, the developer can be sprayed onto the patterned coating material. Spin coating can also be used. In automated processes, a paddle method may be used, which involves pouring the developer onto the coating material in a stationary form. If desired, the development process can be completed using spin washing and / or drying. Suitable cleaning solutions include, for example, ultrapure water, aqueous solution of tetraalkylammonium hydroxide, methyl alcohol, ethyl alcohol, propyl alcohol, and combinations thereof. After the image is developed, the coating material is placed on the substrate as a pattern.

[0070] In some embodiments, solvent-free (dry) development processes may be carried out by appropriate thermal or plasma development processes, such as the process described by Tan et al. in PCT application number PCT / US2020 / 039615, titled "Photoresist Development With Halide Chemistries," which is incorporated herein by reference. For organotin photoresist coatings, dry development may be carried out using halogen-containing plasma and gas, such as HBr and BCl3. See also U.S. Patent Application Publication No. 2023 / 0408916 to Schepper, titled "Gas-Based Development of Organometallic Resist in an Oxidizing Halogen-Donating Environment," which is incorporated herein by reference. In some cases, dry development may offer advantages over wet development, such as reduced pattern breakdown, reduced scum, and finer control of the developer composition, i.e., plasma and / or etching gas.

[0071] After the development process is complete, the coating material may be heat-treated to further compress, dehydrate, and densify the material, or to remove any residual developer from the material. This heat treatment is particularly desirable in embodiments where the oxide coating material is incorporated into a final device, but it is also desirable in some embodiments where the coating material is used as a resist and eventually removed, if stabilization of the coating material is desired to facilitate further patterning. In particular, baking of the patterned coating material may be carried out under conditions that allow the patterned coating material to exhibit a desired level of etching selectivity. In some embodiments, the patterned coating material may be heated to a temperature of about 100 to about 600°C, in further embodiments about 175 to about 500°C, and in additional embodiments about 200 to about 400°C. Heating may be carried out for at least about 1 minute, in other embodiments about 2 minutes to about 1 hour, and in further embodiments about 2.5 to about 25 minutes. Heating may be carried out in an atmosphere of air, vacuum, or an inert gas such as Ar or N2. Those skilled in the art will recognize that an additional range of temperatures and times for heat treatments within the clearly defined range described above is intended and is within the scope of this disclosure. Similarly, non-thermal treatments such as blanket UV exposure or exposure to an oxidizing plasma such as O2 may also be used for similar purposes. [Examples]

[0072] Example 1. Synthesis of 1-Buto-3-enylsutris(t-butyloxide)(MAL) This example describes a one-pot, direct synthesis method for unsaturated organotin trialalkoxides. This method is based on the following reaction, which is carried out by applying heat and adding a tetraalkyl (quaternary) ammonium salt as a catalyst. KSn(OtBu)3+(CH3)(H)C=C(H)(CH2Cl)→(CH3)(H)C=C(H)(CH2)Sn(OtBu)3

[0073] KSn(OtBu)3 was synthesized according to the procedure described in Veith's literature. The KSn(OtBu)3 product, 0.1 molar equivalents of tetrabutylammonium iodide ((n-Bu)4N(I)) as a catalyst (referencing 1 molar equivalent of tin), and toluene were added to a reaction vessel under an inert atmosphere and mixed to form a solution with a concentration of approximately 0.10 g / ml of KSn(OtBu)3 (toluene). The solution was mixed at room temperature. Next, 1.2 molar equivalents of 1-chloro-2-butene ((CH3)(H)C=C(H)(CH2Cl) (a mixture of trans and cis isomers in a ratio of approximately 70:30) were slowly added to the amount of KSn(OtBu)3 with stirring. The reaction mixture was then heated to 45°C and stirred for 3 days. After that, volatile substances were removed under vacuum, and the remaining residue was filtered through a Celite bed containing pentane. The filtrate was pumped down and distilled to obtain the product (CH3)(H)C=C(H)(CH2)Sn(OtBu)3 (1-buto-3-enilsuztris(t-butyl oxide) or MAL) as a mixture of trans and cis isomers. The product was a clear yellow liquid.

[0074] The product was characterized by NMR. 1 ¹H NMR (400MHz, neat): δ 5.70 (m, 2H), 2.41 (cis) + 2.38 (trans) (m, 2H), 1.87 (m, 3H), 1.48 (cis) + 1.49 (trans) (s, 27H) ppm; 119 Sn NMR (149 MHz, neat) δ -225 (trans), -227 (cis) ppm. The results indicate that the dominant isomer is trans, and that the isomer ratio in the MAL product maintains the isomer ratio in the 1-chloro-2-butene reagent. These results also indicate the absence of tin byproducts identified in the conversion of KSn(OtBu)3 to (CH3)(H)C=C(H)(CH2)Sn(OtBu)3.

[0075] This example demonstrates a method for directly synthesizing unsaturated organotin trialalkoxides with high monoorganic specificity. This example also demonstrates that the method can be carried out with both trans and cis isomers of the olefin halide reagent.

[0076] Example 2. UV-based synthesis of 2,2,2-trifluoroethyl tin tris(t-butyl oxide) (TFE) This example describes a one-pot, direct synthesis method for fluorinated organotin trialalkoxides under ultraviolet light. This method is based on the following reaction. Sn2(OtBu)4+CF3CH2I→CF3CH2Sn(OtBu)3

[0077] Sn2(OtBu)4 was synthesized using Veith's method. Sn2(OtBu)4, 1.3 molar equivalents of 2,2,2-trifluoroiodoethane (CF3CH2I) (referencing 1 molar equivalent of tin reactant), and pentane were added to a reaction vessel under an inert atmosphere and mixed to form a solution with a concentration of approximately 0.33 g / ml of Sn2(OtBu)4 (pentane). The solution was mixed at room temperature. The solution was then irradiated with ultraviolet light (40W LED; 365 nm) overnight (approximately 15 hours). The reaction mixture was then filtered on a Celite bed, and volatile substances were removed from the filtrate under vacuum. The resulting filtrate was distilled to obtain the final product CF3CH2Sn(OtBu)3 (2,2,2-trifluoroethylstin tris(t-butyl oxide) or TFE). The product was a clear yellow liquid and was characterized by NMR. 1 H NMR (400MHz, neat) δ1.77(m,2H),1.06(s,27H)ppm; 119 Sn NMR (149 MHz, neat) δ-231(q) ppm; 19 F NMR (neat) δ-53(m) ppm. The NMR results indicate that no tin byproducts were identified in the synthesis of CF3CH2Sn(OtBu)3.

[0078] This example demonstrates a photochemical method for directly synthesizing fluorinated organotin trialalkoxides with high monoorganic specificity.

[0079] Example 3. Synthesis of LED-based 2,2,2-trifluoroethyl tin tris(t-butyl oxide)(TFE) This example describes an optical method for the one-pot, direct synthesis of fluorinated organotin trialalkoxides under visible light (LED). This method is based on the following reaction. KSn(OtBu)3+CF3CH2I→CF3CH2Sn(OtBu)3

[0080] KSn(OtBu)3 was synthesized using Veith's method. The KSn(OtBu)3 product, 1.1 molar equivalents of 2,2,2-trifluoroiodoethane (CF3CH2I) (referencing 1 molar equivalent of tin), and acetonitrile were added to a reaction vessel under an inert atmosphere and mixed to form a solution with a concentration of approximately 0.25 g / ml of KSn(OtBu)3 (acetonitrile). The solution was mixed at room temperature. The solution was then irradiated with visible light for 1 day while stirring. The visible light was provided by a 100W LED and was either violet light (approximately 400 nm) or blue light (approximately 460 nm). The external temperature of the reaction vessel was maintained below 30°C using a fan. Subsequently, the reaction solvent was removed under reduced pressure, and the residual solvent was filtered through a Celite bed containing pentane. The volatile substances in the filtrate were removed under vacuum, and the resulting oil was distilled to obtain the final product CF3CH2Sn(OtBu)3 (2,2,2-trifluoroethyl tin tris(t-butyl oxide) or TFE). The product was a clear yellow liquid.

[0081] Results of the NMR spectrum of the product prepared with violet light: 1 H NMR (400MHz, neat) δ1.57(s,27H),2.27(q,2H)ppm; 119Sn NMR (149 MHz, neat) δ-231(q) ppm. Products prepared under blue light showed indistinguishable results. These results indicate that no tin byproducts were identified in the conversion of KSn(OtBu)3 to CF3CH2Sn(OtBu)3.

[0082] Synthesis performed under green LED light was successful, but not under ambient light.

[0083] This example demonstrates a photochemical method for directly synthesizing fluorinated organotin trialalkoxides with high monoorganic specificity and high yield. This example also demonstrates the effectiveness of this method with visible light of various wavelengths. Furthermore, this example demonstrates that the reaction forming the fluorinated trialalkoxy product is photochemically induced.

[0084] Example 4. Synthesis of 3,4,4-trifluorobut-4-enyl tin tris(t-butyl oxide)(FBEN) This example describes a one-pot, direct synthesis method for fluorinated alkenyl tin trialkoxide represented by formula 1. The reaction is carried out under ultraviolet light. This method is based on the following reaction. Sn2(OtBu)4+CF2CF(CH2)2I→(CF2=CFCH2CH2Sn(OtBu)3 [ka] 1.1 molar equivalents of Sn2(OtBu)4,4-iodo-1,1,2-trifluorobuto-1-ene (CF2CF(CH2)2I) (referencing 1 molar equivalent of tin reactant) and pentane were added to a reaction vessel under an inert atmosphere and mixed to form a solution with a concentration of approximately 40.33 g / ml of Sn2(OtBu) (pentane). The solution was mixed at room temperature. The solution was irradiated with ultraviolet light (40W LED; 365 nm) for 2 days. The reaction mixture was then filtered through a Celite bed, and volatile substances were removed from the filtrate under vacuum. The resulting filtrate was distilled to obtain the final product CF2CF(CH2)2Sn(OtBu)3 (3,4,4-trifluorobuto-4-enyl tin tris(t-butyl oxide) or FBEN). The product was a clear yellow liquid. The product was characterized by NMR. 1 H NMR(C6D6)δ1.24(m,2H),1.37(s,27H),2.37(m,2H); 119 Sn NMR (NEAT) δ-201(d); 19 F NMR (neat) δ-105.8(dd),-123.3(dd),-177.1(dd).

[0085] This example demonstrates a photochemical method for directly synthesizing fluorinated, unsaturated organotin trialalkoxides with high monoorganic specificity.

[0086] Example 5: Synthesis of Buto-4-enylsuztris(t-butyloxide)(BEN) This example describes the synthesis of a non-fluorinated alkenyl tin trialalkide of the formula ((CH2=CHCH2CH2Sn(OtBu)3) represented by formula 2. This method is based on the following reaction: The reaction is carried out by adding heat and a tetraalkyl (quaternary) ammonium salt as a catalyst. KSn(OtBu)3+CH2=CH(CH2)2Br→CH2=CHCH2CH2Sn(OtBu)3 [ka]

[0087] KSn(OtBu)3 (prepared by the method described above or using Veith), 15 mol% tetrabutylammonium iodide ((n-Bu)4N(I)) as a catalyst (relative to Sn moles), and toluene were added to a reaction vessel under an inert atmosphere and mixed to form a solution with a concentration of approximately 0.10 g / ml (toluene) of KSn(OtBu)3. The solution was mixed at room temperature. Then, 1.1 molar equivalents of 4-bromobuto-1-ene (CH2=CH(CH2)2Br) relative to the amount of KSn(OtBu)3 were slowly added while stirring. The reaction mixture was then heated to 80°C and stirred. The reaction was monitored by NMR, and it was confirmed that the reaction stopped when all of the 4-bromobuto-1-ene and KSn(OBu)3 were consumed. The solvent was then removed under vacuum. The remaining residue was dissolved in pentane and filtered on a Celite bed, and volatile substances were removed from the filtrate under vacuum. Using a Pro-Pak® packed column, the obtained filtrate was distilled at 70°C by short-pass distillation to yield the final product CH2=CHCH2CH2Sn(OtBu)3 buto-4-enyl suztris (t-butyl oxide or BEN). The product was a colorless liquid.

[0088] Example 6: Thermal stability of fluorinated and non-fluorinated alkenyl ligands This example describes the production of a photoresist film using fluorination, an unsaturated organotin precursor, and a non-fluorinated derivative precursor, and demonstrates that fluorination can provide increased thermal stability of photoresist films prepared using precursors having an unsaturated ligand.

[0089] The first precursor solution (S1) was prepared by dissolving an appropriate amount of (CF2=CFCH2CH2Sn(OtBu)3 from Example 4 in 4-methyl-2-pentanol to form an organotin solution with a Sn concentration of 0.05 M [Sn]. The second precursor solution (S2) was prepared by dissolving an appropriate amount of (CH2=CHCH2CH2Sn(OtBu)3 from Example 5 in n-propanol to form an organotin solution with a Sn concentration of 0.05 M [Sn]. The precursor solution S1 was spin-coated onto an undoped 4-inch Si wafer at 1500 rpm for 45 seconds to produce a film sample (F1) with an average thickness of approximately 22 nm. The precursor solution S2 was spin-coated onto an undoped 6-inch Si wafer at 1500 rpm for 45 seconds to produce a film sample (F2) with an average thickness of approximately 26 nm. The film thickness was measured by polarization analysis.

[0090] Next, the coated wafers were cut into chips approximately 1 inch in size. The chips coated with film sample F1 were baked on a hot plate at temperatures of 75°C, 150°C, 180°C, 200°C, 230°C, 245°C, 260°C, or 290°C for 2 minutes, or not baked. The chips coated with film sample F2 were baked on a hot plate at temperatures of 50°C, 100°C, 130°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, or 280°C for 2 minutes, or not baked.

[0091] After the selected baking steps for the F1 and F2 film samples were completed, the films were then analyzed by FTIR. For the non-fluorinated alkenyl ligand sample (F2), the midpoint of the alkene CH stretching region was 3075 cm². -1 The peak area was measured at 1300 cm². For the fluorinated alkenyl ligand sample (F1), the peak area corresponding to CF stretching absorption was 1300 cm². -1 , 1238cm -1 , and 1166cm -1The peak areas were calculated as the sum of the measured peak areas. Then, the peak area of ​​each baked film was normalized to the peak area of ​​the corresponding unbaked film. Figure 1 shows the normalized peak areas as a function of bake temperature for film samples F1 (FBEN) and F2 (BEN). The data point for the unbaked film plot is shown at 20°C, which is the peak area point used for normalization. The thermal stability of each ligand type (fluorinated vs. unfluorinated) was evaluated by examining the curves in Figure 1. The FTIR results show high retention of the intrinsic CF absorption in the F1 sample compared to the intrinsic CH absorption in the F2 sample over the studied temperature range. Fluorinated alkenyl ligands showed higher thermal stability than the unfluorinated ligands used for comparison. These results suggest that the high-temperature stability of organotin precursor compositions can be enhanced using fluorinated unsaturated organic ligands.

[0092] This example demonstrates that organotin films prepared using organotin precursors containing fluorinated alkenyl ligands have higher thermal stability than comparative organotin films prepared using organotin precursors containing non-fluorinated alkenyl ligands.

[0093] Example 7: Patterning of organotin photoresist prepared from a precursor blend. This example demonstrates that the radiation sensitivity of organotin photoresists can be improved by blending compounds having fluorinated alkenyl tin ligands with various organotin photoresist compositions.

[0094] A series of photoresist solutions were prepared from the organotin precursors shown in Table 1 and the solvents shown in Table 2. According to Table 3, appropriate amounts of the selected organotin precursors were blended with the selected solvents to form photoresist solutions having a Sn concentration of 0.05 M [Sn]. Blends A and B are photoresist solutions formed from blends of two organotin precursors (A and B) having non-fluorinated saturated ligands: t-butyl and methyl, respectively. The precursors were synthesized as described in U.S. Patent No. 11,673,903 to Edson et al., incorporated herein by reference. Precursor B was synthesized as described in the above-mentioned '244 patent application, and precursors C and D were synthesized as described in the above-mentioned method. Blends C1-C3 are photoresist solutions formed from blends of organotin precursor A having a non-fluorinated saturated ligand and organotin precursor C having a non-fluorinated unsaturated ligand. Blends D1 to D5 are photoresist solutions formed from a blend of two or three precursors, wherein at least one organotin precursor (A and / or B) has a non-fluorinated saturated ligand and one organotin precursor (D) has a ligand that is both fluorinated and unsaturated.

[0095] [Table 1]

[0096] [Table 2]

[0097] [Table 3]

[0098] Photoresist film samples were prepared by spin-coating each photoresist solution shown in Table 2 onto a 300 mm Si wafer coated with 10 nm spin-on-glass (SOG), yielding organotin photoresist film samples with an average thickness of approximately 24 nm. Using an ASML NXE3400B exposure tool, the samples were exposed to EUV radiation to generate line-space patterns with a target limit dimension (CD) of 16 nm on a 32 nm pitch from each photoresist film sample, forming an array of patterns in fields on the wafer, with each field corresponding to a pattern printed at a specific dose. As is customary in the art, this type of exposure is called dose meander exposure. By exposing each photoresist film sample to the same 16p32 pattern at different doses, the dose required to print the desired 16p32 pattern on a given photoresist film sample (i.e., dose-to-size, Dts, for printing 16nm lines at a 32nm pitch) can be determined by inspection of each field after processing is complete. Following EUV exposure, each film was subjected to a post-exposure bake (PEB) for 60 seconds at 160°C, 180°C, 190°C, or 200°C; developed with a 5 wt% acetic acid solution in PGMEA; and finally hard-baked at 250°C for 60 seconds to form the completed patterned wafer.

[0099] Next, the completed patterned wafers were analyzed by CDSEM, and the dose-to-size ratio was determined by inspection for each wafer. The absolute dose corresponding to the desired 16p32 pattern was determined, and then the percentage change in DtS was calculated for photoresist samples prepared from blend A or blend B (control 1 and control 2, respectively) and presented in Table 4. EUV exposure of photoresist samples prepared from blend A (control 1) and blends D1-D5 (resists D1-D5) was performed over a different number of days than EUV exposure of photoresists prepared from blend B (control 2) and blends C1-C3 (resists C1-C3). The DtS of each photoresist sample was subjected to the same PEB temperature on the same day and normalized against the DtS of the associated patterned photoresist to eliminate day-to-day variations in absolute dose due to tool changes, environmental differences, and other potential causes of variation.

[0100] [Table 4]

[0101] Resists C1-C3 were formed from a precursor solution containing a blend of tBuSn(OtAm)3 with one of the following: 5 mol% (resist C1), 10 mol% (resist C2), or 20 mol% (resist C3) of a precursor containing a non-fluorinated alkenyl ligand (CH2=CHCH2CH2Sn(OtBu)3). Referring to Table 4, resists C1 and C2 showed an increase in DtS compared to two control resists (formed from a precursor solution containing a blend of tBuSn(OtAm)3 and 20 mol% tBuSn(OtAm)3) at all tested PEB temperatures. The increase in DtS was higher in resist C1 than in resist C2 at all tested temperatures, ranging from 17.89% to 44.11%. The change in DtS generally increased with increasing PEB temperature. Resist C3 showed a modest decrease in DtS compared to control 2 resists at PEB temperatures of 160°C, 190°C, and 200°C. At a PEB temperature of 180°C, resist C3 showed a modest increase in DtS compared to control 2. The results for resist C3 provide a direct comparison of resist performance when the same weight of unsaturated precursor is used instead of the saturated precursor MeSn(OtAm)3. The results for resists C1-C3 demonstrate the effect on DtS by incorporating various weight percentages of unsaturated precursors into the photoresist film.

[0102] Unlike resist C1, resist D1 (prepared from 20 mol% fluorinated alkenyl tin compound and 380 mol% tBuSn(OtAm)) showed a significant decrease in DtS compared to its control resist (control 1) at each of the PEB temperatures tested. A 23% and 39% decrease in DtS was observed for resist D1 at PEB temperatures of 160°C and 180°C, respectively. This result indicates a significant improvement in photosensitivity for the two-component blend of CF2=CFCH2CH2Sn(OtBu)3 and tBuSn(OtAm)3. At the two highest PEB temperatures tested (190°C and 200°C), the decrease in DtS compared to the control was more pronounced, and therefore, both patterns were irradiated with excessive doses, while the lowest measured dose (30 mJ / cm²) was observed. 2 Even then, it was not possible to capture dose-size values ​​(in Table 4).** (As shown by...). From the results for resist D1, it can be seen that replacing MeSn(OtAm)3 with a fluorinated alkenyl tin compound in a photoresist blend containing tBuSn(OtAm)3 significantly improved DtS.

[0103] Resists D2-D5 were prepared from a three-component blend of organotin compositions: CF2=CFCH2CH2Sn(OtBu)3, MeSn(OtAm)3, and tBuSn(OtAm)3. Each of these three-component blend resists showed a decrease in DtS at each PEB temperature tested. Three-component blend resists prepared with higher relative amounts of fluorinated alkenyl tin compounds showed a correspondingly greater decrease in DtS. Resist D4 (prepared from 15 mol% organotin precursor D) showed a greater decrease in DtS than resists D3 and D2 (prepared from 10 mol% organotin precursor D) and resist D5 (prepared from 5 mol% organotin precursor D) at each PEB temperature tested. At a PEB temperature of 200°C, the DtS for three-component blend resists D2-D5 was too low to be captured on the wafer. Resist D4 (organotin precursor D15%) also showed a greater reduction in DtS than Resist D1 (organotin precursor D20%). The results for Resists D2-D5 suggest that the dose sensitivity improvement provided by the addition of fluorinated alkenyl tin compounds can be further enhanced by incorporating them into blends containing two or more other organotin compounds.

[0104] The results of this study demonstrate that blending organotin compounds containing fluorinated alkenyl ligands into organotin photoresist compositions can significantly increase the dose sensitivity of the photoresist.

[0105] The embodiments described above are intended to be descriptive and not restrictive. Additional embodiments are within the scope of the claims. Furthermore, while the present invention is described in relation to specific embodiments, those skilled in the art will recognize that modifications can be made in form and detail without departing from the spirit and scope of the invention. Any incorporation by reference to the above documents is limited so as not to incorporate subject matter contrary to the express disclosure herein. To the extent that a particular structure, composition and / or process is described together with a component, element, component or other partition, it should be understood that the disclosure herein encompasses specific embodiments, embodiments including a particular component, element, component or other partition or combination thereof, and embodiments that consist essentially of such a particular component, component or other partition or combination thereof, which may include additional features that do not alter the fundamental nature of the subject matter proposed in the discussion unless otherwise specified. The use of the term “about” herein means an expected uncertainty of the relevant value, as will be understood by those skilled in the art in the specific context.

Claims

1. R １ SnL １ ３ and R ２ SnL ２ ３ A composition comprising a blend with R １ and R ２ are each independently different from one another and together contain from 1 to 31 carbon atoms of an organic group containing at least 1 carbon atom having at least one unsaturated carbon-carbon bond and at least 1 carbon atom having a C-F bond, each organic group forms a C-Sn bond, R １ SnL １ ３ and R １ SnL １ ３ each contains at least about 1% of the total Sn atoms in the composition, and L １ and L ２ are independently selected hydrolyzable ligands, a composition.

2. The fluorine atom is R ａ - Provides thermal stabilization of the Sn bond, where a = 1 or 2, R ａ It contains a C-F bond, and the stabilization is equivalent to R ＮＦ -This is for Sn bonds, and the R ＮＦ The ligand has a hydrogen atom instead of each elementary atom, except that R ａ The composition according to claim 1, which is identical to the one described above.

3. R １ and R ２ The composition according to claim 1 or 2, wherein is independently selected from the group consisting of an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated ligand containing a C=C bond, a fluorinated ligand containing an aromatic group, an unsaturated carbon-carbon bond-free non-fluorinated ligand, a non-fluorinated ligand containing a C=C bond, and a non-fluorinated ligand containing an aromatic group.

4. R １ R contains a fluorinated alkenyl ligand, ２ The composition according to claim 1 or 2, wherein the unsaturated carbon bond-free, non-fluorinated ligand is included.

5. R １ It contains an unsaturated carbon-carbon bond-free fluorinated ligand, R ２ The composition according to claim 1 or 2, wherein the nonfluorinated alkenyl ligand is present.

6. R １ and R ２ The composition according to claim 1 or 2, wherein it comprises together at least one carbon atom having two or more C-F bonds.

7. R １ The composition according to claim 1 or 2, wherein it comprises at least one carbon atom having a C=C bond and at least one carbon atom having a C-F bond.

8. R ２ The composition according to claim 7, wherein the composition comprises methyl, n-propyl, isopropyl, n-butyl, t-butyl, t-amyl, propenyl, butenyl, pentenyl, or an isomer thereof.

9. R １ The composition according to claim 1 or 2, wherein it contains at least one carbon atom having both a C=C bond and a C-F bond.

10. R １ SnL １ ３ and R ２ SnL ２ ３ The composition according to any one of claims 1 to 9, wherein each of these comprises at least about 5% of the total Sn atoms in the composition.

11. L １ and / or L ２ The composition according to any one of claims 1 to 10, wherein the composition is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, or a combination thereof.

12. L １ and L ２ The composition according to any one of claims 1 to 10, wherein is an alkoxide.

13. R １ SnL ２ ３ It contains 3,4,4-trifluorobuto-4-enylsustris(t-butyl oxide), R ２ SnL ２ ３ The composition according to claim 1, wherein the composition comprises buto-4-enylsuztris(t-butyl oxide).

14. R １ SnL ２ ３ It contains 3,4,4-trifluorobuto-4-enylsustris(t-butyl oxide), R ２ SnL ２ ３ The composition according to claim 1, wherein the composition comprises t-butylsutris (t-amyl oxide).

15. The aforementioned blend is further R ３ SnL ３ ３ Includes R ３ R １ and R ２ Unlike the above, it is an organic group having 1 to 31 carbon atoms that form a C-Sn bond, R ３ SnL ３ ３ This comprises at least about 1% of the total Sn atoms in the composition, and L ３ The composition according to any one of claims 1 to 14, wherein is a selected hydrolyzable ligand.

16. R ３ The composition according to claim 15, wherein the fluorinated ligand is selected from the group consisting of an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated ligand containing a C=C bond, a fluorinated ligand containing an aromatic group, an unsaturated carbon-carbon bond-free non-fluorinated ligand, a non-fluorinated ligand containing a C=C bond, and a non-fluorinated ligand containing an aromatic group.

17. L １ , L ２ , and / or L ３ The composition according to claim 15 or 16, wherein the composition is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, or a combination thereof.

18. L １ , L ２ and L ３ The composition according to claim 15 or 16, wherein is an alkoxide.

19. R １ SnL ２ ３ It contains 3,4,4-trifluorobuto-4-enylsustris(t-butyl oxide), R ２ SnL ２ ３ It contains t-butylsutris (t-amyl oxide), R ３ SnL ３ ３ The composition according to claim 15, wherein the composition comprises methylsuzutris (t-amyl oxide).

20. A photoresist composition comprising an organic solvent and the composition according to any one of claims 1 to 19.

21. The photoresist composition according to claim 20, wherein the organic solvent comprises an alcohol.

22. The photoresist composition according to claim 20, wherein the organic solvent comprises a primary alcohol or a combination thereof.

23. Formula R ＵＦ Sn(OR') ３ A fluorinated organometallic compound represented by, In the formula, R ＵＦ The fluorinated organometallic compound is an organic group comprising 1 to 31 carbon atoms, having at least one C=C bond and at least one fluorine atom bonded to carbon, wherein the organic group forms a C-Sn bond, and R' is an organic group comprising 1 to 10 carbon atoms.

24. R ＵＦ The fluorinated organometallic compound according to claim 23, wherein is a fluorinated alkenyl ligand.

25. R ＵＦ The fluorinated organometallic compound according to claim 23, wherein it contains at least one carbon atom having both a C=C bond and a C-F bond.

26. R ＵＦ A fluorinated organometallic compound according to any one of claims 23 to 25, wherein the compound essentially consists of C, H, and F atoms.

27. The fluorinated alkenyl ligand contains at least one carbon atom that forms both a C=C bond and one or more C-F bonds, and R' is C ｎ H ２（ｎ－１）＋３ The fluorinated organometallic compound according to claim 24, wherein the branched or linear group has a total stoichiometry (wherein n = 1 to 10).

28. R ＵＦ The fluorinated organometallic compound according to claim 23, which is selected from the group consisting of fluorinated alkenyl ligands, fluorinated aryl ligands, and fluorinated alkynyl ligands.

29. R ＵＦ Sn(OR') ３ The fluorinated organometallic compound according to claim 23, wherein ＵＦ is 3,4,4-trifluorobut-4-enyltin tris(t-butoxide).

30. R' is C ｎ H ２（ｎ－１）＋３ A fluorinated organometallic compound according to any one of claims 23 to 29, wherein the group is a linear, branched, or cyclic group having a stoichiometry of (wherein n = 1 to 10).

31. The fluorinated organometallic compound according to any one of claims 23 to 30, wherein R' is a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, or t-amyl group, or a combination thereof.

32. The aforementioned R ＵＦ -Sn bond has higher thermal stability than an equivalent R ＮＦ -Sn bond, and the R ＮＦ ligand is the same as R except that it has a hydrogen atom in place of each fluorine atom. The fluorinated organometallic compound according to any one of claims 23 to 31. ＵＦ ​

33. A fluorinated organometallic compound according to any one of claims 23 to 32, and formula R ２ SnL' ３ A blend comprising a compound represented by R ２ However, it is an organic group having 1 to 20 carbon atoms, and R ＵＦ Unlike the previous blend, L' is a hydrolyzable ligand.

34. A photoresist composition comprising an organic solvent and a fluorinated organometallic compound according to any one of claims 23 to 33.

35. The photoresist composition according to claim 34, wherein the organic solvent comprises an alcohol or a combination thereof.

36. The photoresist composition according to claim 34, wherein the organic solvent comprises a primary alcohol.

37. R ＵＦ The photoresist composition according to claim 34, wherein it contains at least one carbon atom having both a C=C bond and a C-F bond.

38. R ＵＦ The photoresist composition according to claim 34, wherein is a fluorinated alkenyl ligand.

39. Formula R ＵＦ Sn(OR') ３ (In the formula, R ＵＦ This is an organic group consisting of 1 to 31 carbon atoms having an unsaturated C-C bond and at least one fluorine atom bonded to carbon, R ＵＦ A method for synthesizing fluorinated organometallic compounds represented by a C-Sn bond (where R' is an organic group with 1 to 10 carbon atoms), Under visible light or ultraviolet light, R ＵＦ X (wherein X is Cl, Br, or I) is Sn ２ (OR') ４ or MSn (OR') ３ To make it react Methods that include...

40. R ＵＦ The method according to claim 39, wherein the C=C group is included.

41. R ＵＦ The method according to claim 39 or 40, wherein contains 3 to 12 carbon atoms.

42. R ＵＦ The method according to any one of claims 39 to 41, wherein the method comprises an alkenyl or aryl group.

43. X is Br or I, and MSn (OR') ３ The method according to any one of claims 39 to 42, wherein M is K when used.

44. The method according to any one of claims 39 to 43, wherein the reaction is carried out for less than approximately two days.

45. The method according to any one of claims 39 to 44, wherein the reaction is carried out at a temperature of approximately -20 to approximately 100°C.

46. The method according to any one of claims 39 to 44, wherein the reaction is carried out at room temperature.

47. The method according to any one of claims 39 to 46, wherein the visible light or ultraviolet light is provided by a selected light source.

48. Using distillation, the R ＵＦ Sn(OR') ３ The method according to any one of claims 39 to 47, further comprising purifying the product.

49. R ＵＦ X to Sn ２ (OR') ４ The method according to any one of claims 39 to 48, wherein the reaction is carried out.

50. R ＵＦ X is CF ２ CF(CH ２ ) ２ The method according to claim 49, wherein I is a t-butyl group.

51. R Ｂ SnO （３／２－ｘ／２） (OH) ｘ A composition comprising, where 0 < x < 3, R Ｂ A composition comprising an organic group or a blend of ligands, each of which is an organic group, each organic group independently having 1 to 31 carbon atoms, the organic groups collectively having at least one carbon atom having a C=C bond and at least one carbon atom having a C-F bond, each organic group forming a C-Sn bond, and the composition comprising an oxo-hydroxo reticular structure.

52. R Ｂ The composition according to claim 51, wherein the composition comprises a blend of ligands, each ligand being, within the overall constraints, an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated alkenyl ligand, a fluorinated aryl ligand, an unsaturated carbon-carbon bond-free non-fluorinated ligand, a non-fluorinated alkenyl ligand, a non-fluorinated aryl ligand, or a combination thereof.

53. R Ｂ The composition according to claim 51, wherein it comprises a ligand having at least one carbon atom that forms both a C=C bond and a C-F bond.

54. The composition according to claim 53, wherein the ligand forms at least 95% of the total C-Sn bonds of the composition.

55. R Ｂ The composition according to any one of claims 51 to 54, wherein each ligand independently comprises an organic group having 1 to 31 carbon atoms, each containing at least one carbon atom having a different unsaturated bond and at least one carbon atom having a C-F bond, each organic group forming a C-Sn bond, and each ligand forming at least about 1% of the total C-Sn in the composition.

56. The composition according to claim 55, wherein one ligand comprises 3,4,4-trifluorobuto-4-enyl bonded to tin, and the second ligand comprises buto-4-enyl bonded to tin.

57. The composition according to claim 55, wherein the first ligand comprises 3,4,4-trifluorobuto-4-enyl bonded to tin, and the second ligand comprises t-butyl bonded to tin.

58. The composition according to claim 55, wherein the first ligand comprises 3,4,4-trifluorobut-4-enyl bonded to tin, the second ligand comprises t-butyl bonded to tin, and the third ligand comprises methyl bonded to tin.

59. A substrate having a surface, and a coated substrate comprising the composition according to any one of claims 51 to 58 on the surface of the substrate.

60. The coated substrate according to claim 59, wherein the coated substrate includes a silicon wafer.

61. A method for forming a patterning composition on a substrate surface: The method involves coating the substrate surface with a solution, wherein the solution consists of a solvent and R １ SnL １ ３ and R ２ SnL ２ ３ Includes a dissolved blend and R １ and R ２ These are organic groups of 1 to 31 carbon atoms, each independently containing at least one unsaturated carbon-carbon bond and at least one fluorine atom bonded to a carbon atom, and the organic groups form a C-Sn bond, R １ SnL １ ３ and R ２ SnL ２ ３ Each of these contains at least about 1% of the total Sn atoms in the composition, L １ and L ２ The coating is an independently selected hydrolyzable ligand; R Ｂ SnO （３／２－ｘ／２） (OH) ｘ (In the formula, 0 < x < 3, R Ｂ is R １ and R ２ Removing the solvent in order to form a coating containing a blend of ligands; Methods that include...

62. The method according to claim 61, wherein the solvent comprises an alcohol.

63. R １ The method according to claim 61 or 62, wherein the ligand comprises an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated alkenyl ligand, a fluorinated alkynyl ligand, a fluorinated aryl ligand, or a combination thereof.

64. R ２ The method according to any one of claims 61 to 63, wherein the method comprises an unsaturated carbon-carbon bond-free nonfluorinated ligand, a nonfluorinated alkenyl ligand, a nonfluorinated alkynyl ligand, a nonfluorinated aryl ligand, or a combination thereof.

65. A method for forming a coating on a substrate surface that can form a radiation pattern: The process involves reacting an organotin precursor with a corresponding reactant simultaneously or sequentially to form a patternable organometallic composition on the surface of the substrate, wherein the organotin precursor and the corresponding reactant are supplied as vapors, and the organotin precursor vapor is R １ SnL １ ３ and R ２ SnL ２ ３ Includes R １ and R ２ These are organic groups of 1 to 31 carbon atoms, each independently containing at least one unsaturated carbon-carbon bond and at least one fluorine atom bonded to a carbon atom, and the organic groups form a C-Sn bond, R １ SnL １ ３ and R ２ SnL ２ ３ Each of these comprises at least about 1% of the total Sn atoms in the composition, L １ and L ２ is an independently selected hydrolyzable ligand, The corresponding reactants include water, oxygen molecules, and / or other oxygen-donating compounds, and The process involves forming a coating on the substrate surface that can form a radiation pattern, wherein the radiation pattern-forming coating is R Ｂ SnO （３／２－ｘ／２） (OH) ｘ (In the formula, 0 < x < 3, R Ｂ R １ Ligand and R ２ Forming a coating that includes (a blend with a ligand); Methods that include...

66. R １ The method according to claim 65, wherein the ligand comprises an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated alkenyl ligand, a fluorinated aryl ligand, or a combination thereof.

67. R ２ The method according to claim 65 or 66, wherein the ligand comprises an unsaturated carbon-carbon bond-free fluorinated ligand, a non-fluorinated alkenyl ligand, a non-fluorinated aryl ligand, or a combination thereof.

68. The aforementioned organotin precursor vapor is R １ SnL １ ３ and R ２ SnL ２ ３ The method according to any one of claims 65 to 67, comprising two independent reservoirs.

69. The method according to any one of claims 65 to 68, wherein the reaction is carried out by exposure to an atmosphere containing water vapor and oxygen molecules.

70. R １ SnL １ ３ and R ２ SnL ２ ３ A composition comprising a blend with R １ and R ２ These are independently distinct organic groups containing 1 to 31 carbon atoms, each containing at least one fluorinated group and a C=C bond, and each forms a C-Sn bond, R Ｆ SnL １ ３ L comprises at least about 1% of the total Sn atoms in the composition. １ and L ２ A composition in which is an independently selected hydrolyzable ligand.

71. The composition according to claim 70, wherein the organic group contains 1 to 31 carbon atoms without a C-F bond and forms a C-Sn bond.

72. The aforementioned fluorine group is equivalent to R ＮＦ - Compared to the Sn bond, R ａ - Provides thermal stabilization of the Sn bond (where a = 1 or 2 in the formula), and the R ＮＦ The ligand has a hydrogen atom instead of each fluorine atom, except that R ａ The composition according to claim 70 or 71, which is identical to the one described above.

73. R １ and R ２ The composition according to any one of claims 70 to 72, wherein the group is independently selected from the group consisting of an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated ligand containing a C=C bond, a fluorinated ligand containing an aromatic group, an unsaturated carbon-carbon bond-free non-fluorinated ligand, a non-fluorinated ligand containing a C=C bond, and a non-fluorinated ligand containing an aromatic group.

74. R １ R contains a fluorinated alkenyl ligand, ２ The composition according to any one of claims 70 to 72, wherein the composition comprises an unsaturated carbon bond-free, non-fluorinated ligand.

75. R １ It contains an unsaturated carbon bond-free fluorinated ligand, R ２ The composition according to any one of claims 70 to 72, wherein the composition comprises a non-fluorinated alkenyl ligand.

76. R １ and R ２ The composition according to any one of claims 70 to 72, wherein the composition comprises, collectively, at least one carbon atom having two or more C-F bonds.

77. R １ The composition according to any one of claims 70 to 72, wherein it comprises at least one carbon atom having a C=C bond and at least one carbon atom having a C-F bond.

78. R ２ The composition according to claim 77, wherein the composition comprises methyl, n-propyl, isopropyl, n-butyl, t-butyl, t-amyl, propenyl, butenyl, pentenyl, or a combination thereof.

79. R １ The composition according to any one of claims 70 to 72, wherein it contains at least one carbon atom having both a C=C bond and a C-F bond.

80. R １ SnL １ ３ and R ２ SnL ２ ３ The composition according to any one of claims 70 to 79, wherein each of these comprises at least about 5% of the total Sn atoms in the composition.

81. L １ and / or L ２ The composition according to any one of claims 70 to 80, wherein the composition is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, or a combination thereof.

82. L １ and / or L ２ The composition according to any one of claims 70 to 80, wherein is an alkoxide.

83. R １ SnL ２ ３ It contains 3,4,4-trifluorobuto-4-enylsustris(t-butyl oxide), R ２ SnL ２ ３ The composition according to claim 70, wherein the composition comprises buto-4-enylsuztris(t-butyl oxide).

84. R １ SnL ２ ３ It contains 3,4,4-trifluorobuto-4-enylsustris(t-butyl oxide), R ２ SnL ２ ３ The composition according to claim 70, wherein the composition comprises t-butylsutris (t-amyl oxide).

85. The aforementioned blend is further R ３ SnL ３ ３ Includes R ３ R is independent of １ and R ２ Unlike the above, it is an organic group with 1 to 31 carbon atoms that forms a C-Sn bond, R ３ SnL ３ ３ This comprises at least about 1% of the total Sn atoms in the composition, and L ３ The composition according to any one of claims 70 to 84, wherein is an independently selected hydrolyzable ligand.

86. R ３ The composition according to claim 85, wherein the fluorinated ligand is selected from the group consisting of an unsaturated carbon-carbon bond-free fluorinated ligand, a fluorinated ligand containing a C=C bond, a fluorinated ligand containing an aromatic group, an unsaturated carbon-carbon bond-free non-fluorinated ligand, a non-fluorinated ligand containing a C=C bond, and a non-fluorinated ligand containing an aromatic group.

87. L １ , L ２ , and / or L ３ The composition according to claim 85 or 86, wherein the composition is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, or a combination thereof.

88. L １ , L ２ and / or L ３ The composition according to claim 85 or 86, wherein is an alkoxide.

89. A photoresist composition comprising an organic solvent and the composition according to any one of claims 70 to 88.

90. The photoresist composition according to claim 89, wherein the organic solvent comprises an alcohol.

91. The photoresist composition according to claim 89, wherein the organic solvent comprises a primary alcohol.

92. Formula R ＵＦ SnL ３ A fluorinated organometallic compound represented by the formula, where R ＵＦ R is an organic group having 1 to 31 carbon atoms, with at least one carbon atom forming both a C=C bond and a C-F bond. ＵＦ A fluorinated organometallic compound in which C-Sn bond is formed and L is a hydrolyzable ligand.

93. R ＵＦ However, formula R １ R ２ C=CR ３ R ４ It contains a fluorinated alkenyl group having R in the formula, １ , R ２ , and R ３ F or CF ３ And R ４ The fluorinated organometallic compound according to claim 92, wherein is an alkyl group having 1 to 15 carbon atoms and forming a Sn-C bond.

94. R ４ However, stoichiometry C ｎ H ２（ｎ－１）＋３ The fluorinated organometallic compound according to claim 93, wherein the branched or linear group has (wherein n = 1 to 5 in the formula).

95. A fluorinated organometallic compound according to any one of claims 92 to 94, wherein L is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, or a combination thereof.

96. A fluorinated organometallic compound according to any one of claims 92 to 94, wherein L is a dialkylamide, alkylsilylamide, alkylacetylide, or a combination thereof.

97. R ＵＦ A fluorinated organometallic compound according to any one of claims 92 to 96, wherein the compound essentially consists of C, H, and F atoms.

98. R ＵＦ A fluorinated organotin composition containing a -Sn bond, R ＵＦ However, it is an organic group having 1 to 31 carbon atoms, each having at least one carbon atom that forms both a C=C bond and a C-F bond, and the R ＵＦ A fluorinated organotin composition in which the -Sn bond includes a C-Sn bond.

99. A fluorinated organotin composition according to claim 98, comprising an oxo-hydroxonetic network structure.

100. Formula R ＵＦ -SnL ３ A fluorinated organotin composition according to claim 98 or 99, comprising a compound represented by the formula, where L is a dialkylamide, alkylsilylamide, alkoxide, alkylacetylide, hydroxide, oxo, or a combination thereof.

101. The fluorinated organotin composition according to any one of claims 98 to 100, wherein the C-Sn bond can be cleaved by EUV light.

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