Radiosensitive organotin composition having an oxygen heteroatom in a hydrocarbyl ligand

Abstract

Formula RSnL 3 An organotin composition having the formula RSnL and a corresponding synthesis method are described. R includes an aromatic, cyclic and / or halogenated ether moiety or polyether, and L includes a hydrolyzable group. The organotin composition can be formed as a radiation-patternable coating on a substrate. The coating has an average thickness of from about 1 nm to about 75 nm and has the formula RSnO n (OH) 3-2n and can form an oxo-hydroxone network, where R is a hydrocarbyl ether group having from 1 to 30 carbon atoms, and 0

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims priority to U.S. Provisional Patent Application No. 63 / 343,331, filed May 18, 2022, by Jilek et al., entitled "Organotin Compositions Having Oxygen Heteroatoms in Hydrocarbyl Ligands", which is hereby incorporated by reference herein in its entirety.

Background Art

[0002] Organometallic compounds provide metal ions in the form of solutions and vapors for depositing thin films. Organotin compounds provide high EUV absorption and radiation - sensitive tin - ligand bonds, which can be utilized for thin - film patterning by lithography. To manufacture semiconductor devices that are more highly miniaturized than ever using EUV radiation, new materials with broad process tolerances are needed to achieve the required patterning resolution and low defect density.

Summary of the Invention

Means for Solving the Problems

[0003] One aspect of the present invention relates to an organotin composition having a Sn - C bond and having a hydrocarbyl group having one or more carbons substituted with an oxygen heteroatom represented by the formula R 1 -O - R 2 SnL 3 wherein R 1 is selected from linear, aromatic, cyclic, branched or unsaturated hydrocarbyl ligands having 1 to 30 carbon atoms and further optionally substituted with one or more heteroatoms such as O, F, I, Si, Sn, Te and / or Sb, R 2 is a hydrocarbyl ligand having a Sn - C bond and 2 to 5 carbon atoms, and L is a hydrolyzable ligand. In some particularly interesting embodiments, R 1 -O - R 2- can form a C-Sn bond, introduce cyclic ethers, aromatic ethers, and polyethers, and provide desirable ligands for the tin patterning composition. The organotin compound is an R selected to impart solubility in polar solvents 1 -O-R 2 - may have a ligand. These organotin compounds having an ether ligand with a C-Sn bond and three hydrolyzable ligands can be formulated into a precursor mixture with an R 0 SnL’ 3 compound to design desirable precursor properties, particularly for patterning by EUV radiation.

[0004] Another aspect of the present invention relates to a composition comprising a solvent and an organotin composition represented by the formula R 1 -O-R 2 SnL 3 wherein R 1 is selected from linear, aromatic, cyclic, branched or unsaturated hydrocarbyl ligands having 1 to 30 carbon atoms and optionally further substituted with one or more heteroatoms such as O, F, I, Si, Sn, Te and / or Sb, R 2 is a hydrocarbyl ligand having a Sn-C bond and 2 to 5 carbon atoms, and L is a hydrolyzable ligand.

[0005] Another aspect of the present invention relates to a high-purity organotin composition that is a hydrocarbyl group containing a Sn-C bond, has a hydrocarbyl group having one or more carbons substituted with an oxygen heteroatom, and has a purity greater than 99.9999% on a metal basis.

[0006] Another aspect of the present invention relates to a method of forming a coating on a substrate, the method comprising hydrolyzing a composition represented by the formula R 1 -O-R 2 SnL 3 wherein R 1 is selected from linear, aromatic, cyclic, branched or unsaturated hydrocarbyl ligands having 1 to 30 carbon atoms and optionally further substituted with one or more heteroatoms such as O, F, I, Si, Sn, Te and / or Sb2 is a Sn-C bond and a hydrocarbyl ligand having 2 to 5 carbon atoms, and L is a hydrolyzable ligand.

[0007] Another aspect of the present invention relates to a coating on a substrate, the coating comprising a composition containing an R 1 -O-R 2 Sn moiety, where R 1 has 1 to 30 carbon atoms and is further optionally substituted with one or more heteroatoms such as O, F, I, Si, Sn, Te, and / or Sb, and is selected from linear, aromatic, cyclic, branched, or unsaturated hydrocarbyl ligands, and R 2 is a hydrocarbyl ligand having a Sn-C bond and 2 to 5 carbon atoms.

[0008] Another aspect of the present invention relates to a method of patterning an organotin composition containing an R 1 -O-R 2 Sn moiety, where R 1 has 1 to 30 carbon atoms and is further optionally substituted with one or more heteroatoms such as O, F, I, Si, Sn, Te, and / or Sb, and is selected from linear, aromatic, cyclic, branched, or unsaturated hydrocarbyl ligands, and R 2 is a hydrocarbyl ligand having a Sn-C bond and 2 to 5 carbon atoms, and the patterning is performed using UV, EUV, or ion beam radiation.

[0009] In a further aspect, the present invention relates to an organotin composition represented by the formula RSnL 3 , where L is a hydrolyzable ligand, and R- is A) an aromatic ether represented by the formula Ar-O-(CR’ 2 ) m -, or B) R is a cyclic ether represented by the formula cyclic(O(CR’’ 2 ) n CR’R 0 -), or C) R is of the formula R 1 OR 0 C(R 2 R 3) is a halogenated ether represented by, or D) R is a polyether represented by the formula R1R2R3C-, Ar is an aromatic organic moiety, m is an integer from 1 to 4, R’ is hydrogen or a hydrocarbyl group having from 1 to 6 carbon atoms and optional heteroatoms, n is an integer from 1 to 8, R’’ is hydrogen or a hydrocarbyl group having from 1 to 4 carbon atoms and optional heteroatoms, and optionally, the CR’’ 2 group can be replaced by O to form a cyclic polyether, and two R’’ groups can be bonded to form a polycyclic structure, and R 0 is a bond or a hydrocarbyl group having from 1 to 5 carbon atoms and optional heteroatoms, and R 1 is a hydrocarbyl group having from 1 to 10 carbon atoms, having optional unsaturated bonds and / or optional heteroatoms, and R 2 and R 3 are independently hydrogen, halogen or a hydrocarbyl group having from 1 to 7 carbon atoms, having optional unsaturated bonds and / or optional heteroatoms, and at least one of R 1 , R 2 , R 3 has a halogen atom, and R1, R2 and R3 are independently hydrocarbyl groups having from 1 to 19 carbon atoms, having optional unsaturated bonds and / or optional heteroatoms, at least two of R1, R2, R3 are ether moieties, or at least one of R1, R2, R3 is a diether moiety. Also described is a solution comprising an organotin composition dissolved in an organic solvent.

[0010] In a further aspect, the invention relates to a radiation patterning-capable coated substrate comprising a substrate and a coating comprising any one or more of the above organotin compositions.

[0011] In a further aspect, the invention relates to a substrate and a coating having an average thickness of about 1 nm to about 75 nm, which forms an oxo-hydroxone network, of the formula RSnO n (OH) 3-2nRelates to a radiation - patterning - capable coating substrate comprising a coating represented by, where R is a hydrocarbyl ether group having 1 to 30 carbon atoms, and 0 < n < 3 / 2, and the region of the coating is soluble in 2 - heptanone in a paddle development step after baking at 150 °C for 120 seconds.

[0012] In a further aspect, the present invention relates to a method of forming a radiation - patterning - capable coating substrate comprising a substrate and a coating comprising any one or more of the above - described organotin compositions.

[0013] In a further aspect, the present invention relates to a method of forming a radiation - patterning - capable coating substrate, the method comprising: A) contacting the substrate surface with the vapor of the organotin composition described herein to form a deposit on the substrate surface, and heating the substrate having the deposit on the surface, wherein the conditions of contact and / or heating result in hydrolysis of the hydrolyzable ligand L, and heating is carried out to form an oxo - hydroxo network, RSnO n (OH) 3-2n (where 0 < n < 3 / 2) to form a coating, or B) depositing on the substrate surface a solution comprising an organic solvent and the organotin composition described herein at a concentration of about 0.0025 M to about 1.4 M as measured based on the tin cation concentration to form an initial coating surface, and heating the substrate having the initial coating surface, wherein the conditions of deposition and / or heating result in hydrolysis of the hydrolyzable ligand L, and heating is carried out to form an oxo - hydroxo network, RSnO n (OH) 3-2n (where 0 < n < 3 / 2) to form a coating.

[0014] In a further aspect, the present invention relates to a method of patterning a substrate, the method comprising irradiating a substrate having an organotin coating with patterned EUV radiation to form a latent image, wherein the coating has an average thickness of about 1 nm to about 75 nm and forms an oxo - hydroxo network, of the formula RSnOn (OH) 3-2n having a composition represented by, where R is a hydrocarbyl ether group having 1 to 30 carbon atoms, and 0 < n < 3 / 2, forming, developing the latent image with a developer solvent to remove the unexposed coating to form a developed image, having a critical dimension of about 50 nm or less and a dose of about 80 mJ / cm 2 forming an image at the following dose. The organotin coating is A) contacting the substrate surface with the vapor of the organotin composition to form a deposit on the substrate surface, and heating the substrate having the deposit on the surface, wherein the conditions of contact and / or heating result in the hydrolysis of the hydrolyzable ligand L, heating to form an oxo-hydroxone network, RSnO n (OH) 3-2n (where 0 < n < 3 / 2), or B) depositing on the substrate surface a solution comprising an organic solvent and an organotin composition having a concentration of about 0.0025 M to about 1.4 M measured based on the tin cation concentration to form an initial coating surface, and heating the substrate having the initial coating surface, wherein the conditions of deposition and / or heating result in the hydrolysis of the hydrolyzable ligand L, heating to form an oxo-hydroxone network, RSnO n (OH) 3-2n (where 0 < n < 3 / 2) can be formed by forming a coating.

[0015] In a further aspect, the present invention relates to a method for synthesizing an organotin composition, the method comprising associating a hydrocarbyl halide compound (R-X, where X is a halide atom) with SnL associated with a metal cation M 3Reacting with an organometallic composition containing a moiety to form an alkali metal tin composition, wherein M is an alkali metal, an alkaline earth metal and / or a pseudo-alkaline earth metal (Zn, Cd or Hg), and L is either an amide ligand that results in an alkali metal tin triamide compound or an acetylide ligand that results in an alkali metal tin triacetylide compound, and performing the formation to correspondingly form a monohydrocarbyltin triamide (RSn(NR’ 2 ) 3 ) or a monohydrocarbyltin triacetylide (RSn(C≡CR s ) 3 ), where R s is SiR’’ 3 or R’, three R’’s are independently H or R’, and R’ is independently a hydrocarbyl group having 1 to 31 carbon atoms and optional unsaturated carbon-carbon bonds, optional aromatic groups and optional heteroatoms, and R is a hydrocarbyl ether group having 1 to 31 carbon atoms and optional unsaturated carbon-carbon bonds, optional aromatic groups and optional heteroatoms, represented by an aromatic ether of the formula Ar-O-(CR’ 2 ) m -, or a cyclic ether represented by the formula cyclic (O(CR’ 2 ) n CR’-), or a polyether represented by the formula R1R2R3C-, where Ar is an aromatic organic group, m is an integer from 1 to 4, each R’ is hydrogen, halogen or a hydrocarbyl group having 1 to 6 carbon atoms and optional heteroatoms, n is an integer from 1 to 8, and R1, R2 and R3 are independently hydrocarbyl groups having 1 to 19 carbon atoms, at least two of R1, R2, R3 are ether moieties, or at least one of R1, R2, R3 is a diether moiety. This method can be used to produce any of the organotin compositions described herein.

[0016] In a further aspect, the present invention relates to a method for synthesizing an organotin composition, the method comprising, in a solution containing an organic solvent, RMgX, R 2Zn, RZnNR’ 2 or an alkylating agent selected from the group consisting of combinations thereof with Sn(NR’ 2 ) 4 reacting, wherein X is a halogen, R’ is a hydrocarbyl group having 1 to 10 carbon atoms, and R is an aromatic ether represented by the formula Ar-O-(CR’ 2 ) m -, or a cyclic ether represented by the formula cyclic (O(CR’ 2 ) n CR’-), or a polyether represented by the formula R1R2R3C-, a hydrocarbyl ether group having 1 to 31 carbon atoms and optionally an unsaturated carbon-carbon bond, an optionally aromatic group and an optionally heteroatom, Ar is an aromatic organic group, m is an integer from 1 to 4, each R’ is hydrogen, a halogen or a hydrocarbyl group having 1 to 6 carbon atoms and optionally a heteroatom, n is an integer from 1 to 8, and R1, R2 and R3 are independently hydrocarbyl groups having 1 to 19 carbon atoms, at least two of R1, R2, R3 are ether moieties, or at least one of R1, R2, R3 is a diether moiety. This method can be used to produce any of the organotin compositions described herein.

Brief Description of the Drawings

[0017]

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Mode for Carrying Out the Invention

[0018] Organotin compositions having ligands containing oxygen atoms while forming C-Sn bonds can provide desirable patterning properties related to solubility characteristics in some patterning applications. In particular, certain ether ligands can provide solution stability of the desired precursor and sensitivity of the baked non-irradiated coating that is soluble in the desired developer solvent. To provide these characteristics, the selected ether ligand can have an aromatic ether structure or an alkyl group in which the ether oxygen atom is not directly bonded to the carbon atom providing the C-Sn bond. In some embodiments, the ether ligand can be a cyclic ether, a diether / polyether, or a fluorinated ether. Good patterning results can be obtained by improving the availability of the developer solvent. The organotin material has been shown to be effective in a photosensitive composition that can produce a high-resolution and smooth pattern while being highly sensitive to a suitable radiation source such as extreme ultraviolet (EUV).

[0019] Radiation-sensitive organotin compositions useful as high-resolution and high-sensitivity photoresists are described by Meyers et al. in U.S. Patent No. 9,310,684 entitled "Organometallic Solution Based High Resolution Patterning Compositions" and U.S. Patent No. 10,228,618 entitled "Organotin oxide hydroxide patterning compositions, precursors, and patterning" (hereinafter the '618 patent), both of which are incorporated herein by reference. Generally, radiation-sensitive organotin compositions contain organic ligands bonded to Sn atoms via Sn-C and / or Sn carboxylic acid bonds. Generally, when an organotin material is exposed to ionizing radiation (e.g., extreme ultraviolet light, ultraviolet light, ion beam) irradiation and then processed, it is thought that the Sn-C bonds are cleaved and a condensed metal oxo / hydroxone network containing Sn-O-Sn bonds and Sn-OH bonds is formed in the exposed region. As the concentration of these bonds increases, the material becomes a hydrophilic condensate compared to the state when only coated, resulting in a large chemical and development contrast between the irradiated and non-irradiated regions. Therefore, it is desirable to improve the cleavage efficiency of Sn-C bonds by irradiation. Without wishing to be bound by theory, the cleavage efficiency of Sn-C bonds is thought to be related to the stability of the hydrocarbyl species bonded to Sn via Sn-C bonds. In other words, it is expected that the lower the Sn-C bond dissociation energy (BDE), the higher the sensitivity of the organotin composition to radiation. In some embodiments described herein, it is a hydrocarbyl group having an Sn-C bond and containing an oxygen heteroatom that can affect solubility in a way that improves the solubility contrast during development.

[0020] It has also been found that using mixtures of patterning compositions provides additional aspects for engineering the overall coating properties. Oxygen-containing ligands with C-Sn bonds have provided acceptable EUV patterning results, but the greatest value of these compounds may lie in mixtures with other ligands that allow for arbitrary adjustment of the overall solubility properties of the patterning composition coating. In a non-limiting, predictive example, in compositions containing other organotin species that tend to form generally low-solubility hydrolyzates and condensates (e.g., MeSnL 3 , t BuSnL 3 ), including the organotin oxygen-heteroatom compositions described herein, can increase the overall solubility of the mixed composition and coating, and coatings and patterns with fewer defects such as particles, scum, microbridges, etc. can be obtained. Radiation-sensitive organotin materials generally provide a chemical contrast between irradiated and non-irradiated regions based on the conversion of hydrocarbyl-Sn bonds to Sn-O and / or Sn-OH bonds after exposure to ionizing radiation. Precursors for forming radiation-sensitive organotin compositions for lithographic patterning can generally be described by the formula R n SnL 4-n , where n = 1, 2, or 3, R is a hydrocarbyl ligand having an Sn-C bond, and L is a ligand having a hydrolyzable or hydrolysable Sn-L bond. As a commercial embodiment, there is interest in embodiments where n is about 1. When used in semiconductor lithography, radiation-patternable organotin coatings can generally be produced by promoting a hydrolysis and condensation process that converts monomeric organotin species to a polymeric organotin oxo / hydroxone network by exposing an R n SnL 4-n composition to water and / or other oxygen sources. Generally, either a solution-based deposition method or a vapor deposition method can be used. Hydrolysis to replace the hydrolyzable ligand with an oxo-hydroxone network can occur during and / or after deposition.

[0021] As described herein, the novel photosensitive organotin compound has one or more oxygen heteroatoms in the ether bond structure within the hydrocarbyl ligand of the organotin compound. In particularly interesting embodiments, the ether structure in the R ligand has an alkyl group such as an aromatic group or a cyclic alkyl group, in which case the oxygen atom is not directly bonded to the carbon bonded to the tin atom. Compositions having oxygen heteroatoms can be useful in photoresist compositions, and it has been shown that the presence of oxygen heteroatoms within the organic group provides advantageous properties. Further, the organotin compositions having oxygen heteroatoms described herein can be useful as photoresist compositions, either by themselves or as part of a mixed composition. The compositions described herein are based on the Applicant's initial research on tin having a C-Sn bond and a hydrocarbyl ligand for the three hydrolyzable ligands. The methyl methyl ether ligand is described in U.S. Patent Application Publication No. 2022 / 0064192 to Edson et al., entitled "Methods to Produce Organotin Compositions with Convenient Ligand Providing Reactants", which is incorporated herein by reference (hereinafter the '192 application). Comparative examples using the methyl methyl ether ligand are shown below. Herein, compositions with improved oxygen-containing ligands are described. The methyl methyl ether ligand of the '192 application forms a tin complex after hydrolysis to an oxohydroxy coating with limited solubility in polar solvents, particularly after heating the coating at low to moderate temperatures, such as during post-application baking or post-exposure baking. Herein, another oxygen-containing ligand is described to improve solubility in polar solvents.

[0022] This patterning process relies on the radiation-induced cleavage of hydrocarbyl ligands (R) bonded to tin (Sn) atoms within the oxo-hydroxomatrix of the patternable coating. After radiation absorption, a significant amount of energy from the radiation becomes available for breaking the carbon-tin bond, followed by the R group removing an atom or group to fragment and stabilize the fragmented R, for example, forming RH or ROH. These RH or ROH can be volatile, and as a result, the resulting compounds can leave the coating. Correspondingly, the Sn atom can capture ligands such as -OH or -O bonds. In this way, the irradiated coating can become an organic-species-released and more condensed oxo-hydroxonework. In this process, it is assumed that the fragmented R-based chemical species migrate from the coating before recombining with Sn, and it is considered that by enhancing the efficiency of such a process, patterning at a lower radiation dose can be facilitated.

[0023] The desorption efficiency of the R-based leaving group can depend on the process for forming a coating that can affect the chemical nature and density of the R group, similar to the post-irradiation treatment that promotes the desorption of the R-based chemical species. The desorption of the R-based chemical species can be tracked using spectroscopic techniques. In particular, Fourier transform infrared spectroscopy (FTIR) can be used in combination with intensity measurements from spectra used to quantify the residual degree of the organic group. The FTIR measurements can be adjusted using the vibration frequencies of known hydrocarbyl vibrations, and accordingly, the organic content of the coating can be monitored under different process conditions.

[0024] The removal of R-based species directly from radiation absorption can be called radiolysis, and the effectiveness of radiolysis for a specific radiation dose can be evaluated by FTIR after irradiation with measurements focused on the irradiated portion of the substrate. The post-exposure bake, which is performed after irradiation and before image development, can be utilized to promote the desorption of R-based species. Details of the post-exposure bake (PEB) are described later. The PEB process causes thermal decomposition by radiation, and the desorption of R-based species remaining in the irradiated region of the coating can be promoted. Under typical conditions generally used for PEB, thermal decomposition alone is not effective in removing R-based species from the coating. In other words, the non-irradiated coating generally has less depletion of organic species as a result of PEB and in the non-irradiated case. Nevertheless, thermal decomposition by radiation significantly promotes the depletion of organic chemical species from the irradiated coating and can reduce the dose required for coating processing.

[0025] Generally, the properties of a radiation - patterning - capable coating material can be evaluated at various stages of processing. For example, the composition of the ligand affects the stability of the solution of the precursor, i.e., its shelf - life. As will be described later, the solution of the precursor is also affected by the control of the solvent and the amount of water. The applicant has achieved significant progress in controlling the water content in order to improve the solution stability of the precursor and also obtain a highly reproducible stability of the precursor for commercial purposes. See U.S. Patent No. 11,300,876 to Jiang et al. entitled "Stable Solutions of Monoalkyl Tin Alkoxide and Their Hydrolysis and Condensation Products", which is incorporated herein by reference. Thereafter, the solution of the precursor is used to deposit a patterning - capable coating on a substrate. The deposited coating can also be heated to remove the solvent. Generally, the hydrolyzable ligand is removed during deposition and / or solvent removal and is replaced by oxo - hydroxy ligands within the network in the coating. The hydrolysis of the ligand can be contributed by the supplied water such as ambient water or water vapor. The solution properties of the precursor affect the properties of the resulting coating. Similarly, a mixture of precursors having different R groups is useful in balancing the process conditions.

[0026] In other embodiments, the thermal stability of a coating comprising an organotin compound having a hydrocarbyl ligand substituted with an oxygen heteroatom can be improved compared to a similar composition that does not contain an oxygen-containing ligand. Generally, organotin compounds decompose when heated to a sufficient high temperature, the Sn-C bond is cleaved, and the hydrocarbyl is released from the matrix, mostly becoming an inorganic Sn coating composition. For example, the hydrocarbyl ligand can be released from the coating to enhance the oxide / hydroxide characteristics of the coating composition (e.g., an increase in the amount of Sn-O bonds and / or Sn-OH bonds). Of course, the exact chemical composition of the coating depends on many factors such as the ambient atmosphere composition and the identity of the hydrocarbyl ligand. Some examples explaining the effects of different gases present in the atmosphere on organotin compositions are described in U.S. Patent Application Publication No. 2021 / 0271170 to Telecky et al. entitled "Process Environment for Inorganic Resist Patterning", which is incorporated herein by reference.

[0027] Furthermore, the oxygen heteroatoms within the hydrocarbyl ligand can provide a significant improvement in the solubility of the organotin composition in a selected solvent and solution stability, as compared to an unsubstituted organotin composition, and can improve the shelf life. For example, the oxygen heteroatoms within the hydrocarbyl group can increase the polarity, hydrogen bonding, and / or hydrophilicity of the organotin oxo / hydroxo (i.e., hydrolyzed) composition, and thus can improve the solubility in a suitable solvent. The normal processing and handling of an organotin solution can cause absorption of moisture from the surroundings or exposure to humidity, which can cause hydrolysis of the organotin species. The hydrolyzed organotin species in the photoresist solution can then react to form clusters and larger species, and further oligomerize / polymerize to form insoluble particles in the solution, and these insoluble particles can appear as defects within the coated wafer upon deposition. The compositions described herein can increase the solubility of the hydrolyzed species, thereby reducing the number of insoluble particles and the number of coating wafer defects formed. Another way to evaluate this improvement is the evaluation of the dose-versus-size measurement related to the critical size. By increasing the solubility of the unexposed regions of the film in a polar solvent, unexposed materials and lightly exposed materials, such as the material near the edge of the pattern, can be removed more completely. Furthermore, when the solubility of the unexposed or lightly exposed resist material is improved, scum and residues between features can be reduced. Thus, the radiation dose to achieve a desired feature size can improve the solubility of the intermediate composition near the pattern boundary and reduce potential non-uniformities within the irradiated material. It has also been observed that the patterning compositions having a desirable ether ligand improve the radiation-induced pyrolysis, which results in the removal of the organic species cleaved from the irradiated material.

[0028] In terms of imparting solubility in a highly polar solvent, cyclic ethers, aromatic ethers, fluoroethers, and polyethers can provide desirable ligands for the tin patterning composition. In particular, cyclic ethers, for example, of the formula [-CR(CR 2 ) n O], where n = 2 to 7 or -(CR2 ) n -[CR(CR 2 ) m O] may be present, where [] represents a cyclic structure with n = 1 to 10 and m = 2 to 7, R is hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms and optionally heteroatoms, and R 0 is a bond or a linear or branched hydrocarbyl group having 1 to 5 carbon atoms and optionally heteroatoms. In the first formula, the cyclic ether is directly bonded to the tin atom, and in the second formula, the cyclic ether is separated from the tin atom. The two formulas can be combined as [RR 0 C(CR 2 ) m O], where R 0 is a bond or a linear or branched hydrocarbyl group having 1 to 5 carbon atoms and any heteroatoms, and when R 0 is a bond, the cyclic ether is directly bonded to the Sn atom. The cyclic polyether has CR 2 substituted with -O-, and the cyclic ether can be a polycyclic compound having a plurality of independent rings or overlapping rings. In some polycyclic ethers, two R groups are bonded to form a ring structure.

[0029] The aromatic ether is an aromatic group pendant to the ether, such as -(CR 2 ) n O-(CR 2 ) m CR 3 , where n = 1 to 10, m = 0 to 9, R is hydrogen or a hydrocarbyl group having 1 to 5 carbon atoms optionally substituted with heteroatoms, and one or more H atoms are substituted with an aromatic group -Ar, and Ar is -C 6 H 5 , -C 5 NH 4 , -C 10 H 7 , -CH 2 C 6 H 5 , -C 6 H 4 C 6 H 5and the like. In another embodiment, the aromatic group is of the formula -(CH 2 ) n can be directly bonded to the ether oxygen by O-Ar, and -CH 2 OC 6 H 5 is mentioned as an example. Regarding linear (acyclic) polyethers, as described above, it may be desirable to move the ether oxygen away from the carbon bonded to the Sn atom. These ligands can be represented by the formula -CR 1 R 2 R 3 , where R 1 , R 2 , R 3 are independently H (two or less of the three R groups), or can be represented by -CR 4 R 5 R 6 , where R 4 , R 5 , R 6 are independently H (two or less of the three R groups), or at least one of R 4 , R 5 , R 6 is a hydrocarbyl group having an ether group, and the hydrocarbyl group generally has 1 to 8 carbon atoms. Thus, -CR 1 R 2 R 3 includes groups having a branched structure and two or more ether groups. Suitable polyethers can be linear, branched, and / or cyclic. Examples of polyether ligands include, for example, -CH 2 OCH 2 OCH 2 , -CH 2 CH(OCH 3 ) 2 , -cyclic(CHCH 2 OCH 2 CH 2 O), and the like. In any of the formulas in this paragraph, any of the H atoms can be substituted with a halogen atom (F, Cl, Br, or I) or a group based on another heteroatom, such as hydroxyl, amino, cyano, thio, silyl, ether, keto, ester, or a combination thereof.

[0030] In a further embodiment, the desired ligand can include halogen bonds and ether bonds and provide target solubility, optionally enhanced radiation absorbability, and desired binding properties. The formula R 1 OR 0 C(R 2 R 3 )- In an embodiment of the halogenated ether represented by, R 0 is a straight-chain or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and optional heteroatoms, and R 1 is a hydrocarbyl group having 1 to 10 carbon atoms with optional unsaturated bonds and / or optional heteroatoms, and R 2 and R 3 are independently hydrogen, a halogen, or a hydrocarbyl group having 1 to 7 carbon atoms with optional unsaturated bonds and / or optional heteroatoms, and at least one of R 1 , R 2 , R 3 has a halogen atom.

[0031] As components of a mixture composition for forming a radiation-sensitive coating, the radiation sensitivity, development efficiency, defect reduction, and pattern characteristics can be adjusted to achieve the desired patterning performance. Inclusion of a composition having an oxygen-containing ligand as described in the previous paragraph may be desirable when included in the mixed precursor composition used to form the radiation-sensitive coating, as it can affect developer efficiency and corresponding defect reduction. In some embodiments, the solution of precursors can include a mixture of precursor compounds, and a desirable precursor component having an ether group in a ligand having a C-Sn bond is present in a proportion of about 2 mole percent (mol%) to about 95 mol% of the ether-based precursor. Within this range of these broad mixtures of precursors, there can be desirable mixtures having a lesser amount of about 4 mol% to about 50 mol%, and in further embodiments about 5 mol% to about 40 mol% of ether-based ligands, as well as alternative mixtures having a majority of precursors having about 55 mol% to about 90 mol%, and in further embodiments about 70 mol% to about 85 mol% of ether-based ligands. Those skilled in the art will recognize that additional ranges of the proportion of precursors having oxygen-containing ligands within the above-explicit ranges are envisioned and are within the scope of the present disclosure.

[0032] The film-forming ability of an organotin composition having an oxygen-heteroatom within an ether group in a hydrocarbyl chain may be improved compared to that of an unsubstituted precursor composition. The oxygen heteroatom can strengthen the intermolecular bonds between species within an organotin oxo / hydroxocoating and can provide hydrogen-bonding sites that can enhance the film uniformity compared to an unsubstituted composition. Generally, the improvement in uniformity correlates with a low number of patterning defects, and the visual observation and evaluation of patterning defects can be a source of information for evaluating the coating uniformity.

[0033] The identity of the hydrocarbyl ligand of the organotin composition can also play an important role in the solubility of the partially and / or fully hydrolyzed organotin species after coating formation. RSnL 3 When hydrolyzed, the known ovoid dodecamer (RSn) 12 O14 (OH) 8 Clusters are formed, but the solubility of these clusters varies significantly depending on the identity of the R group. For example, when R = tert-butyl (-C(CH 3 ) 3 ), the resulting dodecamers are generally of low solubility, whereas when R = n-butyl (-(CH 2 ) 3 CH 3 ), the resulting dodecamers are much more soluble. In the organotin compositions having an ether group described herein, since an oxygen atom is present in the hydrocarbyl ligand, the solubility of the partial and complete hydrolyzates can be improved regardless of the possibility of cluster formation.

[0034] In some embodiments, pattern defects such as scum and microbridges can also be reduced in the presently disclosed compositions compared to unsubstituted organotin compositions. Without wishing to be bound by theory, pattern defects can be formed by unintentional radiation exposure in the space / shadow (i.e., regions not intended to be directly irradiated) of the pattern, whereby the Sn-C bond is cleaved and lightly polymerized species of RSn-O-Sn can be formed in the unintended regions. These lightly polymerized species are thought to be not fully exposed, i.e., only a small portion of the Sn-C bond is cleaved, yet they have low solubility in the developer and can remain after development and appear as defects in the pattern. The compositions described herein result in lightly polymerized species of high solubility and can thus reduce the amount of pattern defects.

[0035] The compositions described herein are useful as precursors for forming radiation-patternable coatings and for converting the precursors into other useful compositions, such as compositions having different hydrolyzable ligands or cluster-like compositions having Sn-O-Sn bonds. As noted above, the radiation sensitivity of the organotin materials results from the nature of the Sn-C bonds, and thus it is generally desirable for the Sn-C bonds to remain intact during processing from the precursor to the coating. For related embodiments, the hydrolyzable ligands have little effect on photosensitivity (i.e., substantially do not contain radiation-patternable coatings), and the hydrolyzable ligands can affect the properties of the hydrolyzed coatings with respect to specific structure and density, but are generally selected for desired processing such as further purification, deposition mode, stability, handling, etc. Generally, the hydrolyzable ligands can be hydrolyzed, if desired, prior to photopatterning to provide oxo ligands and / or hydroxy ligands. Some examples of suitable hydrolyzable ligands are -NR’ 2 , -OR’, -CCR’ 3 and -CC(SiR’ 3 ), where R’ is a hydrocarbyl group having 1 to 30 carbon atoms, such as -NMe 2 , -NEt 2 , -OiPr, -OtBu, -OtAmyl, -CC(C 6 H 5 ) [“PhAc”], -CC(Si(CH 3 )) 3 ) [“TMSA”], and the like. The current commercial products of the applicant are based on hydrolyzable ligands having the structure -OR’.

[0036] In one embodiment of forming a radiation-patternable coating, RSnL 3An organotin composition having an oxygen heteroatom in its R ligand is dissolved in a solvent and directly coated onto a substrate, optionally in the presence of water vapor, to produce a coating, and then further baked, additionally or alternatively, in the presence of water vapor to form a radiation-patternable organotin oxo / hydroxy coating. The presence of water vapor during coating deposition and / or during the pre-patterning bake step allows for in-situ hydrolysis to produce a radiation-patternable organotin oxo / hydroxy coating. A plurality of Rs where n = 0, 1 or 2 n SnL 4-n Compound (SnL 4 、RSnL’ 3 and R’SnL’’ 3 etc., where R and R’ may be the same or different, and L, L’ and L’’ may be the same or different) are mixed in a suitable solvent to readily deposit an organotin oxo / hydroxy film having the corresponding R n Sn composition.

[0037] In another embodiment, as described in the previous paragraph, the relatively high vapor pressure and reactivity of many molecular R n SnL 4-n compounds allows for the use of deposition methods for depositing a radiation-patternable organotin oxo / hydroxy coating. Possible deposition methods include, for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD) or modified versions thereof. For example, one or more gaseous R n SnL 4-n compounds are introduced into a reaction chamber and H 2By reacting with a co-precursor such as O or its related decomposition products, a radiation-sensitive organotin oxide hydroxide coating can be produced. Generally, when a hydrolyzable compound deposits on the surface in a subsequent hydrolysis reaction, this process can be considered as a PVD deposition involving in-situ hydrolysis. However, when hydrolysis occurs during a continuous deposition process, it can be considered as a CVD process. Similarly, when a hydrolyzable precursor is sequentially adsorbed, chemisorbed or decomposed on the substrate surface, and a residual film reacts with a second reactive precursor through a plurality of deposition / reaction cycles to deposit the corresponding organotin oxide hydroxide, it can be considered as an ALD process. The advantages of the vapor deposition method include reduction of the defect density of the resist film, improvement of the thickness and composition uniformity, and conformal and sidewall coating of the substrate topography.

[0038] Organotin compositions containing oxygen heteroatoms The precursor of a radiation-sensitive organotin composition having an oxygen heteroatom has the formula R 1 -O-R 2 SnL 3 and can be represented by, where R 1 has 1 to 30 carbon atoms and is selected from linear, aromatic, cyclic, branched or unsaturated hydrocarbyl ligands optionally further substituted with O, F, I, Si, Sn, Te and / or Sb, and R 2 is a hydrocarbyl ligand having a Sn-C bond and 2 to 5 carbon atoms, and L is a hydrolyzable ligand. In some embodiments, the R 1 or R 2 moiety may include a linear, branched or cyclic group having one or more ethers. In some embodiments, R 2 includes a branched carbon atom, i.e., a carbon atom having one or fewer C-H bonds. In a further embodiment, R 1 and R 2 form a ring structure such that one or more O atoms are part of a cyclic ether, and R 1 -O-R 2 is evenly cyclic (-CH[(CH 2 ) n:o O(CH 2 )m:o o) and can be described as Σ o (n:o + m:o + 1) + 2 is the size of the ring, where n + m ≥ 1 and o ≥ 1, and m and n can vary depending on the value of o. In embodiments where a cyclic ether is present, the alkyl moiety can be present between the cyclic ether and the Sn atom, and the formula (-R L [(CH 2 ) n:o O(CH 2 ) m:o o ) can be represented, and RL is a hydrocarbyl ligand having an Sn - C bond and having 2 to 10 carbon atoms. Desirable classes of ether ligands are described in detail throughout this specification and supplement this particular discussion directly.

[0039] R 1 -O-R 2 Some specific examples of structures represented by the formula of Sn are shown below.

Chemical formula

[0040] ​The synthesis of the oxygen-heteroatom organotin compositions disclosed herein has been described previously by the applicant using methods such as those described in U.S. Patent Application Publication No. 2019-0315781 by Edson et al. entitled "Monoalkyl Tin Compounds With Low Polyalkyl Contamination, Their Compositions And Methods" and the '192 application cited above, both of which are incorporated herein by reference. The choice of synthesis technique can be based on practical aspects such as the purity, yield, simplicity of procedure, and availability of simple starting materials obtained by various routes. For example, in the general synthesis of monoalkyltin trialkylamides, desirable results have been obtained when the alkylating agent is a Grignard reagent, a diorganozinc reagent, or a monoorganozinc amide. These syntheses can directly produce monoalkyltin triamides with low polyalkyl contaminants that can be used to form resists or further purified to reduce contaminant levels even further. In a further method developed by the applicant, the alkylating agent is an alkyl halide that reacts with a tin composition complexed with an alkali, an alkali metal ion, and / or a pseudo-alkali metal ion. Unless otherwise indicated, the synthesis process and storage of the compositions are carried out in a state isolated from the ambient atmosphere, such as in a glove box, a closed system, or a sealed container.

[0041] In some embodiments, a Grignard-type reaction can be utilized to synthesize the desired R 1 -O-R 2 SnL 3 compound. The general Grignard reaction to form R 1 -O-R 2 SnL 3 can be represented by the following reaction. RMgX + SnL 4 → RSnL 3

[0042] In some embodiments, the oxidative stannylation reaction is the desired route for forming the desired R 1 -O-R 2 SnL 3 compound, as further described in the '192 application cited above. In a typical oxidative stannylation reaction, a tin dihalide (e.g., SnCl 2 ) is first reacted with an organoalkali (R'M, e.g., R'Li) compound to form an alkali metal stannamide or alkali metal stannylacetylide, which is then reacted with an organic halide containing the desired R group that is to be bonded to the tin atom. The synthesis can be represented by the following reactions. 3R’M + 3HL + SnX 2 → MSnL 3 MSnL 3 + RX → RSnL 3

[0043] In the above reactions, the organotin RSnL 3 product generally contains an amide or acetylide as the hydrolyzable ligand L. In some embodiments, the hydrolyzable ligand L is an amide, such as -NMe 2 , -NEt 2 , -NiPr 2 , etc. Amides are particularly suitable as hydrolyzable ligands for the vapor treatment of organotin oxide hydroxide coatings due to their high vapor pressure and high reactivity, and are also suitable for the conversion to the corresponding organotin alkoxide. In some embodiments, the hydrolyzable ligand is an acetylide. Organotin acetylide (RSn(C≡CR')) 3 is particularly suitable as a precursor for preparing the corresponding organotin alkoxide, and particularly useful R' groups are trialkylsilyl, such as -Si(CH 3 ) 3 [「TMSA」], -Si(CH 2 CH 3 ) 3, [「TESA」], and phenyl (「PhAc」). Generally, the efficient conversion of an organotin acetylide to the corresponding organotin alkoxide depends on the alcohol, the identity of the R and R’ groups, and can be obtained by routine experiments.

[0044] In some embodiments, the hydrolyzable ligand of the radiation patterning precursor composition is an alkoxide. Alkoxides can be particularly suitable as hydrolyzable ligands for the treatment of oxide hydroxide coatings by either solution treatment or vapor treatment due to their storage stability, hydrolysis sensitivity, relatively mild hydrolysis products such as alcohols, and vapor pressure for vapor deposition. The conversion of organotin amides and acetylides to organotin alkoxides generally follows the following reactions: RSn(NR’ 2 ) 3 + 3R’’OH → RSn(OR’’) 3 + 3HNR’ 2 , or RSn(CCR’) 3 + 3R’’OH → RSn(OR’’) 3 + 3HCCR’ (wherein R’ and R’’ are the same or different and are usually alkyl groups having 10 or fewer carbon atoms) can be achieved by alcoholysis as described by. Particularly suitable R’ groups and R’’ groups are methyl, ethyl, propyl, butyl, pentyl (amyl), phenyl, and, where applicable, their respective isomers such as tert - amyl, etc.

[0045] R 1 -O-R 2 SnL 3Once produced, the compound can be further purified by any suitable means such as distillation to obtain a suitably pure composition. Purification varies depending on the nature of the compound but generally involves separating the desired product from by-products and potentially any unreacted reagents. Purification can also include removing volatile compounds such as solvents from the product mixture by drying or exposure to vacuum. For products with significant vapor pressure, it is desirable to purify and highly purify the product by vacuum distillation or fractional distillation as necessary. See U.S. Patent Application Publication No. 2020 / 0241413 to Clark et al. entitled "Monoalkyl Tin Trialkoxides and / or Monoalkyl Tin Triamides With Low Metal Contamination and / or Particulate Contamination and Corresponding Methods" (hereinafter the "'413 application"), which is incorporated herein by reference.

[0046] It is also possible to react the initially purified or unpurified product to form derivatives such as organotin trialkoxides, which can be further purified by the above techniques and other means known in the art. After preparation of the trialkoxide composition, further purification of the composition can be carried out as necessary. In some embodiments, a fractional distillation method can be used as described in U.S. Patent No. 10,787,466 to Edson et al. entitled "Monoalkyl tin compounds with low polyalkyl contamination, their compositions and methods", which is incorporated herein by reference.

[0047] The purity can be evaluated by the presence of undesirable impurities such as metals other than Sn or undesirable by-products. In semiconductor applications where trace impurities, such as non-Sn trace metals, can affect the nano-scale properties, it is desirable for the organotin compound to be of high purity. The purity of the metal can generally be evaluated by any suitable means known in the art, such as mass spectrometry techniques including inductively coupled plasma mass spectrometry (ICP-MS) and similar techniques. In some embodiments, R 1 -O-R 2 SnL 3 compounds can have a metal purity greater than about 99.99% (<100 ppm non-Sn metals), in other embodiments greater than about 99.999% (<10 ppm non-Sn metals), in further embodiments greater than about 99.9999% (<1 ppm non-Sn metals), and in still further embodiments greater than about 99.99999% (<0.1 ppm non-Sn metals). In some applications, it may be desirable to be of high purity on a mass ratio basis relative to other tin compounds (i.e., impurities). Optionally, the synthesis of the organotin compound can result in by-product impurities. Optionally, the synthesis of the organotin compound can produce a mixture of tin-containing reaction products (e.g., a majority of the target monoalkyltin compound with small amounts of dialkyltin and / or inorganic tin impurities present in the product), and the separation and purification of the single-phase monoalkyltin can be difficult. Nuclear magnetic resonance (NMR) and gas chromatography mass spectrometry (GC-MS) techniques are useful for analyzing the purity of organotin compounds such as the oxygen-heteroatom organotin compositions disclosed herein. In some embodiments, R 1 -O-R 2 SnL 3 compounds can have a purity of at least about 90% by mass, in other embodiments at least about 95% by mass, in further embodiments at least about 99% by mass, and in other embodiments at least about 99.9% by mass.

[0048] Solution composition The organotin compounds described herein are useful as precursors for forming radiation-patternable coatings for semiconductor lithography applications. Thus, the organotin compounds are suitable for producing smooth, uniform, and dense coatings that enable high-resolution patterning by EUV lithography due to their high absorption at EUV wavelengths and high etching resistance. In some embodiments, the organotin compounds described herein can be dissolved in a solvent to form an organotin photoresist solution, enabling solution deposition onto the radiation-patternable coating.

[0049] Suitable solvents include those in which the organotin photosensitive composition dissolves preferably, and the solvent can be further selected based on physical properties such as flammability, viscosity, toxicity, or volatility, considering the processing approach used. Further considerations for selecting a suitable solvent can include potential interactions with partially and / or fully hydrolyzed organotin species, such as alleviation of undesirable particle formation and aggregation. In some embodiments, although not wishing to be limited by theory, primary alcohols can be beneficial in the solvent composition because of their ability to impede hydrolysis and can also further improve the interaction and solubilization with organotin hydrolyzates and condensation products. Other points to consider as suitable solvents are cost and the possibility of interaction with other processing materials. Some examples of suitable solvents include alcohols (e.g., 4-methyl-2-pentanol, 1-butanol, cyclohexanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 2-isopropoxyethanol), esters (e.g., ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate), ethers (e.g., propylene glycol monomethyl ether), ketones (e.g., 2-heptanone, cyclopentanone, cyclohexanone, 1-butanone, 4-methyl-2-pentanone), mixtures thereof, and the like. Those skilled in the art will understand that other suitable solvents not explicitly listed are contemplated.

[0050] The organotin solution composition can be simply specified based on the molar concentration of tin ions. Generally, the organotin solution contains tin cations in an amount of about 0.0025 M to about 1.4 M, in some embodiments about 0.004 M to about 1 M, in yet some other embodiments about 0.005 M to about 0.75 M, in additional embodiments about 0.01 M to about 1 M, and in still some other embodiments about 0.01 M to about 0.5 M. Those skilled in the art will recognize that additional concentration ranges and values within the above-explicit ranges are contemplated and are within the scope of the present disclosure.

[0051] In some embodiments, the oxygen - heteroatom - ether organotin composition may be present in a mixed solution with one or more other monoalkyltin compounds and / or other organotin compositions, such as R n SnL 4-n and its hydrolysis products, where n is 0, 1, or 2, and R is another ligand having the same overall structure as R 1 -O-R 2 defined above, or R is a linear, branched, cyclic, aromatic, and / or substituted hydrocarbyl group having an Sn-C bond. Such a mixed solution, such as aR’SnL 3 +(1 - a)R’’ n SnL’ 4-n (where “a” is the proportion of the organotin compound containing the original ether) can be adjusted for optimizing various properties such as solution stability, coating uniformity, and patterning performance. The mixed composition can be achieved by combining two or more organotin compositions such as R n SnL 4-n where L is a hydrolyzable ligand, with or without a solvent. For example, combining RSnL 3 alone with R’SnL’ 3It can be used as a mixed precursor together with the monomer. The mixed composition can be diluted in a solvent if necessary. Alternatively, the individual organotin compositions can be diluted in a desired solvent to form different organotin solutions, and then the individual organotin solutions can be combined to form a mixed solution. Generally, the hydrolyzable ligands can be the same or different for each individual organotin component of the entire mixed composition. In some embodiments, the oxygen-heteroatom-ether composition can contain at least 1 mol%. In further embodiments, the Sn in the mixed solution is at least 10 mol%. In further embodiments, the Sn in the mixed solution is at least 25 mol%. In further embodiments, the Sn in the mixed solution is at least 75 mol%. It is the Sn in the mixed solution. Additional ranges of mol% of the oxygen-heteroatom organotin composition are also envisioned and are also within the scope of the present disclosure.

[0052] In some embodiments, the organotin photoresist solution can be filtered to remove or reduce particulate contaminants. Suitable filtration methods are described in U.S. Patent No. 11,498,934 to Clark et al. entitled "Monoalkyl Tin Trialkoxides And / Or Monoalkyl Tin Triamides With Low Particulate Contamination and Corresponding Methods", which is incorporated herein by reference.

[0053] In some embodiments, the organotin photoresist solution can be partially hydrolyzed in solution (i.e., controlled in-situ hydrolysis) by adding a controlled amount of water to the organotin photoresist solution composition. A suitable method for adding a controlled amount of water to the organotin photoresist solution is described in U.S. Patent No. 11,300,876, entitled "Stable Solutions Of Monoalkyl Tin Alkoxides And Their Hydrolysis And Condensation Products" to Jiang et al., which is incorporated herein by reference (hereinafter the '876 patent). Without wishing to be bound by theory, controlled in-situ hydrolysis is thought to allow for a more favorable distribution and concentration of clusters and similar species for solution-based depositions such as spin coating by allowing some hydrolysis and condensation to occur prior to deposition. In this way, as taught by the '876 patent, a balance between solution stability and film quality can be obtained by varying the combination of water concentration and solvent in the organotin photoresist solution. The stability of the precursor solution can be evaluated by visual observation of the solution for particle formation and / or gelation over time. Commercially available precursor solutions generally have a suitable shelf life that can exceed one month.

[0054] Radiation patterning capable coating A radiation patterning capable coating can be formed by deposition of a photosensitive composition onto a selected substrate and subsequent processing. Deposition of the radiation patterning capable coating can be accomplished by a variety of means known to those skilled in the art.

[0055] Generally, after removal of any hydrolyzable ligands by hydrolysis and formation of an oxo-hydroxone network, it is desirable to perform an irradiation step for patterning. Thus, the stable precursor solution is appropriately converted between deposition and irradiation. Deposition of the radiation-sensitive organotin precursor composition onto a radiation-patternable coating is generally achieved by hydrolysis and condensation processes. For example, solution deposition of a radiation-patternable organotin coating is described in the Meyers reference above. Vapor deposition techniques employing hydrolysis / condensation-based reactions are also incorporated by reference in the pamphlet of Published PCT Patent Application International Publication No. 2019 / 217749 to Wu et al. entitled "Methods for Making EUV Patternable Hard Masks" and in the '618 patent above. In either case, the radiation-sensitive organotin composition can be significantly converted to an organotin hydroxide oxide in which the radiation-sensitive organic ligand having an Sn-C bond to the Sn atom is incorporated into a loosely associated network of Sn-O-Sn and Sn-OH bonds. In the case of the organotin composition having an oxygen heteroatom described herein, the radiation-patternable coating can have additional intermolecular and / or network bonds. The presence of an oxygen atom within the hydrocarbyl chain can enable intermolecular hydrogen bonding and / or polar interactions within the organotin oxo / hydroxone network.

[0056] When solution deposition is desired, a particularly useful solution deposition method is spin coating. Spin coating is well known in the art and can be particularly useful in photoresist processing in semiconductor manufacturing. In a typical spin coating method, a photoresist solution is supplied to the surface of a substrate such as a Si wafer, and the substrate is rapidly rotated to form a coating. During the spin coating process, the hydrolyzable ligands of the organotin precursor composition react with ambient water to undergo significant hydrolysis and condensation, forming a coating on the substrate that includes Sn—O—Sn and Sn—OH networks along with radiation-sensitive Sn—C bonds. In some embodiments, the improved photoresist precursor solution is spin coated at a spin rate of 500 to 3000 rpm. The rotation speed used is not particularly limited, but is generally adjusted to obtain the desired coating thickness. Generally, for a given photoresist solution, a lower rotation speed results in a thicker coating than a higher rotation speed. One of ordinary skill in the art will understand the relationship between rotation speed and coating thickness.

[0057] The thickness of the radiation-patternable coating varies depending on the desired process. When used for single-patterning EUV lithography, the coating thickness is generally selected such that a pattern with few defects and high patterning reproducibility is obtained. In some embodiments, a suitable coating thickness is from 1 nm to 100 nm, in some embodiments from about 1 nm to about 75 nm, in further embodiments from about 1.5 nm to 50 nm, and in further embodiments from about 2 nm to 25 nm. One of ordinary skill in the art will envision further ranges of coating thicknesses and understand that they are within the scope of the present disclosure.

[0058] In other embodiments, the radiation-patternable coating can be formed by various deposition methods such as atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD). In typical deposition techniques, generally, one or more metal-containing precursors serve as sources of O and H for the production of oxides and oxyhydroxides, H 2 O, H 2 O2 、 O 3 、 O 2 or CH 3 It can react with small molecule gas phase reagents such as OH one or more times. Therefore, the hydrolyzable compound can be directly deposited via hydrolysis during the vapor deposition process as the corresponding alkyltin oxide hydroxide coating, which can then be appropriately patterned.

[0059] In the CVD method, usually, two or more reaction gases are mixed in the chamber near the substrate surface. Therefore, in order to control undesirable gas phase reactions and nucleation, sufficient stability can be designed for the reaction conditions. The ALD precursors introduced separately and sequentially into the reaction chamber typically react with chemisorbed co-precursors or decomposition products to saturate the substrate surface. RSnL 3 Desirable characteristics of the precursor include, for example, sufficient volatility for gas phase transport within the system, thermal stability to prevent premature decomposition, and appropriate reactivity with co-precursors to produce the desired product under predetermined process conditions, etc. In some embodiments, RSnL 3 The precursor may include an alkoxide (e.g., L = OR) or a dialkylamide (e.g., L = NR 2 ). The pressure and temperature in the reaction chamber can be selected to control the reaction process.

[0060] The thickness of a radiation-patternable coating fabricated by a vapor deposition technique can generally be controlled by appropriately selecting the reaction time or the process cycle. The thickness of the radiation-patternable coating varies depending on the desired process. When used for single-patterning EUV lithography, the thickness of the coating is generally selected such that a pattern with few defects and high patterning reproducibility can be obtained. In some embodiments, an appropriate coating thickness is from 1 nm to 100 nm, in some embodiments from about 1 nm to about 75 nm, in further embodiments from about 1.5 nm to 50 nm, and in further embodiments from about 2 nm to 25 nm. Those skilled in the art will understand that additional ranges of the coating thickness are envisioned and are within the scope of the present disclosure.

[0061] The substrate generally presents a surface on which a coating material can be deposited, and the surface can include a plurality of layers associated with the outermost layer. The substrate is not particularly limited and can include any reasonable material such as other inorganic materials like silicon, silica, ceramics, and polymer materials.

[0062] After the deposition and formation of the radiation-patternable coating, further processing can be performed before exposure to radiation. In some embodiments, the coating can be heated to a temperature of 30 °C to 300 °C, in further embodiments to a temperature of 50 °C to 200 °C, and in further embodiments to a temperature of 80 °C to 150 °C. The heating can be carried out for about 10 seconds to about 10 minutes in some embodiments, for about several seconds to about 5 minutes in further embodiments, and for about 45 seconds to about 2 minutes in further embodiments. For the temperature and heating time, additional ranges within the above explicit ranges are envisioned and are within the scope of the present disclosure.

[0063] Patterning of the Composition Generally, radiation can be irradiated onto a substrate coated through a mask, or can be scanned while controlling a radiation beam across the substrate. Generally, radiation can include electromagnetic radiation, an electron beam (beta rays), or other suitable radiation. Generally, electromagnetic radiation can have a desired wavelength or wavelength range, such as visible radiation, ultraviolet radiation, X-ray radiation, etc. The resolution achievable for a radiation pattern generally depends on the radiation wavelength, and generally, a higher-resolution pattern can be achieved with shorter-wavelength radiation. Therefore, in order to obtain a particularly high-resolution pattern, it may be desirable to use ultraviolet rays, X-rays, or an electron beam.

[0064] In accordance with the international standard ISO21348 (2007), which is incorporated herein by reference, ultraviolet rays range between wavelengths of 100 nm or more and less than 400 nm. A krypton fluoride laser can be used as a 248-nm ultraviolet light source. The ultraviolet region can be subdivided in several ways according to generally recognized criteria, such as extreme ultraviolet (EUV) of 10 nm or more and less than 121 nm, far ultraviolet (FUV) of 122 nm or more and less than 200 nm, etc. The 193-nm line from an argon fluoride laser can be used as a radiation source for FUV. EUV light with a wavelength of 13.5 nm is used in lithography, and this light is generated from a Xe or Sn plasma light source excited by a high-energy laser or a discharge pulse. Soft X-rays can be defined as 0.1 nm or more and less than 10 nm.

[0065] During exposure to radiation such as ultraviolet (UV) rays, extreme ultraviolet (EUV) rays, or an electron beam, and subsequent processing, Sn-C is cleaved, resulting in a more condensed hydrophilic oxide hydroxide network. The lower the relative concentration of organic ligands in the exposed area, the higher the polarity and hydrophilicity of the exposed area.

[0066] Based on the design of the coating material, there can be a large contrast in material properties between the irradiated area where the coating material has condensed and the unirradiated coating material having substantially intact Sn-C bonds. In embodiments where post-irradiation heat treatment is used, the post-irradiation heat treatment can be carried out at a temperature of about 45°C to about 300°C, in a further embodiment about 50°C to about 250°C, and in a further embodiment about 75°C to about 200°C. The post-exposure heating can generally be carried out over at least about 0.1 minute, in a further embodiment about 0.5 minute to about 30 minutes, and in a further embodiment about 0.75 minute to about 10 minutes. One skilled in the art will envision further ranges of post-irradiation heating temperatures and times within the above-defined ranges and will recognize that they are within the scope of the present disclosure. The post-irradiation bake step may facilitate the removal of radiation-fragmented organic groups, generally R-, which presumably react with other groups to form stable species that leave the coating. The disappearance of organic species from the coating can be confirmed by spectroscopic measurements such as Fourier transform infrared that can measure the vibrations of carbon. This high contrast in material properties further facilitates the formation of high-resolution lines with smooth edges in the pattern after development, as described in the following section.

[0067] Generally, an organotin photoresist can be developed either as a negative or positive type based on the chemical identity of the developer. Nevertheless, in order to improve a particular patterning format, ligands more suitable for the particular patterning format can be suggested. Many of the ether-containing ligands are optimal for negative patterning. The choice of developer can be affected by the solubility parameters regarding the coating material as well as the volatility, flammability, toxicity, viscosity of the developer and potential chemical interactions with other process materials, regardless of irradiation and non-irradiation. As shown in the examples, the organotin coating compositions having oxygen heteroatoms described herein can exhibit significantly different developer solubilities as compared to unsubstituted organotin compositions. Generally, monoalkyltin compositions are mostly nonpolar / hydrophobic due to the presence of alkyl ligands within the unexposed regions of the coating, thus showing negative behavior in organic solvents and therefore imparting solubility to these regions in organic solvents. Similarly, the irradiated regions of the coating are deficient in alkyl ligands and rich in Sn-OH / Sn-O-Sn bonds, resulting in increased polarity / hydrophilicity and increased solubility in polar solvents and / or acid-base solvents. As described above, organotin compounds having oxygen heteroatoms can exhibit an increase in polarity and / or hydrogen bonding ability, thus showing an increase in the interaction between the oxygen heteroatoms within the hydrocarbyl ligand and the polar developer solvent. The ability to effectively use more polar solvents can be effective in forming improved pattern edges with fewer defects. Similar improvements may be possible for dry development by the choice of development conditions.

[0068] In the case of negative imaging, generally, the developer can be an organic solvent such as a solvent used to form a precursor solution. Generally, the choice of developer can be affected by the solubility parameters for the coating material as well as the volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials, regardless of irradiation and non-irradiation. In particular, 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), ketones (pentanone, hexanone, 2-heptanone, octanone), and the like. Development can be carried out over a period of about 5 seconds to about 30 minutes, in a further embodiment about 8 seconds to about 15 minutes, and in a further embodiment about 10 seconds to about 10 minutes. One of ordinary skill in the art will recognize that additional ranges within the above explicit ranges are contemplated and are within the scope of the present disclosure. In addition to the main developer composition, the developer can include additional compositions to facilitate the development process. Suitable additives include, for example, viscosity modifiers, solubilization aids, and other processing aids. If any additives are present, the developer can include up to about 10 wt% additives, and in a further embodiment up to about 5 wt% additives. One of ordinary skill in the art will recognize that additional ranges of additive concentrations within the above explicit ranges are contemplated and are within the scope of the present disclosure. The developer mixtures and additives are further described in U.S. Patent Application Publication No. 2020 / 0326627 to Jiang et al., entitled "Organometallic Photoresist Developer Compositions and Processing Methods", which is incorporated herein by reference.

[0069] In some embodiments, the solventless (dry) development process can be performed using a suitable thermal or plasma development process, such as those described in the PCT patent application publication WO 2020 / 264158 to Tan et al. entitled "Photoresist Development With Halide Chemistries", which is incorporated herein by reference. In the case of an organotin photoresist coating, a halogen-containing plasma and gas, such as HBr and BCl 3 can be used for dry development. Optionally, dry development can offer advantages such as reducing pattern collapse, scum, and fine control of the developer composition, i.e., the plasma gas and / or etch gas, compared to wet development.

[0070] After completion of the development step, the coating material can be heat-treated to further condense the material and further dehydrate, densify, or remove residual developer from the material. This heat treatment can be particularly preferably used in embodiments where the oxide coating material is incorporated into the final device, but may also be desirable for heat treatment in some embodiments where the coating material is used as a resist and is ultimately removed, if stabilization of the coating material is desired to facilitate further patterning. In particular, the bake of the patterned coating material can be performed under conditions where the patterned coating material exhibits a desired level of etch selectivity. In some embodiments, the patterned coating material can be heated to a temperature of about 100°C to about 600°C, in further embodiments about 175°C to about 500°C, and in further embodiments about 200°C to about 400°C. The heating can 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 minutes to about 25 minutes. The heating can be carried out in air, in a vacuum, or in an inert gas atmosphere such as Ar or N 2 2. Such inert gas atmospheres can be used. Those skilled in the art will recognize that additional ranges of heat treatment temperature and time are envisioned within the above explicit ranges and are within the scope of the present disclosure. Similarly, blanket UV exposure or O 2Non-thermal treatments, including exposure to an oxidation plasma or the like, can also be used for the same purpose.

[0071] Wafer throughput is a factor that substantially limits the implementation of EUV lithography in high-volume semiconductor manufacturing and is directly related to the dose required to pattern a given feature. However, although there are chemical strategies to reduce the imaging dose, in EUV photoresists, a negative correlation is generally observed between the imaging dose required to print the target characteristics and the uniformity of feature size (such as LWR) at feature sizes and pitches less than 50 nm. As a result, the operability of the final device and the wafer yield are limited. The patterning performance can be represented by the dose-to-gel value. By forming an exposure pad array, changing the exposure time stepwise for each pad, and varying the exposure dose, the required imaging dose can be evaluated. Then, the film can be developed, and the remaining resist thickness can be evaluated for all pads using, for example, spectroscopic ellipsometry. A characteristic curve can be created by normalizing the measured thickness by the maximum value of the measured resist thickness and plotting it against the logarithm of the exposure dose. The maximum gradient of the normalized thickness versus logarithm dose curve is defined as the photoresist contrast (γ), and the dose value at which the tangent line passing through this point equals 1 is defined as the photoresist dose-to-gel ratio (Dg). D 0 corresponds to the onset dose of the initial increase in the film thickness of the negative resist. In this way, the general parameters used for photoresist characteristic evaluation can be approximated according to Mack, C. ("Fundamental Principles of Optical Lithography", John Wiley & Sons, Chichester, U.K.; pp 271-272, 2007, incorporated herein by reference).

[0072] The patterned structure can be evaluated using an automated imaging device, typically using the imaging device of a scanning electron microscope. For example, certain commercially available CD-SEM devices can measure critical line sizes (line widths) and also evaluate defects such as microbridging. In some embodiments, the patterning by improved development based on the resist engineering described herein can result in an increase in critical dimensions with uniform development, coating formation, and irradiation. Viewed another way, the concept of the limit size can be represented as a dose-versus-size value, which is the radiation dose used to obtain a particular feature size. Thus, an increase in the limit size corresponds to a decrease in the dose-versus-size value, which is consistent with being able to use a lower dose to achieve a particular patterning goal. As shown in the results, in the mixed resist, 30 mJ / cm 2 Based on the following dose, the dose-versus-size based on a critical size of 16 nm could be obtained.

Example

[0073] Example 1: R 1 OR 2 -Sn-L 3 Synthesis of compounds The following examples include the synthesis and NMR property evaluation of R 3 tris(trimethylsilylacetylide) (TMSA) 3 and tris(tert-butoxide) (OtBu) 1 OR 2 SnL 3 compounds having a hydrolyzable ligand group L. As the R 1 OR 2 - group, CH 3 OCH 3 CH- or methoxyethyl (MOE), CH 3 OCH 2 - or methoxymethyl (MOM), CH 3 O(CH 3 ) 2 C- or methoxypropyl (MOP), [(CH 2 ) 2 OCH 2CH]- or 3 - tetrahydrofurfuryl (THF), [(CH 2 ) 2 O(CH 2 ) 2 CH]- or 4 - tetrahydropyranyl (THP), [(CH 2 ) 2 O(CH 2 ) 2 C(CH 3 )]- or 4 - methyl - 4 - tetrahydropyranyl (mTHP), methyl - tert - butyl ether or (CH 3 ) 3 COCH 2 -(MTBE), methyl phenyl ether or C 6 H 5 OCH 2 -(MPE), dimethoxyethyl or (CH 3 O) 2 CHCH 2 -(DME) and trifluoroethoxymethyl or CF 3 CH 2 OCH 2 -(FET) etc. may be mentioned. The synthesis reaction was carried out using an oxidative stannylation reaction, except for two syntheses using the Grignard reagents described below.

[0074] (CH 3 OCH(CH 3 )Sn(CC(SiCH 3 )) 3 , MOE - Sn - (TMSA) 3 of synthesis Ethynyltrimethylsilane (3.1 equivalents) and diethyl ether (1.5 mL / equivalent) were added to a vacuum-purged reaction vessel equipped with a thermometer, a stirrer, and an addition funnel. The solution was cooled below 0 °C, and n-butyllithium (2.0 M in diethyl ether, 3.0 equivalents) was slowly added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred for 30 minutes, and tin(II) chloride (1 M in THF, 1.0 equivalent) was added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred at 20 °C for 2 hours. Then, the internal temperature was brought below 0 °C, and 1-chloro-1-methoxyethane (1.1 equivalents) was added while maintaining the internal temperature below 10 °C. The solution was stirred for an additional 30 minutes, and the volatiles were removed under vacuum. The solid was washed with pentane and filtered. The volatiles were removed under vacuum, and recrystallization from hexane (ca. 1 mL / 1 g of product) was carried out at -20 °C to give MOE-Sn-(TMSA) 3 as a crystalline solid. The 1H and 119Sn NMR spectra of MOE-Sn-(TMSA) 6 in benzene-d 3 are shown in Figures 1 and 2, respectively. The spectra showed the following chemical shifts: 1 1H NMR (C 6 D 6 ) δ 0.1 (s, 27H, CH 3 ), δ 1.7 (d, 3H, CH 3 ), δ 3.3 (s, 3H, CH 3 ), δ 3.9 (q, 1H, CH); 119 119Sn NMR (C 6 D 6 ) δ -323.

[0075] Conversion of MOE-Sn-(TMSS) 3 to (CH 3 OCH(CH 3 )Sn(OtBu) 3 and MOE-Sn-(OtBu) 3 MOE-Sn-(TMSA) 3 and 2% Cu(OtBu) were placed in an inerted flask equipped with a stir bar. tert-Butanol (10 equivalents) and triethylamine (10 equivalents) were added, and the volatiles were slowly removed to give a viscous liquid. Benzene-d 6 ​MOE-Sn-(OtBu) in 3 The 1H and 119Sn NMR spectra of are shown in Figures 3 and 4, respectively. The spectra showed the following chemical shifts: 1 H NMR(C 6 D 6 ) δ1.3(s,27H,CH 3 ), δ1.5(d,3H,CH 3 ), δ3.3(s,3H,CH 3 ), δ3.9(q,1H,CH); 119 Sn NMR(C 6 D 6 )δ-271.

[0076] (CH 3 ) 2 COCH 3 Sn(CC(SiCH 3 )) 3 , MOP-Sn-(TMSA) 3 Synthesis of Ethynyltrimethylsilane (3.1 equiv) and diethyl ether (1.5 mL / eq) were added to a vacuum purged reaction vessel equipped with a thermometer, stirrer and addition funnel. The solution was cooled to below 0°C and n-butylithium (2.0 M in diethyl ether, 3.0 equiv) was added slowly, maintaining the internal temperature below 10°C. Upon completion, the solution was stirred for 30 minutes and tin(II) chloride (1 M in THF, 1.0 equiv) was added while maintaining the internal temperature below 10°C. Upon completion, the solution was stirred at 20°C for 2 hours. The internal temperature was then allowed to drop below 0°C and 2-chloro-2-methoxypropane (1.1 equiv) was added while maintaining the internal temperature below 10°C. The solution was stirred for an additional 30 minutes and the volatiles were removed under vacuum. The solids were washed with pentane and filtered. Volatiles were removed under vacuum and recrystallized from hexane (approximately 1 mL / g product) at -20 °C to give MOP-Sn-(TMSA). 3 was obtained as a crystalline solid. 6 MOP-Sn-(TMSA) in 3 The 1H and 119Sn NMR spectra of are shown in Figures 5 and 6, respectively. The spectra showed the following chemical shifts: 1 H NMR(C 6 D 6) δ0.0(s,27H,CH 3 ), δ1.6(s,6H,CH 3 ), δ3.3(s,3H,CH 3 ); 119 Sn NMR(C 6 D 6 )δ-315.

[0077] THP-Sn-(dimethylamide) using Grignard reagent 3 Synthesis of THP-Sn-(OtBu) 3 Conversion to Diethyl ether (1.5 mL / eq) and tetrakis(dimethylamido)tin (1 eq) were added to a vacuum purged reaction vessel equipped with a thermometer, stirrer, and addition funnel, and the vessel was cooled to -20°C. Tetrahydropyranylmagnesium bromide (1.0 eq in THF) was added dropwise over 1 h. The solution was allowed to warm overnight and then filtered to remove precipitate. The filtrate was concentrated and volatiles removed in vacuo to give THP-Sn-(dimethylamido) 3 was obtained as a liquid. A sample of this material was extracted and analyzed by NMR.

[0078] THP-Sn-(dimethylamide) 3 From THP-Sn-(OtBu) 3 Conversion of THP-Sn-(dimethylamide) 3 This was achieved by opening the vessel containing the benzene-d to a bubbler and slowly adding tert-butanol in pentane (1M / 3.5 equiv.). The solution was then distilled to obtain a viscous liquid. 6 THP-Sn-(OtBu) in 3 The 1H and 119Sn NMR spectra of are shown in Figures 7 and 8, respectively. The spectra showed the following chemical shifts: 1 H NMR(C 6 D 6 ) δ1.4(s,27H,CH 3 ),δ1.7(m,1H,CH),δ1.9(m,4H,CH 2 ), δ3.2(m,2H,CH 2 ), δ3.8(m,2H,CH 2 ); 119Sn NMR (C 6 D 6 ) δ -231.

[0079] Synthesis of mTHP-Sn-(OtBu) using Grignard reagent 3 THF (50 mL) containing 4-bromo-4-methyltetrahydropyranyl magnesium bromide (11.2 mmol) was slowly added to a reaction vessel containing tetrakis(dimethylamino)stannane (3.3 g, 11.2 mmol) at -20 °C and warmed to room temperature over 12 hours. After 12 hours, the reaction mixture was filtered and the solvent was removed under reduced pressure. The residue was recrystallized from n-octane and 3.25 equivalents of tert-butanol was added to convert it to mTHP-Sn-(OtBu) 3 . The product was distilled under dynamic vacuum and further purified by fractional distillation.

[0080] Synthesis of THF-Sn-(OtBu) 3 To a cold solution (-50 °C) of trimethylsilylacetylene (0.248 g, 2.53 mmol) in diethyl ether (4 mL) was added n-butyllithium (1.03 mL, 2.53 mmol, 2.45 M in hexane). After several minutes, a slurry of tin(II) chloride (0.160 g, 0.845 mmol) in THF (4 mL) was added. The contents were warmed to 0 °C and stirred for 2 hours. The flask was recooled to -50 °C and 3-iodotetrahydrofuran (0.167 g, 0.845 mmol) was added. The resulting reaction mixture was warmed to room temperature over 16 hours and the solvent was distilled off under reduced pressure. After solvent removal, the residue was recrystallized from pentane and converted to THF-Sn-(OtBu) 3 using an excess of 5 M triethylamine / t-butanol and further purified by fractional distillation.

[0081] (CH 3 ) 3 O(CH 2 )Sn(CC(SiCH 3 )) 3 , Synthesis of MTBE-Sn-(TMSA) 3 and (CH 3 ) 3 ​​O(CH 2 )Sn(OtBu) 3 , MTBE-Sn-(OtBu) 3 Conversion to Ethynyltrimethylsilane (3.1 equivalents) and diethyl ether (1.5 mL / equivalent) were added to a vacuum-purged reaction vessel equipped with a thermometer, stirrer, and addition funnel. The solution was cooled below 0 °C, and n-butyllithium (2.0 M in diethyl ether, 3.0 equivalents) was slowly added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred for 30 minutes, and tin(II) chloride (1 M in THF, 1.0 equivalent) was added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred at 20 °C for 2 hours. Then, the internal temperature was brought below 0 °C, and 2-chloro-2-methoxypropane (1.1 equivalents) was added while maintaining the internal temperature below 10 °C. The solution was stirred for an additional 30 minutes, and the volatiles were removed under vacuum. The solid was washed with pentane and filtered. The volatiles were removed under vacuum, and recrystallization from hexane (ca. 1 mL / 1 g of product) was carried out at -20 °C to obtain MTBE-Sn-(TMSA) 3 as a crystalline solid. The 1H and 119Sn NMR spectra of MTBE-Sn-(TMAS) 6 in benzene-d 3 are shown in Figures 9 and 10, respectively. The spectra showed the following chemical shifts: 1 1H NMR (C 6 D 6 ) δ 0.0 (s, 27H, CH 3 ), δ 0.9 (s, 9H, CH 3 ), δ 3.6 (s, 2H, CH 2 ); 119 119Sn NMR (C 6 D 6 ) δ -313.

[0082] MTBE-Sn-(TMSS) 3 and 2% Cu(OtBu) were placed in an inerted flask equipped with a stir bar, and tert-butanol (10 equivalents) and triethylamine (10 equivalents) were added. The volatiles were slowly removed to obtain MTBE-Sn-(OtBu) 3 as a viscous liquid. Benzene-d 6MTBE-Sn-(OtBu) in 3 The 1H and 119Sn NMR spectra of are shown in Figures 11 and 12, respectively. The spectra showed the following shifts: 1 1H NMR(C 6 D 6 ) δ 1.4 (s, 9H, CH 3 ), δ 1.5 (s, 27H, CH 3 ), δ 4.0 (s, 2H, CH 2 ); 119 119Sn NMR(C 6 D 6 ) δ -245.

[0083] (C 6 H 5 )O(CH 2 )Sn(CC(SiCH 3 )) 3 , Synthesis of MPE-Sn-(TMSA) 3 and conversion to (C 6 H 5 )O(CH 2 )Sn(OtBu) 3 , MPE-Sn-(OtBu) 3 Conversion Ethynyltrimethylsilane (3.1 equivalents) and diethyl ether (1.5 mL / equivalent) were added to a vacuum-purged reaction vessel equipped with a thermometer, stirrer, and addition funnel. The solution was cooled below 0 °C, and n-butyllithium (2.0 M in diethyl ether, 3.0 equivalents) was slowly added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred for 30 minutes, and tin(II) chloride (1 M in THF, 1.0 equivalent) was added while keeping the internal temperature below 10 °C. After completion, the solution was stirred at 20 °C for 2 hours. Then, the internal temperature was brought below 0 °C, and chloromethoxybenzene (1.1 equivalents) was added while maintaining the internal temperature below 10 °C. The solution was stirred for an additional 30 minutes, and the volatiles were removed under vacuum. The solid was washed with pentane and filtered. The volatiles were removed under vacuum, and recrystallization from hexane (ca. 1 mL / 1 g of product) was carried out at -20 °C to obtain MPE-Sn-(TMSA) 3 as a crystalline solid. MPE-Sn-(TMSA) 6 in benzene-d 3The 1H and 119Sn NMR spectra are shown in Figures 13 and 14, respectively. The spectra showed the following chemical shifts: 1 H NMR(C 6 D 6 ) δ 0.0 (s, 27H, CH 3 ), δ 4.0 (s, 2H, CH 2 ), δ 6.8 (d, 3H, CH), δ 7.0 (t, 2H, CH); 119 Sn NMR(C 6 D 6 ) δ -317.

[0084] MPE-Sn-(TMAS) 3 and 2% Cu(OtBu) were placed in an inert flask with a stirring bar, and tert-butanol (10 equivalents) and triethylamine (10 equivalents) were added. The volatiles were slowly removed to obtain MPE-Sn-(OtBu) 3 as a viscous liquid. The 1H and 119Sn NMR spectra of MPE-Sn-(OtBu) 6 in benzene-d 3 are shown in Figures 15 and 16, respectively. The spectra showed the following chemical shifts: 1 H NMR(C 6 D 6 ) δ 1.8 (s, 27H, CH 3 ), δ 4.8 (s, 2H, CH2), δ 7.3 (d, 3H, CH), δ 7.7 (t, 2H, CH); 119 Sn NMR(C 6 D 6 ) δ -248.

[0085] (CH 3 O) 2 CHCH 2 Sn(CC(SiCH 3 )) 3 , Synthesis of DME-Sn-(TMSA) 3 ​Ethynyltrimethylsilane (3.1 equivalents) and diethyl ether (1.5 mL / equivalent) were added to a vacuum-purged reaction vessel equipped with a thermometer, a stirrer, and an addition funnel. The solution was cooled to below 0 °C, and n-butyllithium (2.0 M in diethyl ether, 3.0 equivalents) was slowly added while maintaining the internal temperature below 10 °C. After completion, the solution was stirred for 30 minutes, and tin(II) chloride (1 M in THF, 1.0 equivalent) was added while keeping the internal temperature below 10 °C. After completion, the solution was stirred at 20 °C for 2 hours. Then, the internal temperature was brought below 0 °C, and 1,1-dimethoxy-2-bromoethane (1.1 equivalents) was added while maintaining the internal temperature below 10 °C. The solution was stirred for an additional 30 minutes, and the volatiles were removed under vacuum. The solid was washed with pentane and filtered. The volatiles were removed under vacuum, and recrystallization from hexane (about 1 mL / 1 g of product) was carried out at -20 °C to obtain DME-Sn-(TMSA) 3 as a crystalline solid. The 1H and 119Sn NMR spectra of DME-Sn-(TMAS) 6 in benzene-d 3 are shown in Figures 17 and 18, respectively. The spectra showed the following chemical shifts: 1 1H NMR (C 6 D 6 ) δ 0.0 (s, 27H, CH 3 ), δ 1.5 (d, 2H, CH 2 ), δ 3.1 (s, 6H, CH 3 ), δ 4.5 (m, 1H, CH); 119 119Sn NMR (C 6 D 6 ) δ -301.

[0086] CF 3 CH 2 OCH 2 Sn(OtBu) 3 , Synthesis of FET-Sn-(OtBu) 3 ​A cold solution (-50 °C) of trimethylsilylacetylene (0.248 g, 2.53 mmol) in diethyl ether (4 mL) was treated with n-butyllithium (1.03 mL, 2.53 mmol, 2.45 M in hexane). After several minutes, a slurry of tin(II) chloride (0.160 g, 0.845 mmol) in THF (4 mL) was added. The contents were warmed to 0 °C and stirred for 2 h. The flask was recooled to -50 °C and 2-(chloromethoxy)-1,1,1-trifluoroethane (0.125 g, 0.845 mmol) was added. The resulting reaction mixture was warmed to room temperature over 16 h and the solvent was removed in vacuo to give CF 3 CH 2 OCH 2 Sn(TMSA) 3 . The contents were recrystallized from pentane and converted to FET-Sn(OtBu) 3 with excess 5 M triethylamine / t-butanol and further purified by fractional distillation.

[0087] CH 3 OCH 2 Sn(OtBu) 3 , MOM-Sn-(OtBu) 3 Synthesis MOM-Sn-(OtBu) 3 was synthesized according to the method of the above '192 patent.

[0088] Example 2: Preparation of solutions and storage stability An appropriate amount of the organotin alkoxide synthesized in the above example was dissolved in 4-methyl-2-pentanol (solvent 1) or n-propanol (solvent 2) containing a controlled amount of water to form a number of approximately 0.05 M [Sn] solutions.

[0089] The results of observing the prepared solutions over time to examine the formation of precipitates are shown in Table 1 below. For each sample, a grade of A - F was assigned according to the level of stability observed according to the following scale: A = no precipitate was observed, B = precipitate was observed after 1 month, C = precipitate was observed after 1 week, D = precipitate was observed after 1 day, F = precipitate was observed in less than 1 day.

[0090]

Table 1

[0091] The R shown in Table 1 1 OR 2 SnL 3 In the composition, a compound having a hydrocarbyl ligand in which the R 1 group and / or the R 2 group has two or more carbon atoms was observed to have higher stability against precipitation in a solution with a higher water content than the methoxymethyltin tris(tert-butoxide) composition.

[0092] Example 3: Resist Coating, Film Processing and Image Formation This example demonstrates the formation, solubility and patterning of a radiation-patternable coating or film containing the R 1 OR 2 SnL 3 compound of Example 1.

[0093] Solubility of the film A series of solutions containing the R 1 OR 2 SnL 3 compound of Example 1 were prepared by dissolving an appropriate mass of the organotin compound in several solvents with controlled water concentration to create a 0.05 M [Sn] solution. This solution was then spin-coated onto a thermal oxidation / Si substrate (about 100 nm SiO x ) to prepare a coating. The coating was baked at 100 °C for 120 seconds or at 150 °C for 120 seconds.

[0094] The baked coating was immersed in various developers to evaluate their solubility. Developers A to M shown in Table 2 were used. The solubility was evaluated by visually checking the film thickness remaining on the substrate after development. The solubility of the film was evaluated on a scale from A to F based on the thickness of the remaining film, where A = completely dissolved (i.e., substantially no film remained), B = mostly dissolved with some remaining, C = partially dissolved, D = mostly insoluble, and F = no loss of thickness was observed.

[0095] The indicated organotin compositions were dissolved in 4-methyl-2-pentanol (solvent 1), n-propanol (solvent 2), or tert-amyl alcohol (solvent 3). For each sample, the amount of water added to the solvent was controlled before adding the organotin compound, and the water concentration measured by Karl Fischer titration was set at a low concentration (300 ppm H 2 O), medium concentration (2000 ppm H 2 O), or high concentration (4000 ppm H 2 O).

[0096] Tables 3 and 4 show the solubility of the films baked at 100 °C for 120 seconds and 150 °C for 120 seconds, respectively.

[0097]

Table 2

[0098]

Table 3

[0099]

Table 4

[0100]

Table 5

[0101] As shown in Tables 3 and 4, the MOE-based film showed high solubility in most solvents except non-polar solvents (such as toluene and hexane). In contrast, in the comparative examples containing the MOM-based film, solubility was shown only in a non-aqueous acidic developer (e.g., 10% acetic acid in PGMEA) at 100 °C. At 150 °C, the MOM-based film became insoluble in the solvents tested, but the MOE-based film maintained solubility even at 150 °C. The high solubility of the MOE-based film after filming enables the removal of the non-irradiated areas of the coating, thus improving the negative patterning behavior and reducing defects such as scum. Interestingly, the MOE-based film dissolves in water even after baking at 150 °C. Similarly, films containing the cyclic ether hydrocarbyl ligands THP and mTHP showed high solubility in polar solvents at both 100 °C and 150 °C compared to the MOM-based film. R 1 groups and / or R 2 groups having hydrocarbyl ligands can improve the available process window of the organotin photoresist, allowing for higher processing temperatures and alternative developers to be used.

[0102] Contrast 300 ppm of H measured by Karl Fischer titration 2 O in 4-methyl-2-pentanol with an appropriate mass of THP-Sn-(OtBu) 3 precursor was dissolved and thoroughly mixed to obtain THP-Sn-(OtBu) 3A 0.05 M [Sn] solution was prepared. A solution of the precursor was deposited by spin coating onto a silicon wafer with a spin-on glass (SOG) coating (10 nm), and a dry film thickness of 24.0 ± 0.4 nm was obtained. After deposition and formation of the coating, the wafer was baked at 100 °C for 60 seconds. The ASML NXE3400C EUV scanner was operated in open frame and exposed to patterned EUV radiation to generate a contrast array. The exposed sample was then baked at temperatures of 140 °C, 160 °C, and 180 °C, and subsequently developed with 5% acetic acid in PGMEA. Finally, the developer residue was removed and the film was baked at 250 °C to densify the pattern. The thickness of each exposed pad was measured by polarization analysis and plotted against the dose to create the contrast curve of Figure 19. The data was summarized in Table 5 below, and the dose to gel (Dg) and the dose at the initial increase (D 0 ) were determined from the plot.

[0103]

Table 6

[0104] Example 4: Radiation-Induced Pyrolysis This example shows an improvement in carbon loss during the post-exposure bake process in a composition containing an oxygen-substituted hydrocarbyl ligand.

[0105] THP-Sn-(OtBu) 3 (Precursor 1), mTHP-Sn-(OtBu) 3 (Precursor 2) and n-butyl-Sn-(OtAm) 3(OtAm, which is the alkoxide of tert-amyl alcohol) was used to prepare three types of resist solutions. The solution prepared by dissolving precursor 1 in methyl isobutyl carbinol (MIBC) was prepared at a [Sn] concentration of 0.04 M, and the solution prepared by dissolving precursor 2 in 1-propanol was prepared at a [Sn] concentration of 0.028 M. Due to differences in viscosity and volatility, they were prepared at different concentrations so that resist films of the same thickness could be obtained after spin coating. n-Butyl-Sn-(OtAm) prepared at a [Sn] concentration of 0.05 M in MIBC 3 was also prepared as a comparative example.

[0106] The resist solutions were spin-coated under conditions where a film with a thickness of approximately 24 nm could be obtained. After deposition, each wafer was subjected to a post-deposition bake at 100 °C for 60 seconds to completely dry the sample. Next, using an ASML TwinScan NXE 3400 exposure tool, the wafer was exposed by creating an array of open-frame exposure pads with various doses over the entire wafer. Then, the wafer was subjected to a post-exposure bake at 180 °C for 60 seconds. After the post-exposure bake, each pad on each wafer was analyzed by FTIR spectroscopy, and the peak area corresponding to the absorbance in the region of C-H stretching vibration (2800 cm -1 ~3000 cm -1 was measured to determine the amount of carbon remaining in each pad. Subsequently, the measured peak area was normalized with respect to the peak area of the non-exposed region on the same wafer, and the relative peak area was calculated. Then, the relative peak area was plotted against the dose. This is shown in Figure 20.

[0107] As shown in Figure 20, in all cases, the peak area corresponding to the C-H absorbance decreases with an increase in dose. In other words, when baking is performed after EUV irradiation, the carbon content in the irradiated portion is lost. In the resist films deposited from precursor 1 and precursor 2, the amount of carbon loss after exposure and baking is greater than that of the comparative example. The carbon loss rate as a function of dose (i.e., the decrease in the relative peak area with respect to dose) was significantly improved in the resists prepared from precursor 1 and precursor 2, and showed the highest value with precursor 2. For example, 20 mJ / cm 2After the dose and baking at 180 °C for 60 seconds, about 70% of the carbon remains in the precursor 1, and about 55% remains in the precursor 2. In contrast, in the comparative example, about 85% of the carbon remains even under the same conditions. Generally, the higher the carbon loss rate, the higher the cutting efficiency of the Sn-C bond after EUV exposure and post-exposure baking. As a result, the contrast becomes higher, the dose is reduced, and patterning is improved.

[0108] Furthermore, it was revealed that the carbon loss amount of the resist film deposited from the precursor 2 is the largest. This result suggests that an organotin resist having a tertiary C bonded to Sn and oxygen in the hydrocarbyl ligand brings about an improvement in the carbon loss rate.

[0109] Example 5: Mixed Composition This example shows the influence of the dose (dose vs. size) on the mixed resist film when a pattern with a pitch of 32 nm and a line width of 16 nm is drawn on the resist film. Using the precursors listed in Table 6, mixtures 1 to 9 and a mixture for comparison were prepared. Table 7 shows the molar ratios and solvents used for the preparation of the mixtures.

[0110]

Table 7

[0111]

Table 8

[0112] Next, for comparison with mixtures 1 - 9, a mixture was spin-coated onto a Si wafer with a 10 nm SOG coating, and then a post-deposition bake was performed at 100 °C for 60 seconds to form a resist film with a thickness of approximately 24 nm. Subsequently, the resist-coated wafer was exposed to EUV radiation on an ASML TwinScan NXE 3400 exposure tool by exposing an array of fields across each wafer at different doses. After EUV exposure, each wafer was subjected to a post-exposure bake at a temperature of 160 °C, 170 °C, 180 °C, 190 °C, or 200 °C for 60 seconds, and then developed with 5% acetic acid in PGMEA. Thereafter, the wafer was hard-baked at 250 °C for 60 seconds.

[0113] Thereafter, the wafer was analyzed using Hitachi's CDSEM, and the dose-to-size (DtS) corresponding to 16 nm lines (16p32) with a 32 nm pitch was measured. The critical dimension (CD) of each 16p32 feature was measured, plotted against the field dose, and the DtS was interpolated. In some cases, the DtS values deviated from the tested conditions, and the corresponding DtS values were shown to be below the minimum dose tested. The results are shown in Table 8.

[0114]

Table 9

[0115] Lower dose-to-size values than the comparative examples were obtained from most of the mixtures in which Compound 1 and Compound 2 were mixed with a PEB at 180 °C compared to the control mixture. At higher temperatures, much lower dose-to-size values were obtained.

[0116] Example 6: Unmixed Composition To demonstrate the sensitivity improvement of an organotin resist having an ether-based ligand, cyclopentyl Sn(OtAm) 3 a resist film prepared from the precursor and THP Sn(OtBu) 3The lithographic performance of resist films prepared from precursors was directly compared. The precursors were dissolved in MIBC to obtain 0.05 M of cyclopentyl Sn(OtAm) 3 and 0.04 M of THP Sn(OtBu) 3 . Next, the samples were spin-coated onto Si wafers with a 10 nm SOG coating, and then post-application baking was performed at 100 °C for 60 seconds to form a resist film with a thickness of approximately 24 nm. Subsequently, the resist-coated wafers were exposed to EUV radiation on an ASML TwinScan NXE 3400 exposure tool by exposing an array of fields across each wafer at different doses. After EUV exposure, each wafer was subjected to post-exposure baking at 180 °C for 60 seconds and then developed with 5% acetic acid in PGMEA. Thereafter, the wafers were hard-baked at 250 °C for 60 seconds.

[0117] Thereafter, the wafers were analyzed using a Hitachi CDSEM, and the dose-to-size (DtS) corresponding to 16 nm lines (16p32) with a 32 nm pitch was measured. The critical dimension (CD) of each 16p32 feature was measured and plotted against the field dose, and the DtS was interpolated. In some cases, the DtS values deviated from the tested conditions, and the corresponding DtS values were shown to be below the minimum dose tested. The results are shown in Table 9.

[0118]

Table 10

[0119] As shown in Table 9, the presence of oxygen atoms in the alkyl group bonded to Sn corresponds to much lower dose-to-size values than the unsubstituted cyclic alkyl group bonded to Sn.

[0120] The above embodiments are for illustrative purposes and not intended to be limiting. Further embodiments are included within the scope of the claims. Additionally, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that modifications in form and detail may be made without departing from the spirit and scope of the invention. The incorporation by reference of the above documents is limited so that no subject matter that is contrary to the content explicitly disclosed herein is incorporated. As long as a particular structure, composition, and / or process is described herein using components, elements, ingredients, or other partitions, the present disclosure herein may include additional features that do not change the basic nature of the subject matter as suggested in the embodiments and discussions including embodiments that include particular embodiments, particular components, elements, ingredients, other partitions, or combinations thereof, such particular components, ingredients, or other partitions, or combinations thereof, unless otherwise specified. It should be understood that the use of the term "about" herein refers to the expected uncertainty of the relevant value as understood by those skilled in the art in a particular context.

Claims

1. Formula RSnL ３ An organotin composition represented by, where L is a hydrolyzable ligand, and R− is A) an aromatic ether represented by the formula Ar−O−(CR′ ２ ), ｍ or B) R is a cyclic ether represented by the formula cyclic (O(CR′′ ２ ), ｎ CR′R ０ -), or C) R is a halogenated ether represented by the formula R １ OR ０ C(R ２ R ３ ), or D) R is a polyether represented by the formula R １ R ２ R ３ C−, Ar is an aromatic organic moiety, m is an integer from 1 to 4, R′ is hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms and optionally a heteroatom, n is an integer from 1 to 8, R′′ is hydrogen or a hydrocarbyl group having 1 to 4 carbon atoms and optionally a heteroatom, optionally, the CR′′ ２ group can be substituted with O to form a cyclic polyether, and two R′′ groups can be bonded to form a polycyclic structure, R ０ is a bond or a hydrocarbyl group having 1 to 5 carbon atoms and optionally a heteroatom, R １ is a hydrocarbyl group having 1 to 10 carbon atoms with an optional unsaturated bond and / or an optional heteroatom, R ２ and R ３ are independently hydrogen, a halogen, or a hydrocarbyl group having 1 to 7 carbon atoms with an optional unsaturated bond and / or an optional heteroatom, at least one of R １ , R ２ , R ３ has a halogen atom, and R １ , R ２ and R ３ are independently hydrocarbyl groups having 1 to 19 carbon atoms with an optional unsaturated bond and / or an optional heteroatom, R １ , R ２ , R ３ At least two of them are ether portions or R １ , R ２ , R ３ An organotin composition in which at least one of the components is a diether moiety.

2. R- is the same as in the above formula Ar-O-(CR' ２ ) ｍ The organotin composition according to claim 1, wherein the aromatic ether is represented by -, Ar is an aromatic organic moiety, m is an integer from 1 to 4, and R' is a hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms and an optional heteroatom.

3. The organotin composition according to claim 2, wherein m is 1 and R' is hydrogen.

4. Ar is -C ６ H ５ The organotin composition according to claim 3.

5. R- is the same as in the above formula Ar-O-(CR' ２ ) ｍ It is an aromatic ether represented by -, where Ar is -C ５ NH ４ , -C １０ H ７ ien-CH ２ C ６ H ５ or -C ６ H ４ C ６ H ５ The organotin composition according to claim 1.

6. R is the ring of the formula (O(CR') ２ ) ｎ CR'R ０ A cyclic ether represented by -), where R' is a hydrocarbyl group having hydrogen or 1 to 6 carbon atoms and an optional heteroatom, and n is an integer from 1 to 8, optionally CR' ２ The group can be substituted with O to form a cyclic polyether, and the two R' groups can bond to form a polycyclic structure, R ０ The organotin composition according to claim 1, wherein is a bond or a linear or branched hydrocarbyl group having 1 to 5 carbon atoms and an optional heteroatom.

7. R is O(CR'' ２ ) ｎ CR'R ０ Represented by - and R ０ The organotin composition according to claim 6, wherein is a bond, and the cyclic ether is directly bonded to the Sn atom.

8. O(CR' ２ ) ｎ CR' is O(CH ２ ) ３ CH-, O(CH ２ ) ４ CH- or O(CH ２ ) ４ CCH ３ - The organotin composition according to claim 7.

9. at least one CR' ２ The organotin composition according to claim 6, wherein the group is substituted with an oxygen atom such that the cyclic ether is a polyether.

10. O(CR' ２ ) ｎ CR'R ０ - is a ring (CH ２ OCH ２ OCH ２ The organotin composition according to claim 6, wherein it is CH-.

11. R is the same as in the above formula R １ OR ０ C(R ２ R ３ ) is a halogenated ether represented by R ０ R is a linear or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and an optional heteroatom, １ R is a hydrocarbyl group having 1 to 10 carbon atoms, having an optional unsaturated bond and / or an optional heteroatom, ２ and R ３ R is a hydrocarbyl group having 1 to 7 carbon atoms, independently having hydrogen, a halogen, or an optional unsaturated bond and / or an optional heteroatom, １ , R ２ , R ３ The organotin composition according to claim 1, wherein at least one of the elements has a halogen atom.

12. R １ or R ２ -CF ３ The organotin composition according to claim 11, comprising:

13. R ０ is a bond, and R ２ and / or R ３ The organotin composition according to claim 11, comprising a fluorine group.

14. R is a polyether represented by the formula R １ R ２ R ３ C−, where R １ , R ２ and R ３ are each independently a hydrocarbyl group having 1 to 19 carbon atoms with an optional unsaturated bond and / or an optional heteroatom, and at least two of R １ , R ２ , R ３ are an ether moiety, or at least one of R １ , R ２ , R ３ is a diether moiety, the organotin composition according to claim 1.

15. R １ is, -OCH ３ And R ２ OCH ３ And R ３ The organotin composition according to claim 14, wherein is hydrogen.

16. R １ is, -OCH ２ OCH ３ The organotin composition according to claim 14, comprising:

17. A solution comprising an organic solvent and an organotin composition according to any one of claims 1 to 16, at a concentration of about 0.0025 M to about 1.4 M, as measured based on the tin cation concentration.

18. The solution according to claim 17, wherein the organic solvent comprises a secondary or tertiary alcohol having 3 to 8 carbon atoms.

19. The solution according to claim 17, further comprising a second distinct organotin composition according to claim 1.

20. Formula R ａ SnL' ３ The organotin composition further comprises the following, where L' is the same as or different from L, and R ａ is, formula R ｂ R ｃ R ｄ Represented by C-, R ｂ , R ｃ , R ｄ The solution according to claim 17, wherein is independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

21. R ｂ , R ｃ , R ｄ These are -CH, respectively. ３ The solution according to claim 20, which is the base.

22. The organotin composition is the one of the formulas Ar-O-(CR' ２ ) ｍ The solution according to claim 17, having an R group which is an aromatic ether represented by -.

23. The organotin composition is the cyclic (O(CR'')'' of the formula. ２ ) ｎ CR'R ０ The solution according to claim 17, having an R group which is a cyclic ether represented by -).

24. R ０ The bond is such that the cyclic ether is directly bonded to the Sn atom, and O(CR'' ２ ) ｎ CR' is O(CH ２ ) ３ CH-, O(CH ２ ) ４ CH- or O(CH ２ ) ４ CCH ３ - The solution according to claim 23.

25. A method for forming a radiation-patternable coated substrate, A) Contacting the substrate surface with the vapor of the composition described in any one of claims 1 to 16 to form a deposit on the substrate surface, and Heating the substrate having the deposits on the surface, wherein the contact and / or heating conditions result in the hydrolysis of the hydrolyzable ligand L, thereby forming an oxo-hydroxo network, RSnO ｎ (OH) ３－２ｎ Forming a coating containing (wherein 0 < n < 3 / 2 in the formula), or B) Depositing a solution containing an organic solvent and an organotin composition according to any one of claims 1 to 16 at a concentration of about 0.0025 M to about 1.4 M, as measured based on the tin cation concentration, onto the substrate surface to form an initial coating surface, and Heating the substrate having the initial coating surface, wherein the deposition and / or heating conditions result in the hydrolysis of the hydrolyzable ligand L, thereby forming an oxo-hydroxo network, RSnO ｎ (OH) ３－２ｎ Forming a coating containing (where 0 < n < 3 / 2 in the formula) A method that includes this.

26. A substrate and a coating having an average thickness of approximately 1 nm to approximately 75 nm, which forms an oxo-hydroxo network, the formula RSnO ｎ (OH) ３－２ｎ A radiation-patternable coated substrate comprising a coating represented by R, wherein R is a hydrocarbyl ether group having 1 to 30 carbon atoms and 0 < n < 3 / 2, and the region of the coating is soluble in 2-heptanone in a paddle developing step after baking at 150°C for 120 seconds.

27. R- is in the formula Ar-O-(CR' ２ ) ｍ A radiation-patternable coating substrate according to claim 26, wherein the aromatic ether is represented by -, Ar is an aromatic organic moiety, m is an integer from 1 to 4, and R' is a hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms and an optional heteroatom.

28. m is 1, R' is hydrogen, and Ar is -C ６ H ５ The radiation-patternable coated substrate according to claim 26.

29. R is the ring of the formula (O(CR') ２ ) ｎ CR'R ０ A cyclic ether represented by -), where R' is a hydrocarbyl group having hydrogen or 1 to 6 carbon atoms and an optional heteroatom, and n is an integer from 1 to 8, optionally CR' ２ The group can be substituted with O to form a cyclic polyether, and the two R' groups can bond to form a polycyclic structure, R ０ The radiation-patternable coating substrate according to claim 26, wherein is a linear or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and an optional heteroatom.

30. R ０ The bond is such that the cyclic ether is directly bonded to the Sn atom, and O(CR'' ２ ) ｎ CR' is O(CH ２ ) ３ CH-, O(CH ２ ) ４ CH- or O(CH ２ ) ４ CCH ３ - The radiation-patternable coated substrate according to claim 29.

31. R is, Formula R １ OR ０ C(R ２ R ３ ) is a halogenated ether represented by R ０ R is a linear or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and an optional heteroatom, １ R is a hydrocarbyl group having 1 to 10 carbon atoms, having an optional unsaturated bond and / or an optional heteroatom, ２ and R ３ R is a hydrocarbyl group having 1 to 7 carbon atoms, independently having hydrogen, a halogen, or an optional unsaturated bond and / or an optional heteroatom, １ , R ２ , R ３ The radiation-patternable coating substrate according to claim 26, wherein at least one of the atoms is a halogen atom.

32. R １ or R ２ -CF ３ A radiation-patternable coated substrate according to claim 31, including the above.

33. R is, Formula R １ R ２ R ３ A polyether represented by C-, R １ , R ２ and R ３ R is a hydrocarbyl group having 1 to 19 carbon atoms, independently having an optional unsaturated bond and / or an optional heteroatom, １ , R ２ , R ３ At least two of them are ether portions or R １ , R ２ , R ３ The radiation-patternable coated substrate according to claim 26, wherein at least one of the portions is a diether portion.

34. A method of patterning structures, Irradiating a radiation-patternable coated substrate according to any one of claims 26 to 33 to form a latent image, Developing the aforementioned latent image to form a physical pattern A method that includes this.

35. A method for patterning a circuit board, The method involves irradiating a substrate having an organotin coating with patterned EUV radiation to form a latent image, wherein the coating has an average thickness of about 1 nm to about 75 nm and forms an oxo-hydroxo network with the formula RSnO ｎ (OH) ３－２ｎ The composition is represented by and R is a hydrocarbyl ether group having 1 to 30 carbon atoms, and 0 < n < 3 / 2, to form, The latent image is developed with a developer solvent to remove the unirradiated coating and form a developed image with a critical dimension of approximately 50 nm or less and a irradiation rate of approximately 80 mJ / cm². ２ Form the image using the following doses: A method that includes this.

36. The polar organic developer solvent comprises a solvent mixture containing at least two solvents, where at least 55% by volume of one or more solvents independently has a concentration of about 16 (J / cm³). ３ ) １／２ The following Hansen solubility parameters are present in the sum of δH + δP, and one or more solvents in about 0.25% to about 45% by volume each independently have a solubility of at least about 16 (J / cm³). ３ ) １／２ The method according to claim 35, wherein the sum of the Hansen solubility parameters δH + δP is

37. The aforementioned organotin coating is A) Contacting the substrate surface with the vapor of an organotin composition to form a deposit on the substrate surface, and Heating the substrate having the deposits on the surface, wherein the contact and / or heating conditions result in the hydrolysis of the hydrolyzable ligand L, thereby forming an oxo-hydroxo network, RSnO ｎ (OH) ３－２ｎ Forming a coating containing (wherein 0 < n < 3 / 2 in the formula), or B) Depositing a solution containing an organic solvent and an organotin composition at a concentration of approximately 0.0025 M to approximately 1.4 M, as measured based on the tin cation concentration, onto the substrate surface to form an initial coating surface, and Heating the substrate having the initial coating surface, wherein the deposition and / or heating conditions result in the hydrolysis of the hydrolyzable ligand L, thereby forming an oxo-hydroxo network, RSnO ｎ (OH) ３－２ｎ Forming a coating containing (where 0 < n < 3 / 2 in the formula) The method according to claim 35 or 36, formed by...

38. The method according to claim 37, wherein the heating of the substrate having the initial coating surface is performed at a temperature of about 50°C to about 250°C for a period of time of about 0.1 minutes to about 10 minutes.

39. The method according to claim 35 or 36, further comprising heating the substrate having the latent image to a temperature of about 50°C to about 250°C for a period of time of about 0.1 minutes to about 10 minutes.

40. R- is in the formula Ar-O-(CR' ２ ) ｍ The method according to claim 35 or 36, wherein the aromatic ether is represented by -, Ar is an aromatic organic moiety, m is an integer from 1 to 4, and R' is a hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms and an optional heteroatom.

41. m is 1, R' is hydrogen, and Ar is -C ６ H ５ The method according to claim 40.

42. R is the ring of the formula (O(CR') ２ ) ｎ CR'R ０ A cyclic ether represented by -), where R' is a hydrocarbyl group having hydrogen or 1 to 6 carbon atoms and an optional heteroatom, and n is an integer from 1 to 8, optionally CR' ２ The group can be substituted with O to form a cyclic polyether, and the two R' groups can bond to form a polycyclic structure, R ０ The method according to claim 35 or 36, wherein is a linear or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and an optional heteroatom.

43. R ０ The bond is such that the cyclic ether is directly bonded to the Sn atom, and O(CR'' ２ ) ｎ CR' is O(CH ２ ) ３ CH-, O(CH ２ ) ４ CH- or O(CH ２ ) ４ CCH ３ - The method according to claim 42.

44. R is, Formula R １ OR ０ C(R ２ R ３ ) is a halogenated ether represented by R ０ R is a linear or branched hydrocarbyl group having a bond or 1 to 5 carbon atoms and an optional heteroatom, １ R is a hydrocarbyl group having 1 to 10 carbon atoms, having an optional unsaturated bond and / or an optional heteroatom, ２ and R ３ R is a hydrocarbyl group having 1 to 7 carbon atoms, independently having hydrogen, a halogen, or an optional unsaturated bond and / or an optional heteroatom, １ , R ２ , R ３ The method according to claim 35 or 36, wherein at least one of the atoms has a halogen atom.

45. A method for synthesizing an organotin composition, wherein a hydrocarbyl halide compound (R-X (wherein X is a halide atom)) is associated with a metal cation M in SnL ３ The alkali metal tin composition is formed by reacting with an organometallic composition containing a portion of the alkali metal tin, wherein M is an alkali metal, an alkaline earth metal and / or a pseudo-alkaline earth metal (Zn, Cd or Hg), and L is either an amide ligand that yields an alkali metal tin triamide compound or an acetylide ligand that yields an alkali metal tin triacetylide compound, thereby forming monohydrocarbyl tin triamide (RSn(NR')). ２ ) ３ ) or monohydrocarbyl tin triacetide (RSn(C≡CR ｓ ) ３ ) including forming R ｓ is SiR'' ３ or R', where the three R'' are independently H or R', and R' is independently a hydrocarbyl group having 1 to 31 carbon atoms and an optional unsaturated carbon-carbon bond, an optional aromatic group and an optional heteroatom, where R is of the formula Ar-O-(CR' ２ ) ｍ Aromatic ethers represented by -, or cyclic (O(CR') ２ ) ｎ A cyclic ether represented by CR'-), or formula R １ R ２ R ３ A hydrocarbyl ether group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, including a polyether represented by C-, where Ar is an aromatic organic group, m is an integer from 1 to 4, each R' is hydrogen, a halogen, or a hydrocarbyl group having 1 to 6 carbon atoms and an optional heteroatom, n is an integer from 1 to 8, R １ , R ２ and R ３ R is an independent hydrocarbyl group having 1 to 19 carbon atoms. １ , R ２ , R ３ At least two of them are ether portions or R １ , R ２ , R ３ A method in which at least one of the parts is a diether part.

46. A method for forming an organotin composition, In a solution containing an organic solvent, RMgX, R ２ Zn, RZnNR' ２ Alternatively, an alkylating agent selected from the group consisting of combinations thereof is Sn(NR' ２ ) ４ This includes causing a reaction, X is a halogen, R' is a hydrocarbyl group having 1 to 10 carbon atoms. R is given by the formula Ar-O-(CR' ２ ) ｍ Aromatic ethers represented by -, or cyclic (O(CR') ２ ) ｎ A cyclic ether represented by CR'-), or formula R １ R ２ R ３ A hydrocarbyl ether group having 1 to 31 carbon atoms, an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, including a polyether represented by C-, where Ar is an aromatic organic group, m is an integer from 1 to 4, each R' is hydrogen, a halogen, or a hydrocarbyl group having 1 to 6 carbon atoms and an optional heteroatom, n is an integer from 1 to 8, R １ , R ２ and R ３ R is an independent hydrocarbyl group having 1 to 19 carbon atoms. １ , R ２ , R ３ At least two of them are ether portions or R １ , R ２ , R ３ A method in which at least one of the parts is a diether part.

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