WO2022102636A1 - 有機錫化合物、その製造方法、これを用いたｅｕｖレジスト膜形成用液組成物及びｅｕｖレジスト膜の形成方法 - Google Patents

有機錫化合物、その製造方法、これを用いたｅｕｖレジスト膜形成用液組成物及びｅｕｖレジスト膜の形成方法 Download PDF

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WO2022102636A1
WO2022102636A1 PCT/JP2021/041260 JP2021041260W WO2022102636A1 WO 2022102636 A1 WO2022102636 A1 WO 2022102636A1 JP 2021041260 W JP2021041260 W JP 2021041260W WO 2022102636 A1 WO2022102636 A1 WO 2022102636A1
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tin
resist film
ray emission
liquid composition
carbon atoms
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PCT/JP2021/041260
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English (en)
French (fr)
Japanese (ja)
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大貴 古山
常俊 本田
広隆 平野
一郎 塩野
真也 白石
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三菱マテリアル株式会社
三菱マテリアル電子化成株式会社
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Publication of WO2022102636A1 publication Critical patent/WO2022102636A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present invention relates to an organotin compound having a low ⁇ -ray emission amount and a method for producing the same. Further, the present invention relates to a liquid composition for forming an EUV resist film having a low ⁇ -ray emission amount using this organotin compound, and a method for forming an EUV resist film having a low ⁇ -ray emission amount.
  • the resist film patterning technique in the semiconductor process has undergone a transition, and a lithography technique using KrF or ArF as a light source has been established, and semiconductor devices are still mass-produced using this technique. ..
  • ITRS International Technology Roadmap for Semiconductor
  • EUV Extreme Ultra Violet
  • a resist film-forming liquid composition a method of introducing a structure that increases the light sensitivity by mainly applying CAR, or a metal species having a high EUV light absorption coefficient is introduced.
  • a method or a method using a non-chemically amplified resist (Non-CAR) having a different mechanism has been proposed and is being developed.
  • Non-CAR non-chemically amplified resist
  • the challenges in developing next-generation resist materials are that the output of EUV light that finally reaches the mask is small, and that the photosensitive mechanism changes due to changes in light rays, so EUV It was necessary to form a resist film with high sensitivity to light.
  • Patent Document 1 for example, Patent Document 1
  • See claim 1, abstract This method is an example of non-CAR.
  • Patent Document 1 describes an organic solvent and the formula R z SnO (2- (z / 2)-(x / 2)) (OH) x (where 0 ⁇ z ⁇ 2 and 0 ⁇ (z + x) ⁇ 4).
  • a coating solution containing a hydrolyzable metal compound represented by (is a combination of) is disclosed.
  • This Patent Document 1 describes an organometallic precursor for creating a high resolution lithography pattern forming coating based on metal oxide hydroxyd chemistry, and the precursor composition thereof is generally under mild conditions. Containing ligands that can be easily hydrolyzed by water vapor or other OH source compositions, the organometallic precursors can generally be effective in forming high resolution patterns at relatively low radiation doses. It is described that it contains a radiation sensitive organoligand to tin, which can result in a coating that is particularly useful in EUV patterning.
  • the detection of metal impurities is a trace amount of the composition such as ICP-MS.
  • the analysis is performed by the analysis method, and this analysis shows that it is less than the detection of metal impurities.
  • metal impurities are contained in the order of ppb that cannot be detected by trace analysis, if metal impurities that can emit radiation due to radioactive decay are contained, radiation such as ⁇ -rays, ⁇ -rays, and ⁇ -rays is emitted. There is a risk of
  • the present inventors have found that when tin (Sn) having a high absorption coefficient of EUV light is used as the resist material for the purpose of increasing the sensitivity of the resist material, Sn is used. Contains a small amount of Pb as an impurity, and ⁇ -rays emitted from 210 Po generated from 210 Pb, which is an isotope of this Pb, cause an unintended structural change in the resist film containing Sn, resulting in random defects. It was found that the present invention was reached.
  • the first aspect of the present invention is an organotin compound having an ⁇ -ray emission amount of 0.01 cph / cm 2 or less.
  • the second aspect of the present invention is an invention based on the first aspect, which is an organotin compound represented by any of the following formulas (1) to (9).
  • R 1 is a hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a hydrocarbon group having 1 to 10 carbon atoms, a is 1 or 2, and b to d are integers having the same or different carbon atoms from 1 to 28, respectively. 0 ⁇ n ⁇ 4.
  • R 2 is a hydrocarbon group having 1 to 10 carbon atoms, p to s are integers having the same or different carbon atoms from 1 to 28, and t is 1 or more and 4 or less. .. Y has an anion species as a counterion.
  • R 3 is a hydrocarbon group having 1 to 10 carbon atoms.
  • R 4 is a hydrocarbon group having 1 to 10 carbon atoms.
  • R 5 is a hydrocarbon group having 1 to 10 carbon atoms
  • R 6 is a hydrocarbon group having 1 to 5 carbon atoms.
  • R 7 is a hydrocarbon group having 1 to 10 carbon atoms.
  • R 8 is a hydrocarbon group having 1 to 10 carbon atoms.
  • R 9 is a hydrocarbon group having 1 to 10 carbon atoms.
  • the third aspect of the present invention is the EUV resist film forming liquid composition using the organic tin compound of the first aspect or the second aspect, and the EUV resist film forming liquid composition is 100% by mass.
  • the EUV resist film-forming liquid composition has a tin content of 0.05% by mass or more and 24% by mass or less.
  • a fourth aspect of the present invention is a method for forming an EUV resist film having an ⁇ -ray emission amount of 0.01 cph / cm 2 or less by using the EUV resist film forming liquid composition of the third aspect.
  • the fifth aspect of the present invention is (a) a step of synthesizing tin tetrachloride from metallic tin having an ⁇ -ray emission amount of 0.01 cf / cm 2 or less, and (b) a monoalkyl tin oxide from the tin tetrachloride.
  • it is a method for producing an organic tin compound including a step of synthesizing an alkyl tin trialkoxide, and in all the steps from the step (a) to the step (c), distillation for removing impurities from the composite is performed a plurality of times.
  • the ⁇ -rays of the organic tin compound are controlled by ⁇ -ray control to shield the ⁇ -rays from the equipment and environment used in all the steps from the step (a) to the step (c). It is a method for producing an organic tin compound, characterized in that the amount released is 0.01 cph / cm 2 or less.
  • the sixth aspect of the present invention is the invention based on the fifth aspect, in which multiple distillations measure the amount of ⁇ -ray emission of the compound or impurity fraction produced in each step, and the ⁇ -ray emission is achieved.
  • This is a method for producing an organic tin compound, which is carried out until the amount becomes 0.01 cph / cm 2 or less.
  • the organotin compound according to the first aspect of the present invention has an ⁇ -ray emission amount of 0.01 cph / cm 2 or less, this organotin compound is used as a raw material for a liquid composition for forming an EUV resist film to form an EUV resist film.
  • a resist film with reduced random defects can be formed due to the small amount of ⁇ -ray emission.
  • the organic tin compound according to the second aspect of the present invention has a hydrocarbon group represented by any of the above-mentioned formulas (1) to (9) bonded to it, the amount of ⁇ -ray emission is 0.01 cph / cm.
  • the OH) bond absorbs the irradiated EUV light with high efficiency and causes a structural change, and the solubility selectivity in the developing solution is greatly enhanced after the irradiation of the EUV light.
  • the EUV resist film-forming liquid composition of the third aspect of the present invention uses the organic tin compound of the first aspect or the second aspect, when the EUV resist film-forming liquid composition is stored. It has the feature that the generation of reactive foreign substances due to the emission of ⁇ -rays is small. Further, since the tin content in the liquid composition is 0.05% by mass or more and 24% by mass or less, when the resist film made of this organotin compound is irradiated with EUV light, EUV light is absorbed with high efficiency. can do. In addition to this excellent effect, it is possible to form a resist film with reduced random defects when a pattern is formed on the EUV resist film due to a small amount of ⁇ -ray emission.
  • the formed EUV resist film uses the liquid composition for forming the EUV resist film according to the third aspect, so that the formed EUV resist film is ⁇ . It is possible to effectively utilize the irradiated EUV light without being affected by the line, and it is possible to achieve both high sensitivity and low defects.
  • tin tetrachloride is synthesized from metallic tin having an ⁇ -ray emission amount of 0.01 cf / cm 2 or less, and monoalkyl tin oxide or alkyl is synthesized from tin tetrachloride.
  • the amount of ⁇ -ray emission of the organic tin compound can be reduced to 0.01 cf / cm 2 or less, and the organic tin compound having this low amount of ⁇ -ray emission can be used to form an EUV resist film.
  • a resist film having reduced random defects can be formed due to a small amount of ⁇ -ray emission.
  • the amount of ⁇ -ray emission of a compound or impurity distillate produced in each step by multiple distillations is measured, and the amount of ⁇ -ray emission is 0.01 cph. Since it is carried out until it becomes / cm 2 or less, the ⁇ -ray emission amount of the final organic tin compound can be 0.01 cph / cm 2 or less.
  • the patterned (drawn) resist film of the present embodiment is made from metallic tin (Sn) as a starting material. Specifically, an organotin compound is first produced using metallic tin (Sn) having a low ⁇ -ray emission amount, and a liquid composition for forming an EUV resist film is produced from this organotin compound. The liquid composition is then coated on the substrate and the coating film is baked. Next, the baked resist film is exposed to EUV and subjected to development and post-treatment to obtain a patterned resist film.
  • the low ⁇ -ray emission amount of metallic tin (Sn) of the present embodiment is selected from those having an ⁇ -ray emission amount in the range of 0.01 cf / cm 2 or less, preferably those having an ⁇ -ray emission amount of less than 0.0005 cf / cm 2 .
  • Examples of the metallic tin having a low ⁇ -ray emission amount include metallic tin produced by the method shown in Japanese Patent No. 6512354.
  • the “ ⁇ -ray emission amount” refers to a value measured for 96 hours with a gas flow type ⁇ -ray measuring device (MODEL-1950, lower limit of measurement: 0.0005 cph / cm 2 ) manufactured by Alpha Science. The measurement was performed so that the temperature was within the range of 20 ° C to 30 ° C.
  • Organotin compounds with low alpha ray emission The organotin compound produced from the metallic tin having a low ⁇ -ray emission amount of the present embodiment is represented by any of the following formulas (1) to (9).
  • R 1 is a hydrocarbon group having 1 to 10 carbon atoms.
  • Examples thereof include -sec-butyl tin oxide, monophenyl tin oxide represented by the formula (1-10), monononyl tin oxide represented by the formula (1-11), and monodecyl tin oxide represented by the formula (1-12). ..
  • R 2 is a hydrocarbon group having 1 to 10 carbon atoms, a is 1 or 2, and b to d are the same or different carbon atoms 1 respectively. It is an integer of ⁇ 28, and 0 ⁇ n ⁇ 4.
  • Specific examples of this multimeric organic tin compound include [(BuSn) 12 O 14 (OH) 6 ] 2+ , [(PhSn) 12 O 14 (OH) 6 ] 2+ , [(tert-BuSn) 12 ).
  • Bu represents a butyl group
  • Ph represents a phenyl group
  • tert-Bu represents a tertiary butyl group
  • iso-Pr represents an isopropyl group
  • tert-Am represents a tertiary rearyl group.
  • R 2 is a hydrocarbon group having 1 to 10 carbon atoms
  • p to s are integers having the same or different carbon atoms from 1 to 28, and t. Is 1 or more and 4 or less.
  • Y has an anion species as a counterion. This anionic species is due to an acid used in synthesizing an organic tin compound, and examples of the acid include p-toluenesulfonic acid, phenylacetic acid, oxalic acid, malonic acid, and benzoic acid.
  • this multimeric organic tin compound examples include [(BuSn) 12 O 14 (OH) 6 ] (SO 3 C 6 H 4 CH 3 ) 2 , [(sec-BuSn) 12 O 14 (OH) 6 ] (SO 3 C 6 H 4 CH 3 ) 2 , [(iso-PrSn) 12 O 14 (OH) 6 ] (SO 3 C 6 H 4 CH 3 ) 2 , [(tert-BuSn) 12 O 14 (OH) ) 6 ] (C 6 H 5 CH 2 COO) 2 , [(sec-BuSn) 12 O 14 (OH) 6 ] (OCOCOO), [(iso-PrSn) 12 O 14 (OH) 6 ] (OCOCH 2 COO) ), [(BuSn) 12 O 14 (OH) 6 ] (HCOO) 2 , [(BuSn) 12 O 14 (OH) 6 ] (C 6 H 5 COO) 2 , [(PhSn) 12 O 14 (OH) 6 ] Cl 2
  • the organotin compound represented by the formula (3) can be selected by the functional group Y, and the sensitivity to EUV light can be adjusted by the selected functional group Y.
  • this organic tin compound when used as a raw material for a liquid composition for forming a resist film to form a pattern on an EUV resist film, a resist with a small amount of ⁇ -ray emission reduces random defects. A film can be formed.
  • R 3 is a hydrocarbon group having 1 to 10 carbon atoms.
  • a resist film with reduced random defects can be formed by reducing the amount of ⁇ -ray emission.
  • the organic tin compounds of the formulas (4-2) to (4-8) are exemplified.
  • Bu is a butyl group
  • Et is an ethyl group
  • Me is a methyl group
  • Pr is a propyl group
  • Hex is a hexyl group
  • iso-Pr is an isopropyl group
  • tert-Bu is a tertiary butyl group
  • sec-Bu is a secondary butyl. Represents each group.
  • R 4 is a hydrocarbon group having 1 to 10 carbon atoms.
  • the sensitivity of the EUV resist film can be adjusted by utilizing the cleavage of the bond between Sn and C in a state where the amount of ⁇ -ray emission is small. In addition to this effect, a resist film with reduced random defects can be formed by reducing the amount of ⁇ -ray emission.
  • the organotin compounds of the formulas (5-2) to (5-8) are exemplified.
  • Bu is a butyl group
  • Et is an ethyl group
  • Me is a methyl group
  • Pr is a propyl group
  • Hex is a hexyl group
  • iso-Pr is an isopropyl group
  • tert-Bu is a tertiary butyl group
  • sec-Bu is a secondary butyl. Represents each group.
  • R 5 is a hydrocarbon group having 1 to 10 carbon atoms
  • R 6 is a hydrocarbon group having 1 to 5 carbon atoms.
  • This organic tin compound has an alkoxide structure, and when it is used as a raw material for a liquid composition for forming an EUV resist film and the liquid composition is applied and baked, the hydrolysis reaction easily proceeds.
  • a tin-containing resist film having high sensitivity to EUV light can be formed, and a resist film having reduced random defects can be formed by reducing the amount of ⁇ -ray emission.
  • the organotin compounds of the formulas (6-2) to (6-22) are exemplified.
  • iso-Pr is an isopropyl group
  • Et is an ethyl group
  • Pr is a propyl group
  • Me is a methyl group
  • Bu is a butyl group
  • iso-Bu is an isobutyl group
  • sec-Bu is a secondary butyl group
  • tert-Bu is a Tasha.
  • R 7 is a hydrocarbon group having 1 to 10 carbon atoms.
  • Specific examples of this organotin compound include tetrabutyltin (R 7 having 4 carbon atoms) represented by the following formula (7-1).
  • This organotin compound is an intermediate compound produced during the synthesis of the monobutyltin oxide represented by the above formula (1-1).
  • the organic tin compounds of the formulas (7-2) to (7-8) are exemplified.
  • R 8 is a hydrocarbon group having 1 to 10 carbon atoms.
  • This organotin compound is an intermediate compound produced during the synthesis of the monobutyltin oxide represented by the above formula (1-1).
  • the organotin compounds of the formulas (8-2) to (8-11) are exemplified.
  • R 9 is a hydrocarbon group having 1 to 10 carbon atoms.
  • the organotin compounds of the formulas (9-2) to (9-10) are exemplified.
  • the organotin compound of the present embodiment produces tin chloride from metallic tin and is made from this tin chloride.
  • metallic tin it is preferable to use metallic tin having an ⁇ -ray emission amount of 0.01 cph / cm 2 or less. By using such metallic tin, the number of distillations for removing impurities from the synthetic material described later can be reduced.
  • the metallic tin at this time is preferably in the form of granules, foils, or powders in order to enhance the reactivity.
  • a method for producing tin chloride from metallic tin and a method for producing an organic tin compound from this tin chloride a known method is adopted.
  • distillation for removing impurities from the synthetic substance is performed a plurality of times, and ⁇ rays are used to shield ⁇ rays from the equipment and environment used in all the processes. It is essential that management be done.
  • distillation for removing impurities from a compound is performed a plurality of times in all manufacturing processes means that the amount of ⁇ -ray emission of the compound or impurity distillate generated in each step is measured, and the amount of ⁇ -ray emission is calculated. It means repeating distillation multiple times until it becomes 0.01 cph / cm 2 or less. Distillation is preferably performed at a temperature slightly lower than 130 ° C., which is the temperature at which Po, which is an ⁇ -ray source, sublimates.
  • ⁇ -ray control is performed on the equipment in all manufacturing processes means that the equipment to be used is pickled and then alkaline-cleaned before each process.
  • an aqueous solution of sulfuric acid or an aqueous solution of hydrochloric acid having a concentration of 15% by mass to 30% by mass at a temperature of 45 ° C. to 55 ° C. is supplied to an instrument placed in a washing tank for 60 to 80 minutes for acid cleaning, and then ion-exchanged water is applied at room temperature. Then, the washed equipment is supplied with an aqueous solution of ammonium carbonate, an aqueous solution of ammonium bicarbonate, water of ammonia, etc. at a concentration of 35% by mass to 41% by mass at a temperature of 30 ° C. to 40 ° C. for 40 to 50 minutes for alkaline cleaning. do.
  • the environment used is a highly clean environment. For example, a clean room or an environment of a cleanliness class of Class 6 or higher based on the international standard ISO 14644-1: 2015 can be mentioned. In consideration of the safety of the substances produced, the substances unstable in the air should be handled by substituting with an inert gas or in a glove box in which the amount of water is controlled.
  • the environment in which it is used should be an environment that shields ⁇ rays that may be mixed into the equipment and facilities used in all manufacturing processes.
  • granular, foil-like or powder-like metallic tin is prepared by using the above-mentioned acid-cleaning and then alkali-cleaning instruments.
  • the metallic tin it is preferable to use a metallic tin having a low ⁇ -ray emission amount of 0.01 cph / cm 2 or less. This metallic tin is reacted with chlorine (Cl 2 ) gas to synthesize tin tetrachloride (SnCl 4 ) as shown in FIG. 2 and the formula (10).
  • FIG. 2 shows a production flow chart from metal tin having a low ⁇ -ray emission amount to obtaining tin tetrachloride having a low ⁇ -ray emission amount.
  • tin tetrachloride having a low ⁇ -ray emission amount is reacted with chlorine gas to distill tin tetrachloride in one distillation. Then, the distilled tin tetrachloride is distilled and purified to obtain purified tin tetrachloride. The amount of ⁇ rays emitted from this purified tin tetrachloride is measured.
  • tin tetrachloride is dissolved in a methanol solution and sprayed in the air onto a clean glass substrate surface heated to 700 ° C. using a glass atomizer.
  • a method of forming a tin oxide thin film as an electrode material. That is, a tin oxide (IV) film is formed in an environment where the generated hydrogen chloride gas can be sucked, a spray temperature of 20 ° C. to 25 ° C., and a humidity of 48% to 53%, and the ⁇ of this tin oxide film is formed. Measure the amount of ray emitted.
  • FIG. 3 shows a production flow chart from tin tetrachloride having a low ⁇ -ray emission amount to obtaining a monoalkyl tin oxide having a low ⁇ -ray emission amount.
  • the process until monobutyltin oxide is obtained as monoalkyltin oxide will be described.
  • purified tin tetrachloride SnCl 4
  • an organic magnesium halide of a Grignard reagent to obtain tetraalkyl tin as shown in the formula (11).
  • Synthesize tetrabutyltin is used as the organic magnesium halide.
  • the synthesized tetrabutyl tin is reacted with tin tetrachloride (SnCl 4 ) synthesized by the formula (10) to synthesize a monobutyl tin trichloride, which is a monoalkyl tin trichloride, as shown in FIG. 3 and the formula (12). do.
  • tin tetrachloride SnCl 4
  • tributyltin chloride is produced as a by-product.
  • the reaction mixture represented by the formula (12) is concentrated and precision distillation is repeated a plurality of times to obtain monobutyltin trichloride.
  • This monobutyltin trichloride is dissolved in an organic solvent, an alkaline aqueous solution is added dropwise to this solution and stirred to obtain a precipitate, which is then solid-liquid separated and monobutyltin trichloride as shown in FIG. 3 and formula (13).
  • precision distillation is repeated a plurality of times until the ⁇ -ray emission amount becomes 0.01 cph / cm 2 or less to obtain a monobutyltin oxide having a low ⁇ -ray emission amount.
  • butylmagnesium chloride for synthesizing the monobutyltin oxide represented by the formula (1-1) synthesized by the formula (13) has been described.
  • the organic magnesium halides are shown in the formulas (14) to (21). Using these organomagnesium halides, the amount of ⁇ -ray emission represented by the above-mentioned formulas (1-2) to (1-9) is 0.01 cph / cm 2 or less in the same manner as in the above-mentioned method.
  • Organic tin compounds are synthesized.
  • the formula (14) is isopropylmagnesium chloride, from which the monoisopropyltin oxide represented by the above formula (1-2) is produced.
  • the formula (15) is octylmagnesium bromide, and the monooctyltin oxide represented by the above-mentioned formula (1-3) is produced from the octylmagnesium bromide.
  • the formula (16) is tertiary butyl magnesium chloride, and the mono-tert-butyl tin oxide represented by the above formula (1-4) is produced from the tertiary butyl magnesium chloride.
  • Formula (17) is propylmagnesium bromide, and from this propylmagnesium bromide, the monopropyl tin oxide represented by the above-mentioned formula (1-5) is produced.
  • the formula (18) is pentylmagnesium bromide, and the monopentyltin oxide represented by the above-mentioned formula (1-6) is produced from the pentylmagnesium bromide.
  • Formula (19) is hexyl magnesium bromide, from which hexyl magnesium bromide produces the monohexyl tin oxide represented by formula (1-7) above.
  • Formula (20) is magnesium bromide, and from this magnesium bromide, monoheptyl tin oxide represented by the above formula (1-8) is produced.
  • Formula (21) is bromide secondalibutylmagnesium, and the mono-sec-butyltin oxide represented by the above-mentioned formula (1-9) is produced from this bromide secondalibutylmagnesium.
  • the above organic tin compound is added and mixed with an organic solvent in a closed space where ⁇ -ray control is performed with respect to the instrument and the environment, and the mixture is centrifuged or a syringe filter. By removing the insoluble solid, the ⁇ -ray emission amount is 0.01 cph / cm 2 or less.
  • a liquid composition for forming an EUV resist film having a predetermined viscosity can be obtained depending on the mixing ratio of the organic tin compound and the organic solvent.
  • the tin content is 0.05% by mass or more and 24% by mass or less.
  • the tin content is preferably 0.5% by mass to 9% by mass. If it is less than 0.05% by mass, it becomes difficult to efficiently absorb EUV light irradiated to the resist film made of this organic tin compound. Further, if it exceeds 24% by mass, the EUV resist film forming liquid composition becomes unstable from the viewpoint of the solubility of the tin compound, and the metal residue after etching becomes a problem.
  • the tin content is a content using a value converted as the tin content contained in the organic tin compound.
  • the organic solvent used in the liquid composition for forming an EUV resist film is xylene, an aromatic compound such as toluene, ethers such as methylphenyl ether or methanol, 2-methoxy-1-methylethyl acetate, and the like.
  • ethers such as methylphenyl ether or methanol
  • 2-methoxy-1-methylethyl acetate examples thereof include esters such as ethyl acetate, ethyl lactate and n-butyl acetate, alcohols such as 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol and butanol, and ketones such as methyl ethyl ketone.
  • the EUV resist film obtained by the above method by a method such as spin coating on a cleaned substrate after applying a photosensitive substance in a state where ⁇ -ray control is performed for the equipment and the environment.
  • the forming liquid composition is coated.
  • a resist film is formed by holding and baking this coating film at a temperature of 120 ° C. to 210 ° C. for 3 to 10 minutes.
  • the coating amount of the liquid composition at the time of coating is adjusted so that the film thickness after baking is 5 nm to 90 nm.
  • the formed resist film is exposed to EUV and subjected to post-treatment such as development to produce a resist film having a patterned ⁇ -ray emission amount of 0.01 cph / cm 2 or less.
  • the resist film is formed by using the liquid composition for forming an EUV resist film using the organic tin compound of the present invention, but in addition to this, the organic tin compound of the present invention (for example, A resist film can also be formed by a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method using the monoalkyl tin trichloride represented by the above formula (8).
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • organotin compounds represented by the above-mentioned formulas (1-1) to (1-9), which are organotin compounds are the examples and comparative examples of the organotin oxide compounds, and the organotin compounds obtained in the examples and the comparative examples.
  • the results of the amount of ⁇ -ray emission will be described, and then the liquid composition for forming an EUV resist film using the organotin trialkoxide compounds represented by the formulas (1-1) to (1-9) and (9) will be described.
  • the results after film formation of the test example and the comparative test example and the EUV resist film forming liquid composition obtained in these test examples and the comparative test example will be described.
  • FIG. 4 shows a flow chart from metallic tin purified to emit low ⁇ rays in Examples and Comparative Examples to defect evaluation by CD-SEM (Critical Dimensions-SEM).
  • Example 1-1 Comparative Examples of Monobutyltin Oxide (Organic Tin Oxide Compound) of Formula (1-1)] ⁇ Example 1-1> Tin tetrachloride was synthesized from metallic tin. First, a three-necked glass flask with a volume of 500 mL and another flask with ⁇ -ray control were prepared. Specifically, the three-necked flask to be used and another flask were pickled and then alkaline-washed.
  • Sulfuric acid first prepared to a concentration of 15% by mass was raised to 45 ° C., and this sulfuric acid was circulated for 60 minutes in the part where the product of the three-necked flask to be used and the product of another flask came into contact, and this contact part was circulated. Washed. Subsequently, the ammonium carbonate solution prepared to a concentration of 38% by mass was circulated at room temperature for 40 minutes, and the contact portion was washed. Then, after cleaning with ion-exchanged water, the cleaning treatment was performed with a cleaning liquid containing a surfactant, the mixture was replaced with ion-exchanged water again, and then the drying treatment was performed with a dryer.
  • the above three ⁇ -ray controlled ports were used as a chlorine gas supply port, a nitrogen gas supply port, and a connection port for connecting to another flask.
  • 15 g of granular metallic tin as a starting material was placed in the three-necked flask. This metallic tin was less than 0.0005 cf / cm 2 .
  • 0.3 mol of chlorine gas was flowed in to react metallic tin with chlorine gas.
  • White smoke was generated and the reaction was sufficient, and tin chloride was synthesized from metallic tin.
  • the three-necked flask was heated to around 120 ° C., which is close to the boiling point of tin tetrachloride.
  • tetrabutyltin was synthesized from the tin tetrachloride.
  • a 2 L volumetric flask consisting of a stirrer, a reflux condenser and an isobaric dropping funnel, which is ⁇ -ray controlled
  • a tetrahydrofuran solution of butylmagnesium chloride which is a Grignard reagent
  • 2.8 of butylmagnesium chloride I put it in a mole. 250 mL of toluene was added thereto, and the mixture was heated to 110 ° C. to distill off the solvent in the Grignard reagent.
  • monobutyltin oxide was produced from the above monobutyltin trichloride.
  • 20 g of monobutyltin trichloride obtained in the above synthesis is dissolved in 900 mL of ethanol, and while cooling and stirring the solution so that the temperature is 40 ° C. or lower, 12 g of ammonia water having a concentration of 28% by mass is added to this solution for 40 minutes. And dropped.
  • the temperature was raised to 55 ° C., and the mixture was stirred at this temperature for 4 hours.
  • the resulting precipitate was suction filtered, washed with ion-exchanged water and centrifuged.
  • the white solid obtained after centrifugation was dried under reduced pressure at 80 ° C. for 18 hours to obtain 8.8 g of monobutyltin oxide.
  • the production of this monobutyltin oxide is represented by the above formula (13).
  • Example 1-2 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.002 cf / cm 2 was used. Except for this, monobutyltin oxide was produced in the same manner as in Example 1-1.
  • Example 1-3 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.01 cph / cm 2 was used. Except for this, monobutyltin oxide was produced in the same manner as in Example 1-1.
  • Example 1-1 As a starting material, a commercially available product of granular metallic tin having an ⁇ -ray emission amount of 0.5 cph / cm 2 was used. Except for this, monobutyltin oxide was produced in the same manner as in Example 1-1.
  • Example 1-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. However, unlike Example 1-1, the total number of distillations was 2 without performing ⁇ -ray control for the equipment and environment used. Except for this, monobutyltin oxide was produced in the same manner as in Example 1-1.
  • Example 2 Comparative Examples of Monoisopropyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-2)]
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • isopropylmagnesium chloride was used instead of the butylmagnesium chloride used in Example 1-1.
  • the total number of distillations was four. Except for this, monoisopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 2-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butyl magnesium chloride used in Example 1-1, the same isopropyl magnesium chloride as in Example 2 was used. Except for this, monoisopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 2-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butyl magnesium chloride used in Example 1-1, the same isopropyl magnesium chloride as in Example 2 was used. However, unlike Example 1-1, the total number of distillations was 2 without performing ⁇ -ray control for the equipment and environment used. Except for this, monoisopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 3 Comparative Examples of Monooctyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-3)
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • octylmagnesium bromide was used instead of the butylmagnesium chloride used in Example 1-1. The total number of distillations was four. Except for this, monooctyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 3-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same octylmagnesium bromide as in Example 3 was used. Except for this, monooctyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 3-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same octylmagnesium bromide as in Example 3 was used. However, unlike Example 1-1, the total number of distillations was 2 without performing ⁇ -ray control for the equipment and environment used. Other than that, monoioctyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 4 Comparative Examples of Mono-tert-Butyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-4)
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • tertiary butylmagnesium chloride was used instead of the butylmagnesium chloride used in Example 1-1. The total number of distillations was four. Except for this, mono-tert-butyltin oxide was produced in the same manner as in Example 1-1.
  • Example 4-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same tertiary butylmagnesium chloride as in Example 4 was used. Except for this, mono-tert-butyltin oxide was produced in the same manner as in Example 1-1.
  • Example 4-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same tertiary butylmagnesium chloride as in Example 4 was used. However, unlike Example 1-1, the total number of distillations was 2 without performing ⁇ -ray control for the equipment and environment used. Except for this, mono-tert-butyltin oxide was produced in the same manner as in Example 1-1.
  • Example 5 Comparative Examples of Monopropyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-5)]
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • propylmagnesium bromide was used instead of the butylmagnesium chloride used in Example 1-1.
  • the total number of distillations was 5. Except for this, monopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 5-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same propylmagnesium bromide as in Example 5 was used. Except for this, monopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 5-2> As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same propylmagnesium bromide as in Example 5 was used. However, unlike Example 1-1, the total number of distillations was 3 without performing ⁇ -ray control for the equipment and environment used. Except for this, monopropyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 6 Comparative Examples of Monopentyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-6)
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • pentylmagnesium bromide was used instead of the butylmagnesium chloride used in Example 1-1. The total number of distillations was four. Except for this, monopentyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 6-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same pentyl magnesium bromide as in Example 6 was used. Except for this, monopentyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 6-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same pentyl magnesium bromide as in Example 6 was used. However, unlike Example 1-1, the total number of distillations was 3 without performing ⁇ -ray control for the equipment and environment used. Except for this, monopentyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 7 Comparative Examples of Monohexyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-7)] ⁇ Example 7> As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, hexylmagnesium bromide was used. The total number of distillations was four. Except for this, monohexyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 7-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same hexylmagnesium bromide as in Example 7 was used. Except for this, monohexyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 7-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same hexylmagnesium bromide as in Example 7 was used. However, unlike Example 1-1, the total number of distillations was 3 without performing ⁇ -ray control for the equipment and environment used. Except for this, monohexyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 8 Comparative Examples of Monoheptyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-8)]
  • a starting material granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, heptylmagnesium bromide was used. The total number of distillations was 5. Except for this, monoheptyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 8-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same heptylmagnesium bromide as in Example 8 was used. Except for this, monoheptyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 8-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same heptylmagnesium bromide as in Example 8 was used. However, unlike Example 1-1, the total number of distillations was 3 without performing ⁇ -ray control for the equipment and environment used. Except for this, monoheptyl tin oxide was produced in the same manner as in Example 1-1.
  • Example 9 Comparative Examples of Mono-sec-Butyl Tin Oxide (Organic Tin Oxide Compound) of Formula (1-9)
  • granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used.
  • the bromide secondalibutylmagnesium was used instead of the butylmagnesium chloride used in Example 1-1. The total number of distillations was four. Except for this, mono-sec-butyltin oxide was produced in the same manner as in Example 1-1.
  • Example 9-1 As a starting material, granular metallic tin having an ⁇ -ray emission amount of 0.5 cf / cm 2 , which is the same commercially available product as in Comparative Example 1-1, was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same second bromide butylmagnesium as in Example 9 was used. Except for this, mono-sec-butyltin oxide was produced in the same manner as in Example 1-1.
  • Example 9-2 As a starting material, granular metallic tin having the same ⁇ -ray emission amount of less than 0.0005 cf / cm 2 as in Example 1-1 was used. Further, instead of the butylmagnesium chloride used in Example 1-1, the same second bromide butylmagnesium as in Example 9 was used. However, unlike Example 1-1, the total number of distillations was 3 without performing ⁇ -ray control for the equipment and environment used. Except for this, mono-sec-butyltin oxide was produced in the same manner as in Example 1-1.
  • the ⁇ -ray emission amount of 29 kinds of organic tin oxide compounds obtained in Examples 1-1 to 1-3, Examples 2 to 9 and Comparative Examples 1-1 to 9-2 was measured.
  • the results are shown in Table 1 below.
  • Table 1 shows the types of organotin compounds, the amount of ⁇ -ray emission of metallic tin as a starting material, the implementation or non-implementation of ⁇ -ray control during production, the number of distillations during production, and the ⁇ of organotin oxide compounds.
  • the amount of ray emitted is described.
  • the number of distillations at the time of manufacture is the cumulative number of times.
  • Comparative Example 1-2 Comparative Example 2-2, Comparative Example 3-2, Comparative Example 4-2, Comparative Example 5-2, Comparative Example 6-2, Comparative Example 7-2, Comparative Example 8-2 and In Comparative Example 9-2, since ⁇ -ray control was not performed at the time of production, even though monoalkyl tin oxide was produced from metallic tin as a starting material having an ⁇ -ray emission amount of less than 0.0005 cf / cm 2 .
  • the amount of ⁇ -ray emission of the final target substance, monoalkyltin oxide was in the range of 0.011 cf / cm 2 to 0.017 cf / cm 2 , which was high.
  • monoalkyltin oxide is produced from metallic tin as a starting material having an ⁇ -ray emission amount of less than 0.01 cf / cm 2 , and ⁇ -ray control is performed at the time of production.
  • This monobutyltin oxide and 5.8 g of p-toluenesulfonic acid as an acid were placed in a round bottom flask having a volume of 500 mL to which a Dean-Stark apparatus was connected and mixed. After reacting the mixture under reflux with toluene for 48 hours, the unreacted product was removed using a filter with a filtration accuracy of 10 ⁇ m to 16 ⁇ m. Then, 2-propanol was used as a solvent to dissolve the tetrabutylammonium hydroxide, and the solution was crystallized at a temperature of ⁇ 15 ° C. Finally, THF was added to the crystallized product and the solvent was removed under reduced pressure to produce a compound consisting of three types of monobutyltin oxides.
  • a liquid composition for forming an EUV resist film was prepared using this synthesized 12-mer cluster-type or cage-type tin compound. Specifically, the above-mentioned cluster type or cage type tin compound is weighed so that the tin content ratio is contained in the range of 0.05% by mass or more and 24% by mass or less in this liquid composition, and the tin compound is subjected to 29. Tests with different tin content in liquid compositions by dissolving in 8 mL of methyl ethyl ketone, stirring in a closed space for 24 hours, and removing insoluble solids with a 0.45 ⁇ m filtration precision syringe filter.
  • Example 10-1 to Test Example 10-2 and Comparative Test Example 10-1 to Comparative Test Example 11-1 Six kinds of EUV resist film forming liquid compositions of Example 10-1 to Test Example 10-2 and Comparative Test Example 10-1 to Comparative Test Example 11-1 were produced.
  • the types of the organic tin oxide compound used in the above example, the amount of ⁇ rays emitted thereof, and the content ratio of tin in the liquid composition are shown in Table 3 below.
  • FIG. 5 shows a production flow chart from tin tetrachloride having a low ⁇ -ray emission amount to obtaining an alkyl tin trialkoxide having a low ⁇ -ray emission amount.
  • Example 10-1 The organic tin trialkoxide compound t-butyl tin tributoxide was synthesized from tin tetrachloride and lithium dimethylamide.
  • tin tetrachloride (SnCl 4 ) having an ⁇ -ray emission amount of less than 0.0005 cf / cm 2 was used in order to obtain t-butyl tin tributoxide.
  • the t-butyl tin trimethyl amide represented by the above formula (9-2) required for the synthesis of t-butyl tin tributoxide was synthesized.
  • This reaction is represented by the following formula (23). Due to the high reactivity of the starting material, the reaction was carried out in a glove box filled with an argon atmosphere.
  • the synthesized tetrakis tin dimethylamide is purified using t-butylmagnesium chloride (see formula (16)), which is a Grignard reagent in THF, and then distilled to obtain the desired t-butyltin trimethyl. Amides were selectively collected.
  • t-butyl tin tributoxide was synthesized by substituting the purified t-butyl tin trimethylamide with an alcohol.
  • This reaction is represented by the following formula (24).
  • the dehydrated 1-butanol was slowly added to the purified t-butyltin trimethylamide in a glove box in which the atmosphere was made inert with argon, and the substitution reaction was carried out in an ice bath at ⁇ 5 ° C.
  • the valve was opened to relieve the pressure of the gas generated from the alcohol.
  • the temperature was returned to room temperature to volatilize the solvent, and then the produced t-butyl tin tributoxide was maintained at 90 ° C.
  • FIG. 5 is a production flow chart showing the process of obtaining an alkyl tin trialkoxide having a low ⁇ -ray emission amount from tin tetrachloride having a low ⁇ -ray emission amount. Specifically, as shown in FIG. 5, the first production flow diagram is shown.
  • Example 10-1 Distillate-purified t-butyltin tributoxide was applied to a clean Si wafer surface in the air, fired, and then hydrolyzed, and the amount of ⁇ -ray emission of this hydrolyzate was measured. When the amount of ⁇ -ray emission exceeded 0.01 cph / cm 2 , distillation was repeated. In Example 10-1, ⁇ -ray control was performed until the final target substance was synthesized, in order to prevent contamination with an ⁇ -ray source and to prevent an increase in the amount of ⁇ -ray emission. In the reaction pathways of the formula (22), the formula (23) and the formula (24), the total number of distillations was 5 times each.
  • Example 10-2 As a starting material for synthesizing t-butyltin trimethylamide, tin tetrachloride (SnCl 4 ) having an ⁇ -ray emission amount of 0.002 cf / cm 2 was used. Other than that, t-butyl tin tributoxide was obtained in the same manner as in Example 10-1.
  • Example 10-2 As a starting material for synthesizing t-butyltin trimethylamide, tin tetrachloride (SnCl 4 ) having an ⁇ -ray emission amount of 0.0005 cf / cm 2 was used. However, unlike Example 10-1, ⁇ -ray control was not performed to prevent contamination of the ⁇ -ray source and to prevent an increase in the amount of ⁇ -ray emission. The total number of distillations was three. Other than that, t-butyl tin tributoxide was obtained in the same manner as in Example 10-1.
  • Example 10-1 The ⁇ -ray emission amounts of the four types of t-butyl tin tributoxide obtained in Example 10-1, Example 10-2, Comparative Example 10-1 and Comparative Example 10-2 were measured. The results are shown in Table 4 below. Table 4 shows the types of organotin compounds, the amount of ⁇ -ray emission of tin (SnCl 4 ) as a starting material, the implementation or non-implementation of ⁇ -ray control during production, the number of distillations during production, and t. -The amount of ⁇ -ray emission of butyltin tributoxide is described.
  • Examples 10-1 and 10-2 tin tetrachloride to t-butyl as a starting material having ⁇ -ray emission amounts of less than 0.0005 cf / cm 2 and 0.002 cf / cm 2 , respectively. Since tin tributoxide was produced and ⁇ -ray control was performed at the time of production, the ⁇ -ray emission amount of t-butyl tin tributoxide, which is the final target substance, was in the range of 0.002 cf / cm 2 or less, which was low. ..
  • Example of Production of Liquid Composition for Forming EUV Resist Film from Organic Tin Trialkoxide Compound of Formula (9) From the four types of t-butyl tin tributoxide obtained in Example 10-1, Example 10-2, Comparative Example 10-1 and Comparative Example 10-2, Test Example 11-1, Test Example 11-2, Four kinds of EUV resist film forming liquid compositions of Comparative Test Example 12-1 and Comparative Test Example 12-2 were produced. Specifically, four types of t-butyl tin tributoxide are weighed so that the tin content of the liquid composition is 0.05 mol / L, and this tin compound is dissolved in 29.8 mL of methyl ethyl ketone.
  • the Si wafer was placed at a temperature of 120 ° C. for 40 minutes with hexamethyldisilazane (HMDS). After exposure to steam, baking and hydrophobization for dehydration were performed.
  • HMDS hexamethyldisilazane
  • the EUV resist film forming liquid composition obtained in the above-mentioned test example and the comparative test example was spin-coated on the Si wafer thus pretreated using a spin coater (MS-B100 manufactured by Mikasa). A coating film was formed. The coating film was held at a temperature of 150 ° C. for 5 minutes for baking.
  • the coating amount of the liquid composition at the time of coating was adjusted so that the film thickness after baking was 20 nm. After allowing the baked Si wafer to stand for 120 minutes, a positive simulated resist film was formed using 2.38% by mass of tetramethylammonium hydroxide (TMAH) as a developing solution, and the simulated resist film was subjected to development treatment. Was done.
  • TMAH tetramethylammonium hydroxide
  • Comparative Test Example 1-2 Comparative Test Example 2-2, Comparative Test Example 3-2, Comparative Test Example 4-2, Comparative Test Example 5-2, Comparative Test Example 6-2, Comparative Test Example 7-2.
  • Comparative Test Example 8-2 and Comparative Test Example 9-2 the ⁇ -ray emission amount of the monoalkyl tin oxide used was in the range of 0.011 cf / cm 2 to 0.017 cf / cm 2 , and 0.01 cf / cm. Since it was higher than cm 2 , the number of defects of 5 nm or more in the simulated resist film was 1 to 2, and the judgment was "impossible" in all the comparative test examples.
  • the ⁇ -ray emission amount of the monoalkyl tin oxide used was in the range of 0.0020 cf / cm 2 or less, which was lower than 0.01 cf / cm 2 , and therefore the simulated resist.
  • the number of defects of 5 nm or more in the film was 0, and the judgment was "OK" in all the test examples.
  • the ⁇ -ray emission amount of the monobutyltin oxide used was 0.013 cf / cm 2
  • the tin in the EUV resist film forming liquid composition was The content ratio of was 0.07% by mass. Since the amount of ⁇ -ray emission of monobutyltin oxide exceeds 0.01 cph / cm 2 , the number of defects of 5 nm or more in the simulated resist film is 1, and the judgment is “impossible”.
  • the ⁇ -ray emission amount of the monobutyltin oxide used was 0.011 cf / cm 2
  • the content ratio of tin in the EUV resist film forming liquid composition was 25.1 mass by mass. %Met. Since the ⁇ -ray emission amount of monobutyltin oxide exceeded 0.01 cph / cm 2 and the tin content in the EUV resist film forming liquid composition exceeded 24% by mass, the number of defects of 5 nm or more in the simulated resist film There were more than 3 in Comparative Test Example 10-1, and the judgment was "impossible".
  • the ⁇ -ray emission amount of the monobutyltin oxide used was 0.011 cf / cm 2 , and the content ratio of tin in the EUV resist film forming liquid composition was 7.98 mass. %Met. Since the amount of ⁇ -ray emission of monobutyltin oxide exceeded 0.01 cph / cm 2 , the number of defects of 5 nm or more in the simulated resist film was 2, and the judgment was “impossible”. Further, in Comparative Test Example 11-1, the ⁇ -ray emission amount of the monobutyltin oxide used was 0.012 cf / cm 2 , and the content ratio of tin in the EUV resist film forming liquid composition was 8.12 mass. %Met. Since the amount of ⁇ -ray emission of monobutyltin oxide exceeded 0.01 cph / cm 2 , the number of defects of 5 nm or more in the simulated resist film was 2, and the judgment was “impossible”.
  • the ⁇ -ray emission amount of the monoalkyl tin oxide used was both in the range of less than 0.0005 cf / cm 2 , and the EUV resist film forming liquid was used.
  • the tin content in the composition was 0.05% by mass and 23.1% by mass, respectively. Since the ⁇ -ray emission amount of monobutyltin oxide was 0.01 cph / cm 2 or less and the tin content in the EUV resist film forming liquid composition was 24% by mass or less, defects of 5 nm or more in the simulated resist film The number was 0, and the judgment was "OK" in all the test examples.
  • the ⁇ -ray emission amount of t-butyltin tributoxide used was less than 0.0005 cf / cm 2 and 0.002 cf / cm 2 , respectively.
  • the content ratio of tin in the EUV resist film forming liquid composition was 0.5% by mass and 0.8% by mass. Since the ⁇ -ray emission amount of t-butyl tin tributoxide was 0.01 cf / cm 2 or less and the tin content in the EUV resist film forming liquid composition was 24% by mass or less, 5 nm in the simulated resist film. The above number of defects was 0, and the judgment was "OK" in all the test examples.
  • the organotin compound and the liquid composition for forming an EUV resist film of the present invention are used in the field of forming an EUV resist film.

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JP2018124354A (ja) * 2017-01-30 2018-08-09 Jsr株式会社 レジスト膜形成方法及び保護膜形成用組成物
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