WO2023176192A1 - 半導体洗浄液および半導体洗浄液の製造方法 - Google Patents

半導体洗浄液および半導体洗浄液の製造方法 Download PDF

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Publication number
WO2023176192A1
WO2023176192A1 PCT/JP2023/003901 JP2023003901W WO2023176192A1 WO 2023176192 A1 WO2023176192 A1 WO 2023176192A1 JP 2023003901 W JP2023003901 W JP 2023003901W WO 2023176192 A1 WO2023176192 A1 WO 2023176192A1
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Prior art keywords
distillation column
isopropyl alcohol
semiconductor cleaning
cleaning liquid
stage
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PCT/JP2023/003901
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English (en)
French (fr)
Japanese (ja)
Inventor
俊輔 保坂
貴史 徳永
義晶 山下
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Tokuyama Corp
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Tokuyama Corp
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Priority to JP2023535854A priority Critical patent/JP7402385B1/ja
Priority to US18/842,549 priority patent/US20250171718A1/en
Priority to KR1020247033182A priority patent/KR20240163660A/ko
Priority to DE112023001404.3T priority patent/DE112023001404T5/de
Priority to CN202380022672.XA priority patent/CN118742996A/zh
Publication of WO2023176192A1 publication Critical patent/WO2023176192A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/10—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H10P70/15—Cleaning before device manufacture, i.e. Begin-Of-Line process by wet cleaning only

Definitions

  • the present invention relates to a semiconductor cleaning liquid and a method for manufacturing a semiconductor cleaning liquid.
  • a substrate such as a semiconductor substrate or a glass substrate is cleaned with a semiconductor cleaning liquid and then dried.
  • a semiconductor cleaning liquid For example, isopropyl alcohol is used as the semiconductor cleaning liquid.
  • Patent Document 1 As a method for producing isopropyl alcohol, for example, a direct hydration method of propylene (see Patent Document 1) is known.
  • isopropyl alcohol produced by the direct hydration method of propylene contains t-butyl alcohol as an impurity, so when used as a semiconductor cleaning solution, the t-butyl alcohol residue may have an adverse effect on semiconductor devices. There are concerns. For this reason, it is desired to reduce the content of t-butyl alcohol in the semiconductor cleaning solution, but since t-butyl alcohol has approximately the same boiling point as isopropyl alcohol (82°C) Difficult to separate.
  • An object of the present invention is to provide a semiconductor cleaning liquid with a reduced content of t-butyl alcohol and a method for producing a semiconductor cleaning liquid that can reduce the content of t-butyl alcohol.
  • One aspect of the present invention is a semiconductor cleaning liquid containing isopropyl alcohol, in which the mass ratio of t-butyl alcohol to isopropyl alcohol is 1 ppm or less.
  • the above semiconductor cleaning liquid may have a mass ratio of pentanone to isopropyl alcohol of 1 ppb or more and 50 ppb or less, and a mass ratio of crotonaldehyde to isopropyl alcohol of 0.5 ppb or more and 10 ppb or less.
  • Isopropyl alcohol may be produced by a direct hydration method of propylene.
  • Another aspect of the present invention is a method for producing a semiconductor cleaning solution, in which a crude isopropyl alcohol aqueous solution containing t-butyl alcohol as an impurity is supplied to a raw material supply stage of a first distillation column, and
  • the first distillation step includes extracting a first distillate containing low-boiling impurities having a boiling point lower than that of isopropyl alcohol, and extracting a first bottoms from the bottom of the first distillation column, and the first distillation step includes: , the first distillation is carried out so that the water content in the liquid phase in three or more stages as the theoretical number of stages from the raw material supply stage to the top of the first distillation column is 15% by mass or more.
  • a fluid containing water is supplied from the outside of the first distillation column to a predetermined stage which is two or more theoretical stages above the raw material supply stage of the tower.
  • the method for producing the semiconductor cleaning liquid described above includes supplying the first distillate to a raw material supply stage of a second distillation column, and extracting the second distillate containing the low-boiling point impurities from the top of the second distillation column.
  • the second distillation step further includes a second distillation step of extracting a second bottom liquid from the bottom of the second distillation column, and in the second distillation step, the second distillation column is placed in a predetermined stage of the second distillation column. Water may be supplied from the outside, and the second bottoms may be supplied as the water-containing liquid in the first distillation step.
  • the predetermined stage of the second distillation column may be a stage between the raw material supply stage and the top of the second distillation column.
  • the above method for producing a semiconductor cleaning liquid may further include a reaction step of obtaining the crude isopropyl alcohol aqueous solution by a direct hydration method of propylene.
  • the present invention it is possible to provide a semiconductor cleaning liquid with a reduced content of t-butyl alcohol and a method for producing a semiconductor cleaning liquid that can reduce the content of t-butyl alcohol.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 0% by mass.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 18% by mass.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 36% by mass.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 54% by mass.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 72% by mass.
  • FIG. 1 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 0% by mass.
  • FIG. 2 is an xy diagram of t-butyl alcohol/isopropyl alcohol when the water content is 90% by mass.
  • FIG. 2 is an xy diagram of water/isopropyl alcohol. It is a figure showing an example of a low-boiling distillation process in the manufacturing method of the semiconductor cleaning liquid of this embodiment. It is a figure which shows another example of the low-boiling distillation process in the manufacturing method of the semiconductor cleaning liquid of this embodiment.
  • the semiconductor cleaning liquid of this embodiment contains isopropyl alcohol, and the mass ratio of t-butyl alcohol to isopropyl alcohol is 1 ppm or less, more preferably 0.5 ppm or less, and still more preferably 0.3 ppm or less. Therefore, even if the substrate is cleaned using the semiconductor cleaning liquid of this embodiment, the t-butyl alcohol residue will not have an adverse effect on the semiconductor device.
  • the mass ratio of t-butyl alcohol to isopropyl alcohol is not particularly limited, but if it is too low, the cost will increase, so it is preferably 0.01 ppm or more, more preferably 0.1 ppm or more.
  • the mass ratio of t-butyl alcohol to isopropyl alcohol is measured by gas chromatography mass spectrometry (GC-MS method).
  • GC-MS method gas chromatography mass spectrometry
  • Isopropyl alcohol can be produced, for example, by a direct hydration method of propylene.
  • isopropyl alcohol produced by the direct hydration method of propylene inevitably contains impurities such as 2-pentanone and crotonaldehyde.
  • the mass ratio of 2-pentanone to isopropyl alcohol in the semiconductor cleaning solution of the present embodiment is not particularly limited, but is, for example, 1 ppb or more and 50 ppb or less, preferably 2 ppb or more and 30 ppb or less.
  • the mass ratio of crotonaldehyde to isopropyl alcohol in the semiconductor cleaning solution of the present embodiment is not particularly limited, but is, for example, 0.5 ppb or more and 20 ppb or less, preferably 2 ppb or more and 10 ppb or less.
  • the content of isopropyl alcohol in the semiconductor cleaning solution of this embodiment is preferably 99.99% by mass or more, and more preferably 99.999% by mass or more, when expressed as a content excluding water. preferable.
  • the content of water in the semiconductor cleaning liquid of this embodiment is not particularly limited, but is, for example, 0.1 ppm or more and 100 ppm or less, preferably 1 ppm or more and 20 ppm or less.
  • the semiconductor cleaning liquid of this embodiment can be manufactured by a method for manufacturing a semiconductor cleaning liquid of this embodiment that will be described later.
  • a crude isopropyl alcohol aqueous solution containing t-butyl alcohol as an impurity is supplied to the raw material supply stage of the first distillation column, and the boiling point is higher than that of isopropyl alcohol from the top of the first distillation column.
  • the method includes a first distillation step in which a first distillate containing low-boiling impurities is extracted, and a first distillate is extracted from the bottom of the first distillation column.
  • the water content in the liquid phase in 3 or more theoretical stages from the raw material supply stage to the top of the first distillation column is 15% by mass or more.
  • a water-containing fluid is supplied from outside the first distillation column. This reduces the content of t-butyl alcohol in the semiconductor cleaning solution.
  • the content of water in the liquid phase in the theoretical number of stages from the raw material supply stage to the top of the first distillation column is 3 or more stages, more preferably 4 stages or more above the stage. It is preferable that the amount is % by mass or more.
  • Figures 1 to 6 show xy diagrams of t-butyl alcohol/isopropyl alcohol when the water content is 0 to 90% by mass.
  • Figure 7 shows an xy diagram of water/isopropyl alcohol.
  • a water/isopropyl alcohol mixture with a water content of 95% by mass has two theoretical stages, the water content is 20% by mass, and four theoretical stages. It can be seen that the content is 15% by mass, and at 6 theoretical stages, the water content is 13% by mass (the content of water in the azeotropic composition is 12.5% by mass).
  • the first distillation column is adjusted so that the water content in the liquid phase in three or more stages is 15% by mass or more as the theoretical number of stages from the raw material supply stage to the top of the first distillation column.
  • a water-containing fluid can be supplied from outside the first distillation column to a predetermined stage that is two or more theoretical stages above the raw material supply stage of the tower.
  • the fluid containing water may be a gas or a liquid.
  • the content of water in the water-containing fluid and the amount of water supplied may be adjusted as appropriate.
  • the water content in the water-containing fluid is preferably 50% by mass or more, more preferably 80% by mass or more.
  • the mass ratio of the amount of water supplied to the amount of raw material is preferably 1/10 to 1/1000, more preferably 1/50 to 1/200. It is. If the amount of water supplied is too large, the amount of water in the system will increase, so it is necessary to increase the diameter of the distillation column, and it is necessary to take out excess water from the system of the entire process. If the amount of water supplied is too small, the separation of t-butyl alcohol will be insufficient.
  • the water removed in the azeotropic distillation step and dehydration step described later can be used in the reaction step described later, but water used in the reaction step and as an additional amount of water that is slightly lost during operation. , water fed to the first distillation column can be used.
  • the method for producing a semiconductor cleaning liquid of this embodiment may further include a reaction step of obtaining a crude isopropyl alcohol aqueous solution by a direct hydration method of propylene.
  • the reaction of propylene in the reaction process is as follows: C 3 H 6 +H 2 O ⁇ CH 3 CH(OH)CH 3 It is expressed as By carrying out such a reaction in a reaction tower, a reaction product containing isopropyl alcohol is obtained.
  • the temperature and pressure in the reaction tower are preferably 200°C or more and 300°C or less and 150 atm or more and 250 atm or less, respectively.
  • various polyanion acid catalysts such as molybdenum-based and tungsten-based inorganic ion exchangers can be used.
  • the acid catalyst phosphotungstic acid, silicotungstic acid, and silicomolybdic acid are preferable from the viewpoint of reaction activity.
  • the reaction product dissolved in water is extracted from the reaction tower. Then, by cooling the reaction product and reducing the pressure, unreacted propylene dissolved in water is recovered as a gas, and a crude isopropyl alcohol aqueous solution is obtained. The recovered propylene is reused as raw material.
  • the content of water in the crude isopropyl alcohol aqueous solution is preferably 80% by mass or more, more preferably 90% by mass or more.
  • the method for manufacturing a semiconductor cleaning liquid of this embodiment includes a first distillation step as a low-boiling distillation step of distilling the crude isopropyl alcohol aqueous solution obtained in the reaction step.
  • Figure 8 shows an example of a low-boiling distillation process.
  • the crude isopropyl alcohol aqueous solution is supplied to the raw material supply stage of the low-boiling distillation column (first distillation column) 1 via a conduit and is distilled.
  • a condenser is provided at the top of the first distillation column 1, and part of the liquid condensed in the condenser is refluxed, and the remainder is extracted as a first distillate. Further, the first bottoms are extracted from the bottom of the first distillation column 1 and purified.
  • the reflux ratio of the first distillation column 1 is not particularly limited, but is, for example, 10 or more and 100 or less, preferably 50 or more and 80 or less.
  • the first distillate extracted from the top of the first distillation column 1 is supplied to the raw material supply stage of the recovery distillation column (second distillation column) 2 and distilled.
  • a condenser is provided at the top of the second distillation column 2, and part of the liquid condensed in the condenser is refluxed, and the remainder is extracted as a second distillate and disposed of.
  • water is supplied to a predetermined stage of the second distillation column 2, and it is preferable to supply water to a stage between the raw material supply stage and the top of the second distillation column 2.
  • the second bottoms from the bottom of the second distillation column 2 and supply it to a predetermined stage two or more theoretical stages higher than the raw material supply stage of the first distillation tower 1. It is more preferable to supply the material to a predetermined theoretical stage that is five or more theoretical stages higher than the raw material supply stage of the distillation column 1.
  • the reflux ratio of the second distillation column 2 is not particularly limited, but is, for example, 5 or more and 50 or less, preferably 10 or more and 30 or less.
  • Examples of low-boiling impurities contained in the first distillate and the second distillate include olefins such as ethylene, propylene, butenes, pentenes, and hexene, methane, ethane, propane, butane, pentane, and hexane.
  • Examples include alkanes such as , aldehydes such as acetaldehyde and propylene aldehyde, and ketones such as acetone and butanone.
  • FIG. 9 shows another example of the low-boiling distillation process.
  • the second distillation column 2 is omitted, and water is supplied instead of the second bottoms to a predetermined theoretical stage two or more stages higher than the raw material supply stage of the first distillation tower 1. has the same configuration as FIG. 8.
  • the crude isopropyl alcohol aqueous solution is supplied to the raw material supply stage of the low-boiling distillation column (first distillation column) 1 via a conduit and is distilled.
  • a condenser is provided at the top of the first distillation column 1, and part of the liquid condensed in the condenser is refluxed, and the remainder is extracted as a first distillate and disposed of.
  • water is supplied to a predetermined theoretical stage two or more stages higher than the raw material supply stage of the first distillation column 1. Furthermore, the first bottoms are extracted from the bottom of the first distillation column 1 and purified.
  • the reflux ratio of the first distillation column 1 is not particularly limited, but is, for example, 10 or more and 100 or less, preferably 50 or more and 80 or less.
  • first distillation column 1 and the second distillation column 2 may be either a tray column or a packed column, respectively, but are preferably a tray column.
  • the number of theoretical plates in each distillation column is not particularly limited, but the number of theoretical plates in the first distillation column 1 is preferably 5 to 80 plates, more preferably 10 to 50 plates.
  • the number of theoretical plates in the second distillation column 2 is preferably 3 to 20, more preferably 5 to 15.
  • the actual number of plates may be adjusted as appropriate to achieve the above-mentioned theoretical plate number, but is, for example, 10 or more and 100 or less, preferably 20 or more and 70 or less. It is.
  • the actual number of plates is, for example, 5 or more and 30 or less, preferably 10 or more and 25 or less.
  • the trays in the tray column include cross-flow trays, shower trays, and the like.
  • the packing in the packed column include Raschig rings and Lessing rings.
  • the material for the tower and the packing include iron, stainless steel, Hastelloy, borosilicate glass, quartz glass, and fluororesin (eg, polytetrafluoroethylene).
  • the positions in which the raw material supply stages are provided in the first distillation column 1 and the second distillation column 2 are not particularly limited, but are preferably three or more theoretical stages below the top of the column.
  • the pressures of the first distillation column 1 and the second distillation column 2 are not particularly limited, but are, for example, 0.0 to 0.2 MPa. At this time, the temperatures at the top and bottom of the first distillation column 1 and the second distillation column 2 may be appropriately set depending on the pressure.
  • the method for manufacturing the semiconductor cleaning liquid of this embodiment may further include a purification step of purifying the first bottom liquid to obtain the semiconductor cleaning liquid of this embodiment.
  • the purification process consists of an azeotropic distillation process in which the first bottoms are supplied to the raw material supply stage of the azeotropic distillation column and distilled to obtain an azeotropic mixture of isopropyl alcohol and water; It is preferable to include a dehydration step of dehydrating the azeotropic mixture, and a high-boiling distillation step of supplying the dehydrated azeotropic mixture to a raw material supply stage of a high-boiling distillation column and distilling it to obtain a semiconductor cleaning liquid.
  • azeotropic distillation process In the azeotropic distillation process, the first bottoms are distilled and an azeotropic mixture of isopropyl alcohol and water is taken out as a distillate from the top of the azeotropic distillation column, and at the bottom of the azeotropic distillation column. The bottoms containing high-boiling impurities with a boiling point higher than that of isopropyl alcohol is taken out.
  • the azeotropic temperature of isopropyl alcohol and water is 80.1°C
  • the isopropyl alcohol and water are distilled from the top of the column.
  • An azeotrope is removed.
  • high-boiling impurities are taken out along with water at the bottom of the column.
  • azeotropic distillation step may be carried out according to the conditions described for the low-boiling distillation step.
  • Dehydration methods include, but are not particularly limited to, distillation, adsorption, membrane permeation, and the like.
  • water can be removed by adding diethyl ether, benzene, toluene, trichloroethylene, dichloromethane, hexene, etc. to create a three-component azeotropic composition. I can do it.
  • the semiconductor cleaning liquid obtained in the high-boiling distillation process may be further purified by methods such as adsorption, or metal particles, inorganic particles, organic particles, etc. may be removed by filter filtration, if necessary. However, metal ions and the like may be removed using an ion exchange resin tower.
  • ⁇ Analysis example 1> Measurement of moisture concentration in samples containing high concentration of moisture
  • ⁇ Analysis example 2> Aldehyde/ketone concentration measurement
  • aldehyde and ketone compounds in isopropyl alcohol containing water were analyzed using this method. Note that even if the sample does not contain water, it can be similarly analyzed using this method.
  • DNPH 2,4-dinitrophenylhydrazine
  • a DNPH hydrochloric acid solution was prepared by mixing 100 mg of DNPH and 100 ml of 2 mol/L hydrochloric acid. 50 ml of isopropyl alcohol and 1 ml of DNPH hydrochloric acid solution were mixed, left to stand for 1 hour, and concentrated 50 times to 1 ml. The obtained concentrated sample was subjected to high performance liquid chromatography (HPLC) analysis under the following conditions. As a result of calculating the lower limit of quantification using standard substances, the lower limit of quantification for acetaldehyde, propionaldehyde, crotonaldehyde, and 2-pentanone was 0.1 ppb.
  • ⁇ Analysis example 3-1> (t-butyl alcohol concentration measurement)
  • the t-butyl alcohol contained in isopropyl alcohol containing water was measured by the headspace method using GC-MS under the measurement conditions shown below.
  • the lower limit of quantification of t-butyl alcohol in a water concentration of 95% and an isopropyl alcohol concentration of 5% was 5 ppb.
  • ⁇ Analysis example 3-2> (t-butyl alcohol concentration measurement)
  • the t-butyl alcohol contained in isopropyl alcohol was measured using GC-MS under the measurement conditions shown below.
  • the lower limit of quantitation for t-butyl alcohol was 10 ppb.
  • the recovered propylene was put into a propylene recovery drum for reuse as raw material.
  • the conversion rate of propylene was 84.0%
  • the selectivity of propylene to isopropyl alcohol was 99.2%
  • the content of water in the crude isopropyl alcohol aqueous solution was 95% by mass.
  • first distillation column An Aldershaw-type low-boiling distillation column (first distillation column) with 60 plates and an Aldershaw-type recovery distillation column (second distillation column) with 20 plates were installed.
  • first distillation column is a container with a 2 L bottom, and the first bottoms are extracted from the bottom of the column.
  • the first distillation column is equipped with a condenser at the top (top of the column), and part of the liquid condensed in the condenser is refluxed to the top of the column, and the remainder is extracted as the first distillate. .
  • the second distillation column is a container with a column bottom of 500 mL, and the second bottom liquid is extracted from the column bottom. Further, the second distillation column is provided with a condenser at the top of the column, and part of the liquid condensed in the condenser is refluxed to the top of the column, and the remainder is extracted as a second distillate.
  • the crude isopropyl alcohol aqueous solution was supplied at 10 L/h to the raw material supply stage (8th stage) located 7 stages below the top (1st stage) of the first distillation column, and the crude isopropyl alcohol aqueous solution was distilled.
  • the temperature at the top of the column was 75 to 85°C
  • the column pressure (gauge pressure) was 0 to 10 kPa.
  • the reflux amount was set to 2.5 L/h
  • the reflux ratio was set to about 62.5
  • the first distillate was extracted from the condenser at a rate of 40 ml/h.
  • the first bottoms were extracted from the bottom of the column at a rate of about 10 L/h so that the liquid volume in the first distillation column was maintained at about 1.5 L.
  • the first distillate was supplied at a rate of 40 ml/h to the raw material supply stage (5 stages) located 4 stages below the top of the second distillation column, and the first distillate was distilled.
  • the temperature at the top of the column was 50 to 80°C, and the column pressure (gauge pressure) was 0 to 10 kPa.
  • the reflux amount was set to 30 mL/h, the reflux ratio was set to about 6, and water was supplied to the top of the second distillation column at 60 ml/h.
  • the second bottoms were extracted from the bottom of the second distillation column at a rate of 95 ml/h and supplied to the top of the first distillation column.
  • the second distillate was extracted from the condenser of the second distillation column at a rate of 5 ml/h and discarded.
  • the first bottoms were supplied to the raw material supply stage of the azeotropic distillation column and distilled to obtain an azeotropic mixture of isopropyl alcohol and water (mass ratio 87.5:12.5).
  • the azeotrope of isopropyl alcohol and water was dehydrated and then distilled using a high-boiling distillation column to obtain a semiconductor cleaning solution.
  • the content of water in the liquid phase 15% by mass or more in 3 or more theoretical stages among the stages from the raw material supply stage to the top of the column, from the top of the first distillation column.
  • the content of water in the liquid phase in the stage three stages below (fourth stage), that is, the stage four stages above the raw material supply stage (eighth stage) of the first distillation column (fourth stage) is 15% by mass or more. That's fine.
  • Example 2 (low-boiling distillation step of crude isopropyl alcohol aqueous solution), water is supplied to the top of the second distillation column at a rate of 120 ml/h, and a second bottoms is extracted from the bottom of the second distillation column at a rate of 155 ml/h.
  • a semiconductor cleaning solution was obtained in the same manner as in Example 1 except that it was supplied to the top of the first distillation column.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 0.3 ppm. Further, the semiconductor cleaning liquid had a mass ratio of 2-pentanone to isopropyl alcohol of 20 ppb, and a mass ratio of crotonaldehyde to isopropyl alcohol of 8 ppb.
  • Example 3> Low-boiling distillation step of crude isopropyl alcohol aqueous solution is the same as in Example 2 except that the second bottoms were supplied from the bottom of the second distillation column to three stages above the raw material supply stage of the first distillation column. A semiconductor cleaning solution was obtained.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 0.8 ppm. Further, the semiconductor cleaning liquid had a mass ratio of 2-pentanone to isopropyl alcohol of 20 ppb, and a mass ratio of crotonaldehyde to isopropyl alcohol of 10 ppb.
  • Example 4> low-boiling distillation step of crude isopropyl alcohol aqueous solution
  • water is supplied to the top of the second distillation column at a rate of 360 ml/h
  • the second bottoms are extracted from the bottom of the second distillation column at a rate of 390 ml/h.
  • a semiconductor cleaning solution was obtained in the same manner as in Example 1 except that it was supplied to the top of the first distillation column.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 0.15 ppm. Further, in the semiconductor cleaning liquid, the mass ratio of 2-pentanone to isopropyl alcohol was 20 ppb, and the mass ratio of crotonaldehyde to isopropyl alcohol was 7 ppb.
  • ⁇ Comparative example 1> (low-boiling distillation process of crude isopropyl alcohol aqueous solution), water is not supplied to the top of the second distillation column, the second bottoms are extracted from the bottom of the second distillation column at a rate of 35 ml/h, and the first distillation A semiconductor cleaning solution was obtained in the same manner as in Example 1 except that it was supplied to the top of the column.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 2.2 ppm. Further, the semiconductor cleaning liquid had a mass ratio of 2-pentanone to isopropyl alcohol of 20 ppb, and a mass ratio of crotonaldehyde to isopropyl alcohol of 10 ppb.
  • ⁇ Comparative example 2> (Low-boiling distillation step of crude isopropyl alcohol aqueous solution) is the same as in Example 2 except that the second bottoms were supplied from the bottom of the second distillation column to one stage above the raw material supply stage of the first distillation column. A semiconductor cleaning solution was obtained.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 1.5 ppm. Further, the semiconductor cleaning liquid had a mass ratio of 2-pentanone to isopropyl alcohol of 20 ppb, and a mass ratio of crotonaldehyde to isopropyl alcohol of 10 ppb.
  • ⁇ Comparative example 3> Low-boiling distillation step of crude isopropyl alcohol aqueous solution
  • water is supplied to the top of the second distillation column at a rate of 40 ml/h
  • the second bottoms are extracted from the bottom of the second distillation column at a rate of 75 ml/h.
  • a semiconductor cleaning solution was obtained in the same manner as in Example 3 except that it was supplied to the top of the first distillation column.
  • the semiconductor cleaning liquid had a mass ratio of t-butyl alcohol to isopropyl alcohol of 2.0 ppm. Further, the semiconductor cleaning liquid had a mass ratio of 2-pentanone to isopropyl alcohol of 20 ppb, and a mass ratio of crotonaldehyde to isopropyl alcohol of 10 ppb.
  • Table 1 shows the simulation results of the water content in the liquid phase in each stage of the first distillation column, the number of theoretical plates where the water content in the liquid phase is 15% by mass or more, and the water in the liquid phase in the 4th stage. The measurement results of the content are shown.
  • Table 2 shows the content of the components in the first bottom liquid. Analysis examples 1, 2, and 3-1 were used.
  • Table 3 shows the mass ratio of the components to isopropyl alcohol. Analysis examples 1, 2, and 3-2 were used.
  • Table 3 shows that the semiconductor cleaning solutions of Examples 1 to 4 have a mass ratio of t-butyl alcohol to isopropyl alcohol of 1 ppm or less.
  • the semiconductor cleaning liquids of Comparative Examples 1 to 3 the water content in the liquid phase of the first distillation column was maintained at 15% by mass or more in the stages from the raw material supply stage to the top of the tower. Since the number of theoretical plates is 2.8, the mass ratio of t-butyl alcohol to isopropyl alcohol exceeds 1 ppm.

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PCT/JP2023/003901 2022-03-16 2023-02-07 半導体洗浄液および半導体洗浄液の製造方法 Ceased WO2023176192A1 (ja)

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US18/842,549 US20250171718A1 (en) 2022-03-16 2023-02-07 Semiconductor cleaning liquid and method for producing semiconductor cleaning liquid
KR1020247033182A KR20240163660A (ko) 2022-03-16 2023-02-07 반도체 세정액 및 반도체 세정액의 제조 방법
DE112023001404.3T DE112023001404T5 (de) 2022-03-16 2023-02-07 Halbleiter-reinigungsflüssigkeit und verfahren zur herstellung einer halbleiter-reinigungsflüssigkeit
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JP7607852B1 (ja) * 2023-09-07 2024-12-27 株式会社トクヤマ 精製イソプロピルアルコール水溶液の製造方法
JP7634139B1 (ja) * 2023-06-13 2025-02-20 株式会社トクヤマ 半導体洗浄用薬液および半導体洗浄用薬液の製造方法
JP7651784B1 (ja) * 2023-11-28 2025-03-26 株式会社トクヤマ 精製イソプロピルアルコールの製造方法
WO2025105774A1 (ko) * 2023-11-15 2025-05-22 주식회사 엘지화학 이소프로필 알코올의 제조방법
WO2025105772A1 (ko) * 2023-11-15 2025-05-22 주식회사 엘지화학 이소프로필 알코올의 정제 방법
WO2025115671A1 (ja) * 2023-12-01 2025-06-05 株式会社トクヤマ 精製イソプロピルアルコールの製造方法および製造装置
WO2025115528A1 (ja) * 2023-11-28 2025-06-05 株式会社トクヤマ 精製イソプロピルアルコールの製造方法

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JP7634139B1 (ja) * 2023-06-13 2025-02-20 株式会社トクヤマ 半導体洗浄用薬液および半導体洗浄用薬液の製造方法
JP7607852B1 (ja) * 2023-09-07 2024-12-27 株式会社トクヤマ 精製イソプロピルアルコール水溶液の製造方法
WO2025105774A1 (ko) * 2023-11-15 2025-05-22 주식회사 엘지화학 이소프로필 알코올의 제조방법
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WO2025115671A1 (ja) * 2023-12-01 2025-06-05 株式会社トクヤマ 精製イソプロピルアルコールの製造方法および製造装置
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