Method for producing detergent for semiconductor component

Abstract

To provide a method for producing a detergent for a semiconductor component which can easily reduce an amount of metal ions contained in detergent itself.SOLUTION: A detergent for a semiconductor component contains a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium. A method for producing the detergent includes a purification step of supplying the detergent to a purification column 3 filled with an adsorbent, and thereby making an adsorbent adsorb metal ions in the detergent. The adsorbent is one or more kinds of resins selected from the group consisting of a cation exchange resin and a chelate resin. The purification step supplies the detergent to the purification column 3 so that space speed based on the volume of a resin having a largest filling amount of the adsorbent is 8.0 h-1 or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a cleaning agent for semiconductor parts.

Background Art

[0002] Semiconductor devices are used in almost all electronic devices close to us, such as information and communication devices and home appliances, and are essential for modern life. In recent years, the role played by semiconductor devices has become even greater due to the spread of IoT and the use of the cloud. So far, the high integration and large capacity of semiconductor chips have been achieved at a remarkable speed, but the demand for higher performance has not stopped, and the importance of microfabrication technology is increasing more and more.

[0003] In order to realize the higher performance of semiconductor devices, for example, a polishing process for polishing the surface of a silicon substrate so as to have a high-quality surface, a chemical mechanical polishing (CMP) process for polishing an insulating layer or a wiring layer formed on the silicon substrate, etc. A process of polishing the surface of a wafer so as to have a desired quality is extremely important. In addition, foreign substances derived from the wafer, polishing agent, polishing liquid, etc. remain on the wafer after polishing is completed. Since these foreign substances may cause defects in semiconductor devices, the wafer is cleaned after polishing is completed.

[0004] As a cleaning agent used for cleaning a wafer, for example, Patent Document 1 describes a cleaning agent for semiconductor parts mainly composed of a (co)polymer having a sulfonic acid (salt) group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the cleaning agent described in Patent Document 1 contains metal ions in the cleaning agent itself, and there is a problem that the surface of the wafer after cleaning is contaminated by the metal ions contained in the cleaning body itself.

[0007] The present invention has been made in view of such a background, and aims to provide a method for manufacturing a cleaning agent for semiconductor parts that can easily reduce the amount of metal ions contained in the cleaning agent itself.

Means for Solving the Problems

[0008] One aspect of the present invention lies in a method for manufacturing a cleaning agent for semiconductor parts according to the following [1] to

[10] .

[0009] 〔1〕A method for manufacturing a cleaning agent for semiconductor parts including a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium, including a purification step of adsorbing metal ions in the cleaning agent to the adsorbent by supplying the cleaning agent to a purification column filled with the adsorbent, wherein the adsorbent is one or more resins selected from the group consisting of cation exchange resins and chelating resins, and in the purification step, the space velocity based on the volume of the resin having the largest filling amount among the adsorbents is 8.0 h -1 or less, and the cleaning agent is supplied to the purification column as described above. A method for manufacturing a cleaning agent for semiconductor parts.

[0010] 〔2〕The method for manufacturing a cleaning agent for semiconductor parts according to [1], wherein the adsorbent is a cation exchange resin. 〔3〕The method for manufacturing a cleaning agent for semiconductor parts according to [1], wherein the adsorbent is a strongly acidic cation exchange resin. 〔4〕The method for manufacturing a cleaning agent for semiconductor parts according to [1], wherein the adsorbent is a macroporous type cation exchange resin or a macroporous type cation exchange resin.

[0011] [5] The purification column has a first purification column filled with a chelating resin as the adsorbent, and a second purification column filled with a cation exchange resin as the adsorbent and connected downstream of the first purification column. In the purification step, the cleaning agent is supplied to the first purification column. The method for producing a cleaning agent for semiconductor parts according to [1].

[0012] [6] The method for producing a cleaning agent for semiconductor parts according to [5], wherein the cation exchange resin is a strongly acidic cation exchange resin. [7] The method for producing a cleaning agent for semiconductor parts according to [5], wherein the cation exchange resin is a macroporous type cation exchange resin or a macroporous type cation exchange resin, and the chelating resin is a macroporous type chelating resin or a macroporous type chelating resin. [8] The production method further includes a pretreatment step of reducing the content of impurities other than the metal ions adsorbed by the adsorbent among the impurities in the cleaning agent, and the purification step is performed after the pretreatment step. The method for producing a cleaning agent for semiconductor parts according to any one of [1] to [7].

[0013] [9] The method for producing a cleaning agent for semiconductor parts according to any one of [1] to [8], wherein the purification step is repeated two or more times.

[10] The method for producing a cleaning agent for semiconductor parts according to any one of [1] to [9], wherein the content of the metal ions in the cleaning agent after the purification step is 70 mass ppb or less for each element. [Advantages of the Invention]

[0014] The method for producing a cleaning agent for semiconductor parts (hereinafter referred to as "cleaning agent") has a purification step of supplying the cleaning agent to a purification column filled with an adsorbent so that the space velocity is within the specific range. By setting the space velocity of the cleaning agent in the purification column within the specific range, the metal ions contained in the cleaning agent itself can be sufficiently adsorbed by the adsorbent.

[0015] Therefore, according to the above aspect, it is possible to provide a method for manufacturing a cleaning agent for semiconductor components that can easily reduce the amount of metal ions contained in the cleaning agent itself.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0017] (Method for Manufacturing a Cleaning Agent for Semiconductor Components) The cleaning agent used in the manufacturing method contains a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium. The polymer can be obtained, for example, by polymerizing at least one monomer selected from monomers having a carboxy group and monomers having a sulfonic acid group and other monomers used as needed by a known polymerization method. Further, a cleaning agent can be prepared by dissolving the polymer thus obtained in an aqueous medium. The more detailed configuration of the cleaning agent will be described later.

[0018] In the cleaning agent after production, in addition to the polymer and the aqueous medium, metal ions derived from raw materials used in the synthesis of the polymer and metal ions such as metal ions eluted from reaction vessels and the like during the synthesis process of the polymer are contained. In the manufacturing method, a purification step is performed in which the cleaning agent is supplied to a purification column filled with an adsorbent and the metal ions in the cleaning agent are adsorbed by the adsorbent, whereby the content of these metal ions can be reduced.

[0019] The total amount of metal ions contained in the cleaning agent before the purification process is not particularly limited. However, the lower the total amount of metal ions in the cleaning agent, the easier it is to reduce the metal ion content in the purification process. From this perspective, the total amount of metal ions contained in the cleaning agent before the purification process is preferably 300,000 mass ppb or less, more preferably 30,000 mass ppb or less, and even more preferably 3,000 mass ppb or less.

[0020] In the purification column used in the purification process, one or more resins selected from the group consisting of cation exchange resins and chelating resins are filled as adsorbents. The number of purification columns may be one or two or more. For example, when using one purification column in the purification process, the purification column may be filled with a cation exchange resin or a chelating resin. It is also possible to fill both a cation exchange resin and a chelating resin in the purification column.

[0021] When using two or more purification columns in the purification process, the same type of adsorbent may be filled in all the purification columns, or the type of adsorbent filled in some of the purification columns may be different from the type of adsorbent filled in other purification columns. For example, when using two or more purification columns in the purification process, all the purification columns may be filled with a cation exchange resin, or some of the purification columns may be filled with a cation exchange resin and other purification columns may be filled with a chelating resin.

[0022] Also, when using two or more purification columns in the purification process, the plurality of purification columns may be connected in series with each other or in parallel with each other. The connection mode of the purification columns can be appropriately set according to the desired flow rate of the cleaning agent, the adsorption performance of metal ions, etc.

[0023] When the type of adsorbent used in the purification column is one type, the adsorbent is preferably a cation exchange resin. The cation exchange resin can adsorb a wide variety of metal ions ranging from metal ions with a small atomic weight to those with a large atomic weight. Therefore, by using the cation exchange resin as the adsorbent, various metal ions contained in the cleaning agent can be adsorbed in the purification column. As a result, the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0024] When the types of adsorbents used in the purification process are two or more, the purification column has a first purification column filled with a chelating resin as the adsorbent and a second purification column filled with a cation exchange resin as the adsorbent and connected downstream of the first purification column. It is preferable to supply the cleaning agent to the first purification column in the purification process. In this way, by connecting the first purification column filled with the chelating resin upstream of the second purification column filled with the cation exchange resin, relatively large atomic weight metal ions among the metal ions contained in the cleaning agent can be adsorbed in the first purification column. Also, when the cleaning agent that has passed through the first purification column passes through the second purification column, metal ions that could not be completely adsorbed in the first purification column can be adsorbed. As a result of these, the metal ions in the cleaning agent can be adsorbed more efficiently, and the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0025] In the purification process, when both a cation exchange resin and a chelating resin are used as adsorbents, the ratio of the volume of the cation exchange resin to the total volume of the cation exchange resin and the chelating resin is preferably 10% by volume or more and 90% by volume or less, more preferably 20% by volume or more and 80% by volume or less, still more preferably 30% by volume or more and 70% by volume or less, and particularly preferably 40% by volume or more and 60% by volume or less. In this case, the effect of adsorbing heavy metal ions by the chelating resin and the effect of adsorbing light metal ions by the cation exchange resin can be exhibited in a well-balanced manner. As a result, metal ions in the detergent can be adsorbed more efficiently, and the total amount of metal ions in the detergent flowing out from the purification column can be further reduced.

[0026] The cation exchange resin used as an adsorbent has an ion exchange group that captures metal ions by ion exchange with metal ions. The ion exchange group is usually bonded to an organic polymer such as a styrene resin or an acrylic resin.

[0027] The cation exchange resin may be a weakly acidic cation exchange resin, that is, an ion exchange resin having a carboxy group (-COOH) as an ion exchange group, or a strongly acidic cation exchange resin, that is, an ion exchange resin having a sulfonic acid group (-SO3H) as an ion exchange group. From the viewpoint of more efficiently removing metal ions, the ionic form of the ion exchange group is preferably a hydrogen ion form (-R - H + ).

[0028] Further, the cation exchange resin may be a gel type cation exchange resin having no pores, or a macroporous type cation exchange resin or a macroporous type cation exchange resin having a large number of pores.

[0029] It is more preferable that the cation exchange resin used as an adsorbent is a strongly acidic cation exchange resin. In this case, the total amount of metal ions in the detergent flowing out from the purification column can be further reduced.

[0030] Further, the cation exchange resin used as the adsorbent is more preferably a macroporous cation exchange resin or a macroporous cation exchange resin. These cation exchange resins have a large number of pores opened on their surfaces. Therefore, by using a macroporous cation exchange resin or a macroporous cation exchange resin as the adsorbent, the contact area between the cleaning agent and the adsorbent can be increased. As a result, the metal ions contained in the cleaning agent can be adsorbed more efficiently, and the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0031] The harmonic mean diameter of the cation exchange resin is preferably 400 μm or more and 1000 μm or less. In this case, the contact area between the cleaning agent and the adsorbent can be increased. As a result, the metal ions contained in the cleaning agent can be adsorbed more efficiently, and the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0032] The total exchange capacity of the cation exchange resin is preferably 1.3 meq / mL or more, more preferably 1.5 meq / mL or more, and even more preferably 1.7 meq / mL or more. By using such a cation exchange resin as the adsorbent, the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced. The total exchange capacity of the cation exchange resin is the equivalent of cations that can be adsorbed by a unit volume of the cation exchange resin in water.

[0033] The chelating resin used as the adsorbent has a chelating group that forms a chelate with metal ions. The chelating group is usually bonded to an organic polymer such as a styrene resin or an acrylic resin.

[0034] The chelating groups in the chelating resin are not particularly limited. Examples of the chelating groups include iminodiacetic acid group, polyamine group, primary amine group, methylglucamine group, amidoxime group, thiourea group, thiol group, phosphonic acid group, aminophosphoric acid group, aminomethylphosphoric acid group, bispicolylamine group, and semicarbamic acid group. From the viewpoint of selectivity for a plurality of metal species, etc., it is preferable that the chelating resin has an aminomethylphosphoric acid group and / or an iminodiacetic acid group as the chelating group.

[0035] Further, the chelating resin may be a gel-type chelating resin having no pores, or may be a macroporous chelating resin or a macroporous chelating resin having a large number of pores.

[0036] The chelating resin used as the adsorbent is more preferably a macroporous chelating resin or a macroporous chelating resin. These chelating resins have a large number of pores opened on their surfaces. Therefore, by using a macroporous chelating resin or a macroporous chelating resin as the adsorbent, the contact area between the cleaning agent and the adsorbent can be made larger. As a result, the metal ions contained in the cleaning agent can be adsorbed more efficiently, and the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0037] The harmonic mean diameter of the chelating resin is preferably 400 μm or more and 1000 μm or less. In this case, the contact area between the cleaning agent and the adsorbent can be made larger. As a result, the metal ions contained in the cleaning agent can be adsorbed more efficiently, and the total amount of metal ions in the cleaning agent flowing out from the purification column can be further reduced.

[0038] The total exchange capacity of the chelating resin is preferably 1.3 meq / mL or more, more preferably 1.5 meq / mL or more, and even more preferably 1.7 meq / mL or more. By using such a chelating resin as an adsorbent, the total amount of metal ions in the cleaning agent flowing out of the purification column can be further reduced. The total exchange capacity of the chelating resin is the equivalent amount of metal ions that a unit volume of the chelating resin can adsorb in water.

[0039] In the purification step, the cleaning agent is supplied to the purification column so that the space velocity based on the volume of the resin with the largest filling amount among the adsorbents is 8.0 h -1 Hereinafter. Here, the "space velocity" refers to the ratio of the volume of the cleaning agent passing through the purification column per hour to the volume of the reference resin. For example, when only a cation exchange resin is used as the adsorbent, the value obtained by dividing the volume of the cleaning agent passing through the purification column per hour by the volume of the cation exchange resin in the purification column is the space velocity. When both a cation exchange resin and a chelating resin are used as the adsorbent, the value obtained by dividing the volume of the cleaning agent passing through the purification column per hour by the volume of the resin with the largest occupied volume in the purification column among the cation exchange resin and the chelating resin is the space velocity.

[0040] In the manufacturing method, by setting the space velocity of the cleaning agent in the purification column within the specific range, sufficient contact time between the cleaning agent and the adsorbent can be ensured, and the metal ions in the cleaning agent can be sufficiently adsorbed by the adsorbent. From the viewpoint of further enhancing the effect of adsorbing metal ions, the space velocity of the cleaning agent in the purification step is preferably 4.0 h -1 Hereinafter, more preferably 2.0 h -1 Hereinafter, even more preferably 0.9 h -1 Hereinafter. If the space velocity of the cleaning agent is too high, the contact time between the cleaning agent and the adsorbent will be shortened, and the effect of reducing the content of metal ions in the cleaning agent may be reduced.

[0041] On the one hand, if the space velocity of the cleaning agent in the purification process is excessively small, the outflow rate of the cleaning agent from the purification column will be slow, which may lead to a decrease in the productivity of the cleaning agent. From the perspective of easily avoiding such problems, the space velocity of the cleaning agent is preferably 0.1 h -1 or more, more preferably 0.2 h -1 or more, still more preferably 0.3 h -1 or more, and even more preferably 0.4 h -1 or more.

[0042] In constituting the preferable range of the space velocity of the cleaning agent in the purification process, the above-mentioned upper limit and lower limit of the space velocity can be arbitrarily combined. For example, the preferable range of the space velocity may be 0.1 h -1 or more and 8.0 h -1 or less, may be 0.2 h -1 or more and 4.0 h -1 or less, may be 0.3 h -1 or more and 2.0 h -1 or less, may be 0.4 h -1 or more and 0.9 h -1 or less.

[0043] The amount of the cleaning agent purified in the purification process is preferably 1 to 30 times, more preferably 2.5 to 20 times, and still more preferably 5 to 15 times the volume of the resin with the largest filling amount among the adsorbents. That is, for example, when only a cation exchange resin is used as the adsorbent, it is preferable that the ratio of the volume of the cleaning agent purified by the purification column to the volume of the cation exchange resin is within the specific range. Also, when both a cation exchange resin and a chelating resin are used as the adsorbent, it is preferable that the ratio of the volume of the cleaning agent purified by the purification column to the volume of the resin with the largest occupied volume in the purification column among the cation exchange resin and the chelating resin is within the specific range.

[0044] By setting the amount of the cleaning agent generated in the purification step to preferably 1 time or more, more preferably 2.5 times or more, and even more preferably 5 times or more with respect to the volume of the resin with the largest filling amount among the adsorbents, the amount of the adsorbent filled in the purification column can be easily reduced. Further, by setting the amount of the cleaning agent generated in the purification step to preferably 30 times or less, more preferably 20 times or less, and even more preferably 15 times or less with respect to the volume of the resin with the largest filling amount among the adsorbents, elution of metal ions due to breakthrough of the adsorbent can be more easily avoided.

[0045] The temperature of the cleaning agent in the purification step is preferably 5°C or higher and 60°C or lower, more preferably 7°C or higher and 50°C or lower, and even more preferably 10°C or higher and 40°C or lower. By setting the temperature of the cleaning agent in the purification step to preferably 5°C or higher, more preferably 7°C or higher, and even more preferably 10°C or higher, metal ions in the cleaning agent can be more efficiently adsorbed by the adsorbent, and the content of metal ions can be further reduced.

[0046] On the other hand, when the temperature of the cleaning agent in the purification step for the adsorbent becomes excessively high, the metal ions adsorbed by the adsorbent tend to desorb from the adsorbent. By setting the temperature of the cleaning agent in the purification step to preferably 60°C or lower, more preferably 50°C or lower, and even more preferably 40°C or lower, desorption of metal ions from the adsorbent can be more easily avoided.

[0047] The number of times of the purification step in the manufacturing method may be 1 time. Further, in the purification method, after supplying the cleaning agent to the purification column to perform the cleaning step, the cleaning agent flowing out of the purification column may be supplied to the purification column again to repeat the purification step. In the manufacturing method, it is preferable to repeat the purification step 2 times or more. By repeating the purification step, the content of metal ions in the cleaning agent can be further reduced.

[0048] The manufacturing method may further include a pretreatment step of reducing the content of impurities other than metal ions adsorbed by the adsorbent among the impurities in the cleaning agent, if necessary, and the purification step may be performed after the pretreatment step. In this way, by reducing the content of impurities other than metal ions in the cleaning agent in the pretreatment step, the total amount of impurities in the cleaning agent can be further reduced.

[0049] As a specific treatment method of the cleaning agent in the pretreatment step, a known separation method according to the type of impurities in the cleaning agent and the like can be appropriately adopted. For example, in the pretreatment step, the cleaning agent may be filtered using a filter. In this case, relatively large particulate impurities can be removed from the cleaning agent. Also, in the pretreatment step, the impurities in the cleaning agent may be separated from the cleaning agent using a separation membrane such as a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, or a reverse osmosis membrane. In the pretreatment step, these separation methods may be performed alone, or two or more separation methods may be combined.

[0050] After the completion of the purification step, the content of metal ions in the cleaning agent is preferably 70 mass ppb or less, more preferably 50 mass ppb or less, and even more preferably 30 mass ppb or less for each element. In this way, by using a cleaning agent having a lower content of metal ions compared to conventional cleaning agents to clean semiconductor components, the amount of metal ions remaining on the semiconductor components after cleaning can be reduced. As a result, the occurrence of semiconductor device defects caused by metal ions can be suppressed.

[0051] (Cleaning Agent for Semiconductor Components) 〔Polymer〕 The cleaning agent used in the manufacturing method contains a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium. The polymer may have at least one repeating unit of a repeating unit having a carboxy group or a repeating unit having a sulfonic acid group. Further, the polymer may be a homopolymer formed by polymerizing one type of monomer, or may be a copolymer formed by polymerizing two or more types of monomers having different structures. When the polymer is a copolymer, the arrangement of the repeating units in the copolymer is not particularly limited. For example, the polymer in the cleaning agent may be a random copolymer or a block copolymer.

[0052] The polymer is obtained by polymerizing at least one monomer of a monomer having a sulfonic acid group or a salt thereof (hereinafter referred to as a sulfonic acid (salt) group-containing monomer) and a monomer having a carboxy group or a salt thereof (hereinafter referred to as a carboxyl (salt) group-containing monomer), and other monomers used as necessary.

[0053] More specifically, as the sulfonic acid (salt) group-containing monomer, for example, an unsaturated monomer having a sulfonic acid group or a salt thereof and a polymerizable unsaturated group such as a vinyl group can be used. Examples of the sulfonic acid (salt) group-containing monomer include unsaturated (meth)allyl ether monomers such as isoprene sulfonic acid, (meth)acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, (meth)allyl sulfonic acid, vinyl sulfonic acid, isoamylene sulfonic acid, 2-hydroxy-3-(meth)allyloxy-1-propane sulfonic acid, conjugated diene sulfonic acids such as sulfoethyl (meth)acrylate and 2-methyl-1,3-butadiene-1-sulfonic acid, 2-hydroxy-3-acrylamidopropane sulfonic acid, and salts thereof.

[0054] When the sulfonic acid group in the sulfonic acid (salt) - containing monomer forms a salt, the type of counter - cation is not particularly limited. For example, the sulfonic acid group may form a metal salt with a metal ion as the counter - cation, or may form a non - metal salt with a non - metal cation as the counter - ion. Examples of the metal salt include alkali metal salts with alkali metals such as potassium as the counter - ion; alkaline earth metal salts with alkaline earth metal ions such as calcium and magnesium as the counter - ion, etc. Examples of the non - metal salt include ammonium salts with ammonium ions as the counter - ion; quaternary ammonium salts with quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion as the counter - ion; alkylamine salts in which an alkylamine such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine is bonded to the sulfonic acid group; alcoholamine salts in which an alcoholamine such as monoethanolamine, triethanolamine, diisopropanolamine is bonded to the sulfonic acid group; organic amine salts in which a polyamine such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, triethylenepentamine, tetraethylenepentamine or an organic amine such as morpholine, piperidine is bonded to the sulfonic acid group, etc.

[0055] When the sulfonic acid group in the polymer forms a salt, from the viewpoint of more easily reducing the content of metal ions in the detergent in the purification step, the sulfonic acid group is preferably a non - metal salt, more preferably an ammonium salt, a quaternary ammonium salt or an organic amine salt.

[0056] The polymer may have repeating units derived from one type of sulfonic acid (salt) group-containing monomer, or may have repeating units derived from two or more types of sulfonic acid (salt) group-containing monomers. From the viewpoint of excellent polymerizability, etc., it is preferable that the polymer has repeating units derived from (meth)acrylamide-2-methylpropanesulfonic acid such as 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.

[0057] As the carboxyl (salt) group-containing monomer, for example, an unsaturated monomer having a carboxyl group or a salt thereof and a polymerizable unsaturated group such as a vinyl group can be used. As the carboxyl (salt) group-containing monomer, for example, carboxyl group-containing vinyl compounds such as (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-carboxyethyl (meth)acrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride; and half-ester compounds of the unsaturated acid anhydride and an alkyl alcohol can be used.

[0058] When the carboxyl group in the carboxyl (salt) group-containing monomer forms a salt, the type of counter cation is not particularly limited. For example, the carboxyl group may form a metal salt having a metal ion as a counter cation, or may form a non-metal salt having a non-metal cation as a counter ion. The specific form of the salt of the carboxyl group is the same as the form of the salt of the sulfonic acid group described above.

[0059] The polymer may have repeating units derived from one type of carboxyl (salt) group-containing monomer, or may have repeating units derived from two or more types of carboxyl (salt) group-containing monomers. From the viewpoint of good polymerizability and the ability to impart sufficient hydrophilicity to the resulting polymer, it is preferable that the polymer has repeating units derived from one or more carboxyl (salt) group-containing monomers among (meth)acrylic acid, maleic acid, and maleic anhydride, and more preferably has repeating units derived from acrylic acid.

[0060] The content of the repeating unit having a sulfonic acid group and the content of the repeating unit having a carboxy group in the polymer may be appropriately set according to the configuration of the semiconductor component to be cleaned and the desired cleaning performance. For example, the content of the repeating unit having a sulfonic acid group may be 1% by mass or more, 2% by mass or more, 5% by mass or more, 10% by mass or more, 30% by mass or more, 60% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass based on the total content of all the repeating units contained in the polymer. Further, the content of the repeating unit having a sulfonic acid group may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 60% by mass or less, 30% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, or 0% by mass based on the total content of all the repeating units contained in the polymer. In constructing the preferable range of the content of the repeating unit having a sulfonic acid group, the upper limit and the lower limit of the above-described content can be arbitrarily combined.

[0061] Also, the content of the repeating unit having a carboxy group may be 1% by mass or more, 2% by mass or more, 5% by mass or more, 10% by mass or more, 30% by mass or more, 60% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass with respect to the total content of all the repeating units contained in the polymer. Further, the content of the repeating unit having a carboxy group may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 60% by mass or less, 30% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, or 0% by mass with respect to the total content of all the repeating units contained in the polymer. In constituting the preferable range of the content of the repeating unit having a carboxy group, the above-mentioned upper limit and lower limit of the content can be arbitrarily combined.

[0062] In the range that does not impair the cleaning performance, the polymer may contain repeating units other than these repeating units in addition to the repeating unit having a sulfonic acid group and the repeating unit having a carboxy group. Examples of such repeating units include repeating units derived from amide group-containing vinyl monomers, repeating units derived from N-vinyl lactam monomers, repeating units derived from hydroxyl group-containing vinyl monomers, repeating units derived from (meth)acrylic acid alkyl ester monomers, repeating units derived from aromatic vinyl monomers, repeating units derived from amino group-containing vinyl monomers, repeating units derived from polyoxyalkylene group-containing vinyl monomers, repeating units derived from alkoxy group-containing vinyl monomers, repeating units derived from cyano group-containing vinyl monomers, repeating units derived from vinyl ether monomers, repeating units derived from vinyl ester monomers, repeating units derived from conjugated dienes, and the like. The polymer may contain one type of these repeating units or two or more types of these repeating units.

[0063] More specifically, examples of the amide group-containing vinyl monomer include (meth)acrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-heptyl(meth)acrylamide, N-octyl(meth)acrylamide, 2-ethylhexyl(meth)acrylamide, N-dodecyl(meth)acrylamide, N-octadecyl(meth)acrylamide and other N-monoalkyl-substituted (meth)acrylamides; N-methylol(meth)acrylamide, N-ethylol(meth)acrylamide, N-propylol(meth)acrylamide and other N-monoalkylol(meth)acrylamides; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N,N-diisobutyl(meth)acrylamide, N,N-di-tert-butyl(meth)acrylamide, N,N-diheptyl(meth)acrylamide, N,N-dioctyl(meth)acrylamide, N,N-di-tert-octyl(meth)acrylamide, N,N-didodecyl(meth)acrylamide, N,N-dioctadecyl(meth)acrylamide and other N,N-dialkyl-substituted (meth)acrylamides; N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide and other N,N-dialkylaminoalkyl(meth)acrylamides; N-(meth)acryloylmorpholine, N-(meth)acryloylthiomorpholine, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine and other N-(meth)acryloyl cyclic amide compounds; N-vinylacetamide, N-vinylpropionamide, N-vinylbutyramide, etc. can be used.

[0064] Examples of the N-vinyl lactam monomer include N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl morpholinone, N-vinyl caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, and the like which can be used.

[0065] Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like which can be used.

[0066] Examples of the (meth)acrylic acid alkyl ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, and the like which can be used.

[0067] Examples of the aromatic vinyl monomer include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, tert-butoxystyrene, vinyltoluene, vinylnaphthalene, halogenated styrene, and the like which can be used.

[0068] Examples of the amino group-containing vinyl monomer include dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-(di-n-propylamino)ethyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate, 2-diethylaminopropyl (meth)acrylate, 2-(di-n-propylamino)propyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 3-diethylaminopropyl (meth)acrylate, 3-(di-n-propylamino)propyl (meth)acrylate, etc., which can be used.

[0069] Examples of the polyoxyalkylene group-containing vinyl monomer include (meth)acrylic acid esters of alcohols having a polyoxyethylene group and / or a polyoxypropylene group, etc., which can be used.

[0070] Examples of the alkoxy group-containing vinyl compound include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(n-propoxy)ethyl (meth)acrylate, 2-(n-butoxy)ethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-(n-propoxy)propyl (meth)acrylate, 2-(n-butoxy)propyl (meth)acrylate, etc., which can be used.

[0071] Examples of the cyano group-containing vinyl monomer include cyanomethyl (meth)acrylate, 1-cyanoethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)acrylate, 2-cyanopropyl (meth)acrylate, 3-cyanopropyl (meth)acrylate, 4-cyanobutyl (meth)acrylate, 6-cyanohexyl (meth)acrylate, 2-ethyl-6-cyanohexyl (meth)acrylate, 8-cyanooctyl (meth)acrylate, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc., which can be used.

[0072] As the vinyl ether monomer, for example, vinyl methyl ether, vinyl ethyl ether, vinyl - n - butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether, etc. can be used.

[0073] As the vinyl ester monomer, for example, vinyl formate, vinyl acetate, vinyl propionate, etc. can be used.

[0074] As the conjugated diene, for example, 1,3 - butadiene, isoprene, 2,3 - dimethyl - 1,3 - butadiene, 1,3 - pentadiene, 2 - methyl - 1,3 - pentadiene, 1,3 - hexadiene, 4,5 - diethyl - 1,3 - octadiene, 3 - butyl - 1,3 - octadiene, chloroprene, etc. can be used.

[0075] In addition, as monomers other than these, for example, maleimide - based compounds such as maleimide, N - methylmaleimide, N - butylmaleimide, N - phenylmaleimide, N - cyclohexylmaleimide; maleic acid ester compounds; itaconic acid ester compounds; N - vinyl heterocyclic compounds such as vinyl pyridine, etc. can be used.

[0076] The content of the repeating unit other than the repeating unit having a sulfonic acid group and the repeating unit having a carboxy group described above may be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 0% by mass with respect to the total content of all the repeating units constituting the polymer.

[0077] The weight average molecular weight of the polymer is preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more. In this case, the cleaning performance of the cleaning agent can be further improved. Also, the weight average molecular weight of the polymer is preferably 50000 or less, more preferably 30000 or less, and even more preferably 15000 or less. In this case, the dispersibility of the polymer in the cleaning agent can be further improved.

[0078] In constituting the preferable range of the weight average molecular weight of the polymer, the above-described upper limit and lower limit of the weight average molecular weight can be arbitrarily combined. For example, the preferable range of the weight average molecular weight of the polymer may be 500 or more and 50000 or less, may be 1000 or more and 30000 or less, or may be 2000 or more and 15000 or less. Note that the weight average molecular weight of the polymer is a value in terms of sodium polyacrylate obtained by gel permeation chromatography (GPC) using sodium polyacrylate as a standard substance.

[0079] 〔Synthesis method of polymer〕 In synthesizing the polymer, a sulfonic acid (salt) group-containing monomer and / or a carboxyl (salt) group-containing monomer and other monomers used as necessary may be polymerized in the presence of a polymerization initiator. The reaction temperature during polymerization may be, for example, 20°C or higher and 200°C or lower, or may be 40°C or higher and 150°C or lower. Also, the reaction time during polymerization may be, for example, 0.1 hour or more and 20 hours or less, or may be 1 hour or more and 15 hours or less.

[0080] The polymerization method of the monomer is not particularly limited and can take various forms. For example, a polymer may be synthesized by sequentially adding the monomer to the reaction system for polymerization. The amount of the monomer added to the reaction system per unit time may be constant, or may be changed according to the progress of the reaction and the like.

[0081] As a method for polymerizing the monomer, it is preferable to adopt a solution polymerization method in which the monomer is polymerized in a polymerization solvent. According to solution polymerization, a uniform solution containing the polymer can be obtained. The polymerization solvent used in solution polymerization is preferably an aqueous solvent such as water, a water-soluble organic solvent, and a mixture of water and a water-soluble organic solvent. In this case, since the purification step can be carried out using the reaction product after polymerization (i.e., the detergent), simplification of the manufacturing process can be expected. As the water-soluble organic solvent, for example, tetrahydrofuran, 1,4-dioxane, dimethylformamide, alcohols, etc. can be used.

[0082] As the polymerization initiator, known polymerization initiators can be used, but radical polymerization initiators are particularly preferably used. As the radical polymerization initiator, water-soluble peroxides, oil-soluble peroxides, azo compounds, etc. can be used.

[0083] As the water-soluble peroxide, for example, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; hydroperoxides such as t-butyl hydroperoxide; hydrogen peroxide, etc. can be used. As the oil-soluble peroxide, for example, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; dialkyl peroxides such as di-t-butyl peroxide and t-butyl cumyl peroxide; peroxy esters such as t-butyl peroxypivalate and t-hexyl peroxypivalate, etc. can be used. As the azo compound, for example, 2,2’-azobisisobutyronitrile, 2,2’-azobis(2,4-dimethylvaleronitrile), 2,2’-azobis(2-methylbutyronitrile), 2,2’-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2’-azobis[2-(2-imidazolin-2-yl)propane] disulfate dihydrate, 2,2’-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, etc. can be used. These radical polymerization initiators may be used alone, or two or more radical polymerization initiators may be used in combination.

[0084] The amount of the radical polymerization initiator used may be appropriately set according to the amount and type of the monomer used during polymerization, etc. For example, the amount of the radical polymerization initiator used may be 0.01% by mass or more and 10% by mass or less, 0.05% by mass or more and 7% by mass or less, or 0.1% by mass or more and 4% by mass or less with respect to the total mass of the monomer used for polymerization.

[0085] It is preferable that the polymerization initiator does not contain a metal atom or has a relatively small metal atom content. Examples of such polymerization initiators include ammonium persulfate, peroxides, and azo compounds. By using such a polymerization initiator, the amount of metal ions contained in the cleaning agent before the purification step can be reduced. And by performing a purification step on such a cleaning agent, the amount of metal ions contained in the cleaning agent after the purification step can be more easily reduced.

[0086] In the polymerization of the monomer, a chain transfer agent can be used as necessary. By adding a chain transfer agent to the reaction system, the molecular weight of the polymer can be more easily adjusted within a desired range. Examples of the chain transfer agent that can be used include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, etc.

[0087] As the method for polymerizing the monomer, from the viewpoint of more easily adjusting the molecular weight distribution of the polymer to a desired mode, it is preferable to adopt a controlled polymerization method such as a living radical polymerization method. Examples of the living radical polymerization method include a reversible addition-fragmentation chain transfer (so-called RAFT) method, a nitroxide-mediated polymerization (so-called NMP) method, an atom transfer radical polymerization (so-called ATRP) method, an organic tellurium-mediated living radical polymerization (so-called TERP) method, and the like.

[0088] In the RAFT method, polymerization proceeds through a reversible chain transfer reaction in the presence of a polymerization regulator (so-called RAFT agent) and a radical polymerization initiator. The molecular weight of the polymer obtained by the RAFT method can be adjusted by the charging ratio of the monomer and the RAFT agent. As the RAFT agent, for example, dithioester compounds, xanthate compounds, trithiocarbonate compounds, dithiocarbamate compounds, etc. can be used.

[0089] The amount of the RAFT agent used may be appropriately set according to the type of the monomer, the type of the RAFT agent, the molecular weight distribution of the desired polymer, etc. The amount of the RAFT agent used may be, for example, 0.01% by mass or more and 5.0% by mass or less, 0.05% by mass or more and 3.0% by mass or less, or 0.1% by mass or more and 2.0% by mass or less based on the total mass of the monomers used in the polymerization step.

[0090] As the polymerization initiator in the NMP method, specific alkoxyamine compounds having nitroxide, etc. are used. In the NMP method, polymerization proceeds through the nitroxide radical derived from the polymerization initiator. The type of the nitroxide radical is not particularly limited, but from the viewpoint of polymerization controllability when polymerizing monomers such as acrylamide derivatives including acrylates and acrylamides, for example, it is preferable to use a compound represented by the general formula (1) as the nitroxide compound.

[0091]

Chemical formula

[0092] However, R in the above general formula (1) 1 is an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, and R 2 is an alkyl group having 1 or more and 2 or less carbon atoms or a nitrile group, and R 3 is -(CH2) m -(where m is an integer of 0 or more and 2 or less), and R 4 and R 5 are each an alkyl group having 1 or more and 4 or less carbon atoms.

[0093] The non-oxidizing acid groups in the monomers used during polymerization may exist in the free acid state or may form salts together with counter cations. When using a monomer in which the acid groups exist in the salt state during the polymerization step, the acid groups may be converted to free acids by adding an acid to the reaction system after the polymerization reaction is completed.

[0094] 〔Aqueous medium〕 The polymer in the cleaning agent is dissolved or dispersed in an aqueous medium. As the aqueous medium, water, water-soluble organic solvents, and mixtures thereof can be used. Examples of water-soluble organic solvents include tetrahydrofuran, 1,4-dioxane, dimethylformamide, and alcohols.

[0095] 〔Solid content of the cleaning agent〕 The solid content of the cleaning agent is mainly composed of the above polymer. The solid content of the cleaning agent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. By setting the solid content of the cleaning agent to 5% by mass or more, the cleaning performance of the cleaning agent can be further improved. On the other hand, if the solid content of the cleaning agent becomes excessively high, the viscosity of the cleaning agent may increase, making it difficult to handle. From the perspective of more easily avoiding an excessive increase in the viscosity of the cleaning agent, the solid content of the cleaning agent is preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0096] In determining the preferred range of the solid content of the cleaning agent, the above-mentioned upper and lower limits of the solid content can be arbitrarily combined. For example, the preferred range of the solid content of the cleaning agent may be 5% by mass or more and 55% by mass or less, may be 10% by mass or more and 50% by mass or less, or may be 15% by mass or more and 45% by mass or less.

[0097] 〔Viscosity of the cleaning agent〕 The viscosity of the cleaning agent at a temperature of 25°C is preferably 1000 mPa·s or less, more preferably 1 mPa·s or more and 1000 mPa·s or less, even more preferably 3 mPa·s or more and 500 mPa·s or less, and particularly preferably 5 mPa·s or more and 300 mPa·s or less. In this case, the handling of the cleaning agent can be made easier.

[0098] 〔pH of the cleaning agent〕 The pH of the cleaning agent is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more. By setting the pH of the cleaning agent to 0.1 or more, it is possible to more effectively suppress the elution of metal from the container and piping of the cleaning agent into the cleaning agent in the manufacturing process of semiconductor components. Also, the pH of the cleaning agent is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. By setting the pH of the cleaning agent to 4.0 or less, the cleaning performance of the cleaning agent can be further improved.

[0099] In constituting the preferable range of the pH of the cleaning agent, the above-mentioned upper limit and lower limit of the pH of the cleaning agent can be arbitrarily combined. For example, the preferable range of the pH of the cleaning agent may be 0.1 or more and 4.0 or less, 0.2 or more and 3.0 or less, or 0.3 or more and 2.0 or less.

[0100] 〔Use and usage method of the cleaning agent〕 The cleaning agent is used for cleaning semiconductor components of various materials and shapes. The semiconductor components to be cleaned may be composed of, for example, silicon, glass, ceramics, etc. Further, at least a part of the surface of the semiconductor component to be cleaned may be composed of, for example, single-crystalline silicon, polycrystalline silicon, amorphous silicon, thermal silicon oxide film, non-doped silicate glass film, phosphorus-doped silicate glass film, boron-doped silicate glass film, phosphorus-boron-doped silicate glass film, tetraethyl orthosilicate (TEOS) film, plasma CVD oxide film, silicon nitride film, silicon carbide film, silicon oxycarbide film, silicon oxynitride film, silicon carbonitride film, or silicon oxycarbonitride film, etc. Furthermore, at least a part of the surface of the semiconductor component to be cleaned may be composed of metal, glass, quartz, crystal, ceramics, etc. Further, the surface of the semiconductor component to be cleaned may be composed of one type of the above-mentioned materials, or may be composed of two or more types of materials. When two or more types of materials are present on the surface of the semiconductor component, these materials may be patterned by techniques such as photolithography, or may be laminated with each other.

[0101] The cleaning agent is used in the cleaning process performed during the manufacturing process of semiconductor components. The cleaning process is carried out at various timings, for example, before CMP, after CMP, before CVD (Chemical Vapor Deposition), after CVD, after resist development, after dry etching, after wet etching, after dry ashing, and after resist stripping. From the viewpoint of effectively utilizing the feature that the cleaning agent has a low metal ion content, it is preferably used in the cleaning process after CMP.

[0102] The cleaning method of the semiconductor component is not particularly limited, and known cleaning methods can be appropriately adopted. More specifically, as the cleaning method of the semiconductor component, there are methods such as dip cleaning in which the semiconductor component is immersed in the cleaning agent in the cleaning tank, spin cleaning in which the semiconductor component is rotated at high speed while the cleaning agent flows down onto the semiconductor component from the nozzle, and spray cleaning in which the cleaning agent is sprayed onto the semiconductor component. Further, as the cleaning device, a batch type cleaning device that simultaneously cleans a plurality of semiconductor components housed in a cassette may be used, or a single wafer type cleaning device that mounts a single semiconductor component taken out from the cassette on a holder and cleans each one may be used.

[0103] The time for bringing the cleaning agent into contact with the semiconductor component in the cleaning process may be appropriately selected according to the cleaning method. For example, when cleaning the semiconductor component using a batch type cleaning device, the contact time between the cleaning agent and the semiconductor component may be 0.5 minutes or more and 1 hour or less, may be 1 minute or more and 30 minutes or less, or may be 1 minute or more and 15 minutes or less. Also, when cleaning the semiconductor component using a single wafer type cleaning device, the contact time between the cleaning agent and the semiconductor component may be 1 second or more and 15 minutes or less, may be 5 seconds or more and 10 minutes or less, or may be 5 seconds or more and 5 minutes or less.

[0104] When cleaning the semiconductor component using a cleaning agent after the polishing process, the cleaning of the semiconductor component may be performed on the polishing platen or after removing it from the polishing device. When cleaning the semiconductor component on the polishing platen, for example, a method of supplying the cleaning agent to the semiconductor component on the polishing platen while moving the polishing pad can be adopted. In this case, in addition to the chemical cleaning action by the cleaning agent, foreign substances on the surface of the semiconductor component can be physically removed by the polishing pad. As a result, impurities such as foreign substances and metal ions on the surface of the semiconductor component can be effectively cleaned.

[0105] When cleaning the semiconductor component after removing it from the polishing apparatus, the cleaning agent may be brought into contact with the semiconductor component removed from the polishing apparatus. In this case, in addition to the chemical cleaning action of the cleaning agent, foreign substances on the semiconductor component can be physically removed by the flow of the cleaning agent when the cleaning agent is brought into contact with the semiconductor component. As a result, impurities such as foreign substances and metal ions on the surface of the semiconductor component can be effectively cleaned. Note that when the polishing pad is not used during cleaning, physical cleaning using a cleaning cloth or a cleaning brush may be used in combination.

[0106] When cleaning the semiconductor component, the cleaning agent can be diluted with an aqueous medium as necessary. The dilution of the cleaning agent may be performed before the cleaning agent reaches the semiconductor component, or may be performed on the semiconductor component.

[0107] Examples of methods for diluting the cleaning agent before it reaches the semiconductor component include, for example, a method of previously diluting the cleaning agent with an aqueous medium and supplying the diluted cleaning agent onto the semiconductor component, and a method of joining a pipe for supplying the cleaning agent and a pipe for supplying the aqueous medium midway and diluting the cleaning agent at the joining point of the pipes and then supplying the cleaning agent onto the semiconductor component. As methods for mixing the cleaning agent and the aqueous medium, various methods can be adopted, such as a method of causing the liquids to collide with each other through a narrow passage under pressure, a method of providing a filler such as a glass tube in the pipe and mixing the cleaning agent and the aqueous medium by disturbing the flow of the liquid in the pipe; a method of stirring the cleaning agent and the aqueous medium by a blade rotating by power.

[0108] Examples of methods for diluting the cleaning agent on the semiconductor component include, for example, a method of simultaneously supplying the cleaning agent and the aqueous medium onto the semiconductor component and mixing the two on the semiconductor component.

[0109] The amount of the aqueous medium added to the cleaning agent upon dilution may be appropriately set according to the type and concentration of the polymer in the cleaning agent before dilution, the desired cleaning performance, and the like. For example, the total mass of the aqueous medium added to the cleaning agent may be 4 times or more and 1,000,000 times or less, 50 times or more and 100,000 times or less, 100 times or more and 50,000 times or less, 500 times or more and 10,000 times or less, or 1000 times or more and 5000 times or less with respect to the mass of the polymer in the cleaning agent before dilution. The aqueous medium used for diluting the cleaning agent may have the same composition as the aqueous medium in the cleaning agent before dilution or may have a different composition.

Example

[0110] Examples of the method for producing the cleaning agent for semiconductor parts will be described below. The cleaning agent in the production method of this example contains a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium. The production method of this example includes a purification step of adsorbing metal ions in the cleaning agent to the adsorbent by supplying the cleaning agent to a purification column filled with the adsorbent. The adsorbent is one or more resins selected from the group consisting of cation exchange resins and chelating resins. Further, in the purification step, the space velocity is 8.0 h based on the volume of the resin having the largest filling amount among the adsorbents. -1 The cleaning agent is supplied to the purification column so as to be as follows.

[0111] In this example, first, three types of cleaning agents (Cleaning agents A to C) were prepared by the following method.

[0112] (Cleaning agent A) Cleaning agent A contains a polymer having both a carboxy group and a sulfonic acid group and water as an aqueous medium. More specifically, the polymer of cleaning agent A is a copolymer having a repeating unit derived from acrylic acid (hereinafter abbreviated as "AA") and a repeating unit derived from acrylamidotertiarybutylsulfonic acid (hereinafter abbreviated as "ATBS").

[0113] The method for preparing Detergent A is as follows. First, 180 parts by mass of ion-exchanged water was put into a perfluoroalkoxyalkane (so-called PFA) flask equipped with a stirrer and a thermometer, and while sealing the flask with nitrogen gas, the temperature of the contents was set to 80 °C. Separately, in a monomer supply tank, 180 parts by mass of ion-exchanged water, 1 part by mass of AA, and 99 parts by mass of ATBS were mixed to prepare a monomer solution.

[0114] Next, 0.5 part by mass of ammonium persulfate (hereinafter abbreviated as "APS") as a polymerization initiator was dissolved in 7.5 parts by mass of ion-exchanged water to prepare an initiator solution. Then, while maintaining the temperature inside the flask at 80 °C, the initiator solution was put into the flask. And 2 minutes after the initiator solution was put into the flask, the supply of the monomer solution to the flask was started to initiate the polymerization of the monomer. The supply of the monomer solution was carried out at a constant supply rate, and the required time from the start of supply to the end of supply was set to 4 hours. Also, while the monomer solution was being supplied, the temperature of the contents of the flask was maintained at 80 °C.

[0115] Separately from the above-mentioned initiator solution, 1.5 parts by mass of APS was dissolved in 22.5 parts by mass of ion-exchanged water to prepare an additional initiator solution. This additional initiator solution was put into the flask in 1 / 8 portions every 30 minutes after the supply of the monomer solution was started.

[0116] The temperature of the contents of the flask was maintained at 80 °C until 1 hour further elapsed after all of the monomer solution was put into the flask. And 5 hours after the supply of the monomer solution to the flask was started, ion-exchanged water was put into the flask so that the solid content became 21.0% by mass, and the contents were stirred until the solids in the flask dissolved. Then, the contents of the flask were cooled to stop the polymerization reaction. Thus, Detergent A was obtained.

[0117] The viscosity of the thus obtained detergent A at a temperature of 25°C was 10 mPa·s. The pH of detergent A was 0.3, and the solid content was 20.9% by mass. The weight average molecular weight of the polymer in detergent A was 11,400.

[0118] (Detergent B) Detergent B contains a polymer having a carboxy group and water as an aqueous medium. More specifically, the polymer of detergent B is polyacrylic acid.

[0119] The method for producing detergent B is as follows. First, 71.1 parts by mass of isopropyl alcohol (hereinafter abbreviated as "IPA") and 85.3 parts by mass of pure water were placed in a PFA flask equipped with a stirrer and a thermometer, and the temperature of the contents was adjusted to 81°C. Separately, 15.3 parts by mass of pure water and 100 parts by mass of AA were mixed in a monomer supply tank to prepare a monomer solution. Further, 11.3 parts by mass of pure water and 2 parts by mass of APS were mixed in an initiator tank to prepare an initiator solution.

[0120] Next, 0.7 part by mass of APS was dissolved in 2.1 parts by mass of pure water, and this solution was placed in the flask. Then, 1 minute after the solution was placed in the flask, the supply of the monomer solution and the initiator solution to the flask was started to polymerize the monomer. The supply of the monomer solution and the initiator solution was carried out at a constant supply rate, and the required time from the start of supply to the end of supply was set to 4 hours. Also, while these solutions were being supplied, the temperature of the contents of the flask was maintained at the boiling point of the contents.

[0121] The temperature of the contents of the flask was maintained at the boiling point until 1.5 hours had elapsed after all of the monomer solution and the initiator solution had been introduced into the flask. Thereafter, the contents of the flask were cooled to 60°C. After the cooling was completed, vacuum distillation was carried out while maintaining the temperature of the contents at 60°C, and 52.6 parts by mass of the solvent was distilled off from the contents. Next, 70 parts by mass of pure water was introduced into the flask. Then, vacuum distillation was carried out again while maintaining the temperature of the contents at 60°C, and 90.8 parts by mass of the solvent was distilled off from the contents.

[0122] After the vacuum distillation was completed, 48.3 parts by mass of pure water was charged into the flask, and the contents were stirred until the solids in the flask dissolved. Then, the contents of the flask were cooled to stop the polymerization reaction. Thus, detergent B was obtained.

[0123] The viscosity of the detergent B thus obtained at 25 °C was 76 mPa·s. Also, the pH of the detergent B was 1.1, and the solid content was 41.7% by mass. The weight-average molecular weight of the polymer in the detergent B was 5600.

[0124] (Detergent C) Detergent C contains a polymer having a carboxy group and water as an aqueous medium. More specifically, the polymer of detergent C is polyacrylic acid.

[0125] The method for producing detergent C is as follows. First, 177.8 parts by mass of IPA was placed in a PFA flask equipped with a stirrer and a thermometer, and the temperature of the contents was set to 80 °C. Separately, 150 parts by mass of IPA and 100 parts by mass of AA were mixed in a monomer supply tank to prepare a monomer solution.

[0126] Next, 2.65 parts by mass of benzoyl peroxide (“Niper (registered trademark) BW” manufactured by NOF Corporation) as a polymerization initiator was dissolved in 22.2 parts by mass of methyl ethyl ketone to prepare an initiator solution. Then, with the temperature in the flask maintained at 80 °C, the initiator solution was added to the flask. And 2 minutes after the initiator solution was added to the flask, the supply of the monomer solution to the flask was started to polymerize the monomer. The supply of the monomer solution was carried out at a constant supply rate, and the required time from the start to the end of the supply was 6 hours. Also, while the monomer solution was being supplied, the temperature of the contents of the flask was maintained at the boiling point of the contents.

[0127] The temperature of the contents of the flask was maintained at the boiling point until 2 more hours had elapsed since all of the monomer solution had been introduced into the flask. Thereafter, the contents of the flask were cooled to 40°C or lower to stop the polymerization reaction. After the cooling was completed, while maintaining the temperature of the contents at 40°C or lower, vacuum distillation was performed under a pressure of 5 kPa, and 268 parts by mass of the solvent was distilled off from the contents. Thereafter, 189 parts by mass of pure water was introduced into the flask. Then, while maintaining the temperature of the contents at 40°C or lower, vacuum distillation was performed again under a pressure of 5 kPa, and 189 parts by mass of the solvent was distilled off from the contents.

[0128] After the vacuum distillation was completed, 58 parts by mass of pure water was introduced into the flask, and the contents were stirred until the solid content in the flask dissolved. Thereafter, the contents of the flask were cooled to a temperature of 30°C or lower. While stirring the cooled contents, the contents were filtered using a filter showing a positive zeta potential (specifically, "Zeta Plus (registered trademark) Adsorption Depth Filter B-90-50S" manufactured by 3M). Thus, cleaning agent C was obtained.

[0129] The viscosity of the cleaning agent C thus obtained at a temperature of 25°C was 38 mPa·s. Also, the pH of the cleaning agent C was 1.9, and the solid content was 40.1% by mass. The weight average molecular weight of the polymer in the cleaning agent C was 2700.

[0130] Next, using cleaning agents A to C, a purification step was performed by the following method.

[0131] (Examples 1 to 5 and Comparative Example 1) In these Examples and Comparative Examples, the cleaning agent A was purified using the purification apparatus 1 shown in FIG. 1. The purification apparatus 1 includes a stock solution tank 2 in which the cleaning agent before purification is held, a purification column 3, and a purified solution tank 4 in which the cleaning agent after purification is stored. The stock solution tank 2 and the inlet of the purification column 3 are connected via a cleaning agent supply pipe 21. Further, a liquid feed pump 22 for sending the cleaning agent from the stock solution tank 2 to the purification column 3 is provided on the path of the cleaning agent supply pipe 21. The outlet of the purification column 3 and the purified solution tank 4 are connected via a cleaning agent discharge pipe 31. Further, a filter 32 (specifically, "YSYP-A5P-508" manufactured by Wies Filter Japan Co., Ltd.) for removing foreign matters is provided on the cleaning agent discharge pipe 31.

[0132] In this example, before purifying the cleaning agent, the purification column 3 was prepared as follows. First, 5% nitric acid was put into the stock solution tank 2, and the inside of the purification apparatus 1 was cleaned by supplying the 5% nitric acid to the empty purification column 3 at a constant flow rate for 1 hour or more. Next, the 5% nitric acid in the stock solution tank 2 was replaced with ultrapure water, and the 5% nitric acid in the purification apparatus 1 was flushed out by supplying the ultrapure water to the empty purification column 3 at a constant flow rate for 30 minutes or more.

[0133] Next, in a non-metal container, a macroporous strongly acidic cation exchange resin as an adsorbent (「Orlite (registered trademark) DS-4」manufactured by Organo Corporation, ion exchange group: sulfonic acid group, ionic form: hydrogen ion form, total exchange capacity 1.7 meq / mL or more) and ultrapure water were mixed to prepare an adsorbent slurry. With the outlet of the purification column 3 closed, this slurry was put into the purification column 3, filling the inside of the purification column 3 with the slurry. Then, the outlet of the purification column 3 was opened to let the ultrapure water in the slurry flow out. After the ultrapure water had flowed out, the outlet of the purification column 3 was closed, and the inside of the purification column 3 was filled with the adsorbent slurry again. Through the above operations, the purification column 3 was filled with a macroporous strongly acidic cation exchange resin (「Orlite (registered trademark) DS-4」manufactured by Organo Corporation) as an adsorbent. Then, ultrapure water was passed through the purification column 3 at a constant flow rate for 30 minutes or more. Thus, the purification column 3 was prepared.

[0134] Next, the ultrapure water in the stock solution tank 2 was replaced with cleaning agent A, and cleaning agent A was supplied to the purification column 3 so that the space velocity was 0.2 h -1 And when the supply amount of cleaning agent A reached twice the volume of the adsorbent, the supply of cleaning agent A was stopped. Through the above operations, the ultrapure water in the purification apparatus 1 was replaced with cleaning agent A. After the replacement with cleaning agent A was completed, the cleaning agent A in the purified liquid tank 4 was discarded.

[0135] Thereafter, cleaning agent A was supplied again from the stock solution tank 2 to the purification column 3. The temperature of cleaning agent A at this time was 23°C, and the space velocity of cleaning agent A in the purification column 3 was set to the value shown in Table 1. And when the supply amount of cleaning agent A reached 2.5 times the volume of the adsorbent, the cleaning agent A flowing out from the purification column 3 was sampled and the content of metal ions was measured. The liquid passing time from the start of the supply of cleaning agent A to the sampling was as shown in Table 1. In Tables 1 to 6, the adsorbent used in this example was denoted as 「DS-4」.

[0136] (Comparative Example 2) The cleaning agent of Comparative Example 2 was cleaning agent A that had been prepared by the method described above and had not undergone a purification process.

[0137] (Example 6) In Example 6, the purification of detergent B and sample collection were carried out in the same manner as in Example 1, except that detergent B was used instead of detergent A, and the space velocity of detergent B during purification was changed to the value shown in Table 2.

[0138] (Examples 7 - 8, Comparative Example 3) In these Examples and Comparative Examples, the purification of detergent B and sample collection were carried out in the same manner as in Example 6, except that a gel - type strongly acidic cation - exchange resin (Amberlite (registered trademark) IR120BH manufactured by Organo Corporation, ion - exchange group: sulfonic acid group, ionic form: hydrogen - ion form, total exchange capacity 2.0 meq / mL or more, harmonic mean diameter: 0.46 - 0.62 mm) was used as the adsorbent, and the space velocity of detergent B during purification was changed to the value shown in Table 2. In Tables 1 - 6, the adsorbent used in this example was designated as "IR120BH".

[0139] (Comparative Example 4) The detergent of Comparative Example 4 is detergent B before the purification step was carried out after being prepared by the method described above.

[0140] (Examples 9 - 10, Comparative Example 5) In these Examples and Comparative Examples, the purification of detergent B and sample collection were carried out in the same manner as in Example 7, except that detergent C was used instead of detergent B, and the space velocity of detergent C during purification was changed to the value shown in Table 3.

[0141] (Comparative Example 6) The detergent of Comparative Example 6 is detergent C that has not undergone the purification step after being prepared by the method described above.

[0142] (Examples 11 - 14) In these Examples, the purification of detergent A and sample collection were carried out in the same manner as in Example 2, except that the supply amount of detergent A until sample collection was changed to the value shown in Table 4.

[0143] (Examples 15 to 18) In these examples, the purification of cleaning agent A and the sampling were carried out in the same manner as in Example 2, except that the temperature of cleaning agent A during purification was changed to the value shown in Table 5.

[0144] (Example 19) In Example 19, the purification of cleaning agent A and the sampling were carried out in the same manner as in Example 2, except that a macroporous chelating resin ("Oralite DS-21" manufactured by Organo Corporation, chelating group: aminomethylphosphonic acid group, ionic form: hydrogen ion form, total exchange capacity 1.75 meq / mL or more) was used as the adsorbent. In Tables 1 to 6, the adsorbent used in this example was denoted as "DS-21".

[0145] (Example 20) In Example 20, the purification of cleaning agent A was carried out while circulating cleaning agent A through an annular path including the purification column 3 using the purification apparatus 102 shown in FIG. 2. The purification apparatus 102 has a stock solution tank 2 in which the cleaning agent before purification is held, a purification column 3, and a purified solution tank 4 in which the cleaning agent after purification is stored. The stock solution tank 2 and the inlet of the purification column 3 are connected via a cleaning agent supply pipe 21. A liquid feed pump 22 for sending the cleaning agent from the stock solution tank 2 to the purification column 3 is provided on the path of the cleaning agent supply pipe 21. The outlet of the purification column 3 and the purified solution tank 4 are connected via a cleaning agent outlet pipe 31. A filter 32 (specifically, "YSYP-A5P-508" manufactured by Wies Filter Japan Co., Ltd.) for removing foreign matters is provided on the cleaning agent outlet pipe 31.

[0146] Further, the purification apparatus 102 has a cleaning agent circulation pipe 34 connecting the purified solution tank 4 and the cleaning agent supply pipe 21, and a circulation pump 35 provided on the cleaning agent circulation pipe 34 for sending the cleaning liquid in the purified solution tank 4 to the cleaning agent supply pipe 21. The purification apparatus 102 of this example can purify the cleaning agent in the purification column 3 while circulating the cleaning agent through an annular path including the purification column 3, the purified solution tank 4, and the cleaning agent circulation pipe 34.

[0147] In this example, before purifying the cleaning agent, the purification column 3 was prepared as follows. First, 5% nitric acid was put into the stock solution tank, and the inside of the purification apparatus 102 was cleaned by supplying the 5% nitric acid to the empty purification column 3 at a constant flow rate for 1 hour or more. Next, the 5% nitric acid in the stock solution tank 2 was replaced with ultrapure water, and the 5% nitric acid in the purification apparatus 102 was flushed out by supplying the ultrapure water to the empty purification column 3 at a constant flow rate for 30 minutes or more.

[0148] Next, the purification column 3 was filled with a macroporous strongly acidic cation exchange resin (「Aurite DS-4」manufactured by Organo Corporation) as an adsorbent. Then, ultrapure water was passed through the purification column 3 at a constant flow rate for 30 minutes or more. Thus, the purification column 3 was prepared.

[0149] Next, the ultrapure water in the stock solution tank 2 was replaced with cleaning agent A, and cleaning agent A was supplied to the purification column 3 so that the space velocity was 0.2 h -1 And when the supply amount of cleaning agent A reached twice the volume of the adsorbent, the supply of cleaning agent A was stopped. By the above operations, the ultrapure water in the purification apparatus 102 was replaced with cleaning agent A. After the replacement with cleaning agent A was completed, the cleaning agent A in the purified liquid tank 4 was discarded.

[0150] Thereafter, cleaning agent A was supplied again from the stock solution tank 2 to the purification column 3. The temperature of cleaning agent A at this time was 23°C, and the space velocity of cleaning agent A in the purification column 3 was set to the value shown in Table 1. And when the supply amount of cleaning agent A reached 2.5 times the volume of the adsorbent, the supply of cleaning agent A was stopped, and cleaning agent A was circulated through the annular path including the purification column 3, the purified liquid tank 4, and the cleaning agent circulation pipe 34 by operating the circulation pump 35. Then, when 10 hours had elapsed since the start of the supply of cleaning agent A, the cleaning agent A flowing out from the purification column 3 was sampled, and the content of metal ions was measured.

[0151] (Examples 21 to 27) In these examples, the cleaning agent A was purified using the purification apparatus 103 shown in FIG. 3. The purification apparatus 103 used in this example includes a stock solution tank 2 for holding the cleaning agent before purification, a first purification column 3a, a second purification column 3b connected downstream of the first purification column 3a, and a purified solution tank 4 for storing the purified cleaning agent. The stock solution tank 2 and the inlet of the first purification column 3a are connected via a cleaning agent supply pipe 21. Further, a liquid feed pump 22 for sending the cleaning agent from the stock solution tank 2 to the first purification column 3a is provided on the path of the cleaning agent supply pipe 21. The outlet of the second purification column 3b and the purified solution tank 4 are connected via a cleaning agent discharge pipe 31. Further, a filter 32 (specifically, "YSYP-A5P-508" manufactured by Wies Filter Japan Co., Ltd.) for removing foreign substances is provided on the cleaning agent discharge pipe 31.

[0152] In this example, before purifying the cleaning agent, the first purification column 3a and the second purification column 3b were prepared as follows. First, 5% nitric acid was put into the stock solution tank 2, and the inside of the purification apparatus 103 was cleaned by supplying the 5% nitric acid to the empty first purification column 3a and second purification column 3b at a constant flow rate for 1 hour or more. Next, the 5% nitric acid in the stock solution tank 2 was replaced with ultrapure water, and the 5% nitric acid in the purification apparatus 103 was flushed out by supplying the ultrapure water to the empty first purification column 3a and second purification column 3b at a constant flow rate for 30 minutes or more.

[0153] Next, a chelating resin ("Organlite (registered trademark) DS-21" manufactured by Organo Corporation) as an adsorbent was filled in the first purification column 3a, and a macroporous strongly acidic cation exchange resin ("Organlite (registered trademark) DS-4" manufactured by Organo Corporation) as an adsorbent was filled in the second purification column 3b. The volume ratio of the adsorbent filled in the first purification column 3a to the adsorbent filled in the second purification column 3b was as shown in Table 6. After filling each purification column 3 with the adsorbent, ultrapure water was passed through each purification column 3 at a constant flow rate for 30 minutes or more. Thus, the purification column 3 was prepared.

[0154] Next, the ultrapure water in the stock solution tank 2 was replaced with cleaning agent A, and cleaning agent A was supplied to the first purification column 3a so that the space velocity was 0.5 h -1 Then, when the supply amount of cleaning agent A reached 4 times the volume of the resin with a large volume ratio among the adsorbents, the supply of cleaning agent A was stopped. By the above operations, the ultrapure water in the apparatus was replaced with cleaning agent A. After the replacement with cleaning agent A was completed, the cleaning agent A in the purified liquid tank 4 was discarded. Note that the space velocity in this example is a value calculated based on the volume of the adsorbent with a large volume ratio among the two types of adsorbents.

[0155] Thereafter, cleaning agent A was supplied again from the stock solution tank 2 to the first purification column 3a. The temperature of cleaning agent A at this time was 23°C, and the space velocity of cleaning agent A was 0.5 h -1 Then, when the supply amount of cleaning agent A reached 2.5 times the volume of the resin with a large volume ratio among the adsorbents, the cleaning agent A flowing out from the second purification column 3b was collected as a sample, and the content of metal ions was measured. The liquid passing time from the start of the supply of cleaning agent A to the sample collection was 5 hours in all cases.

[0156] Tables 1 to 6 show the contents of metal ions contained in the cleaning agents of the examples and comparative examples. Also, the value shown in the "Total of alkali metals" column in these tables is the total content of alkali metal ions with a content of 5 mass ppb or more, and the value shown in the "Total of alkaline earth metals" column is the total content of alkaline earth metal ions with a content of 5 mass ppb or more, and the value shown in the "Total of transition metals" column is the total content of transition metal ions with a content of 5 mass ppb or more, and the value shown in the "Total content" column is the total content of metal ions with a content of 5 mass ppb or more.

[0157] The content of metal ions was measured by inductively coupled plasma mass spectrometry. The method for measuring the content of metal ions is more specifically as follows. First, 4 mL of sulfuric acid ("Ultrapur-100" manufactured by Kanto Chemical Co., Inc.) was added to 5 g of the sample, and the mixture was heated to 180 - 250 °C for concentration. Next, hydrogen peroxide solution was added to the mixture and heated to dry it. After cooling this mixture, 1 mL of nitric acid ("Ultrapur-100" manufactured by Kanto Chemical Co., Inc.) and 10 mL of ultrapure water were added, and it was heated at a temperature of 200 °C for 10 minutes. After the mixture was cooled to room temperature, ultrapure water was added to the mixture to dilute it so that the total mass became 20 g. The sample solution obtained above was introduced into the measuring device, and the content of metal ions was quantified by the calibration curve method. As the measuring device, either the inductively coupled plasma mass spectrometer "7700s" or "7500cs" manufactured by Agilent was used.

[0158]

Table 1

[0159]

Table 2

[0160]

Table 3

[0161]

Table 4

[0162]

Table 5

[0163]

Table 6

[0164] As shown in Table 1, in Examples 1 to 5, detergent A was supplied to the purification column so that the space velocity of detergent A was within the specific range. Therefore, the content of metal ions in detergent A flowing out from the purification column was less than that of detergent A before the purification process (i.e., Comparative Example 2) and detergent A in which the purification process was performed at a space velocity higher than the specific range (i.e., Comparative Example 1). Also, from the comparison of Examples 1 to 5, it can be understood that the lower the space velocity of detergent A in the purification process, the more the content of metal ions in detergent A can be reduced.

[0165] From the comparison between Examples 6 to 8 shown in Table 2 and Comparative Examples 3 to 4, and the comparison between Examples 9 to 10 shown in Table 3 and Comparative Examples 5 to 6, similar to Examples 1 to 5, by setting the space velocity of the detergent in the purification process within the specific range, it can be understood that the content of metal ions in the detergent can be reduced, and the lower the space velocity of the detergent in the purification process, the more the content of metal ions in the detergent can be reduced.

[0166] In Examples 11 to 14 shown in Table 4, the purification process was carried out by variously changing the supply amount of the detergent. From the comparison of Examples 11 to 14, it can be understood that Examples 11 to 13, in which the supply amount of the detergent in the purification process was 15 times or less with respect to the volume of the resin, could reduce the content of metal ions more than Example 14.

[0167] In Examples 15 to 18 shown in Table 5, the purification process was carried out by variously changing the temperature of the detergent. When compared, it can be understood that Examples 15 to 17, in which the temperature of the detergent in the purification process was 50°C or lower, could reduce the content of metal ions more than Example 18. In particular, Examples 15 to 17 were able to reduce the content of alkali metal ions and alkaline earth metal ions compared to Example 18.

[0168] In Example 19, a chelating resin is used as the adsorbent. According to Example 19, even when using a chelating resin, by supplying the cleaning agent A to the purification column so that the space velocity of the cleaning agent A is within the specific range, similar to Examples 1 to 5, it can be understood that the content of metal ions can be reduced.

[0169] In Example 20, purification is performed while circulating the cleaning agent A through the cleaning agent circulation pipe. The cleaning agent A in Example 20 was able to reduce the content of metal ions compared to Example 2, which is the same method except that the cleaning agent A is not circulated. On the other hand, Example 2 where the cleaning agent A is not circulated can shorten the time required for the purification process compared to Example 20.

[0170] In Examples 21 to 27 in Table 6, the purification process is carried out using a first purification column filled with a chelating resin and a second purification column filled with a cation exchange resin. According to Examples 21 to 27, even when using two purification columns in this way, by supplying the cleaning agent A to the purification column so that the space velocity of the cleaning agent A is within the specific range, it can be understood that the content of metal ions can be reduced. Also, from the comparison of Examples 21 to 27, it can be understood that the content of transition metal ions can be reduced as the volume ratio of the chelating resin increases, and the content of alkali metal ions can be reduced as the volume ratio of the cation exchange resin increases.

[0171] As described above, specific embodiments of the method for manufacturing the cleaning agent have been described based on the examples. However, the specific embodiments of the method for manufacturing the cleaning agent for semiconductor parts according to the present invention are not limited to the embodiments of the examples, and the configuration can be appropriately changed without departing from the spirit of the present invention.

Explanation of Signs

[0172] 1, 102, 103 Purification device 2 Stock solution tank 3 Purification column 4 Purified liquid tank

Claims

1. A method for manufacturing a cleaning agent for semiconductor components, comprising a polymer having a carboxy group and / or a sulfonic acid group and an aqueous medium, including a purification step of adsorbing metal ions in the cleaning agent onto the adsorbent by supplying the cleaning agent to a purification column filled with the adsorbent, wherein the adsorbent is one or more resins selected from the group consisting of cation exchange resins and chelating resins, In the purification step, the space velocity based on the volume of the resin with the largest filling amount among the adsorbents is 8.0 h -1 A method for producing a cleaning agent for semiconductor parts, wherein the cleaning agent is supplied to the purification column so as to satisfy the following conditions.

2. The method for manufacturing a cleaning agent for semiconductor components according to claim 1, wherein the adsorbent is a cation exchange resin.

3. The method for manufacturing a cleaning agent for semiconductor components according to claim 1, wherein the adsorbent is a strongly acidic cation exchange resin.

4. The method for manufacturing a cleaning agent for semiconductor components according to claim 1, wherein the adsorbent is a macroporous type cation exchange resin or a macroporous type cation exchange resin.

5. The purification column has a first purification column filled with a chelating resin as the adsorbent, and a second purification column filled with a cation exchange resin as the adsorbent and connected downstream of the first purification column. In the purification step, the cleaning agent is supplied to the first purification column. The method for manufacturing a cleaning agent for semiconductor components according to claim 1.

6. The method for manufacturing a cleaning agent for semiconductor components according to claim 5, wherein the cation exchange resin is a strongly acidic cation exchange resin.

7. The method for manufacturing a cleaning agent for semiconductor components according to claim 5, wherein the cation exchange resin is a macroporous type cation exchange resin or a macroporous type cation exchange resin, and the chelating resin is a macroporous type chelating resin or a macroporous type chelating resin.

8. The manufacturing method further includes a pretreatment step of reducing the content of impurities other than the metal ions adsorbed by the adsorbent among the impurities in the cleaning agent, and the purification step is performed after the pretreatment step. The method for manufacturing a cleaning agent for semiconductor components according to claim 1.

9. The method for manufacturing a cleaning agent for semiconductor components according to claim 1, wherein the purification step is repeated two or more times.

10. The method for manufacturing a cleaning agent for semiconductor components according to any one of claims 1 to 9, wherein the content of the metal ions in the cleaning agent after the completion of the purification step is 70 mass ppb or less for each element.

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