Semiconductor device cleaning solution and method for manufacturing the same

Abstract

This invention provides a semiconductor device cleaning solution and a method for manufacturing the same that effectively control phenolic compounds, which are inevitably generated during the manufacturing process of semiconductor device cleaning solutions, and suppress the generation of residues on the surface of the object being cleaned during semiconductor device cleaning. [Solution] A semiconductor device cleaning solution characterized by containing phenol compounds at a concentration of 10 ppb or less, and having a plasma generation rate of less than 2% per pulse laser irradiation count by a laser-induced breakdown detection method, which effectively controls phenol compounds that inevitably occur during the semiconductor device cleaning solution manufacturing process and suppresses the generation of residues on the surface of the object to be cleaned during semiconductor device cleaning.

Description

Technical Field

[0001] The present invention relates to a semiconductor device cleaning liquid and a method for producing the same.

Background Art

[0002] In the manufacture of highly integrated semiconductor devices, after forming a conductive thin film such as a metal film serving as a wiring material for conduction and an interlayer insulating film for the purpose of insulating between the conductive thin films on an element such as a wafer, a photoresist is uniformly applied to the surface thereof to prepare a photosensitive layer. Selective exposure is performed here, and a development process is carried out to produce a desired resist pattern. Next, a dry etching process is performed on the interlayer insulating film using this resist pattern as a mask to form a desired pattern on this thin film. Then, a process of completely removing residues such as the resist pattern and residues generated by the dry etching process by an ashing method using oxygen plasma or a cleaning method using a cleaning liquid is generally adopted.

[0003] At this time, hydrogen peroxide or the like is used as the cleaning liquid. In particular, hydrogen peroxide is readily soluble in water, ethanol, and ether, and in an aqueous solution, hydrogen ions are partially dissociated to exhibit weak acidity, and it has a strong oxidizing power and is used as an oxidation reactant in various fields. In particular, hydrogen peroxide is used for cleaning semiconductor wafers (wafer cleaning) and etching during the semiconductor and display manufacturing processes. In this case, high-purity hydrogen peroxide with extremely limited impurities is required.

[0004] However, when commercially available hydrogen peroxide is used as it is, since the impurity concentration in hydrogen peroxide is high, it is not only difficult to produce high-quality products such as damage to the semiconductor, but also poor residues remain on the surface of the cleaning target due to aggregation between impurities and nanoparticles in the harsh environment during the semiconductor device cleaning process. However, the technology regarding the cause and countermeasures is not sufficient.

[0005] On the other hand, U.S. Patent No. 8,715,613 discloses a method for producing high-purity hydrogen peroxide. However, the concentration of impurities such as phenolic compounds in the purified hydrogen peroxide solution remains high, which is a problem as it does not meet the purity requirements in the field of fine chemistry. Furthermore, it has not solved the problem of residue generation on the surface of the object being cleaned during semiconductor device cleaning.

[0006] Therefore, there is a need to develop a semiconductor device cleaning solution and a method for manufacturing the same that can satisfy the purity required in the field of precision chemistry, such as the semiconductor industry, and suppress the generation of residues on the surface of the object being cleaned during semiconductor device cleaning. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Registered Patent No. 8,715,613 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention provides a semiconductor device cleaning solution and a method for manufacturing the same that can effectively control phenolic compounds that inevitably occur in the semiconductor device cleaning solution manufacturing process and suppress the generation of residues on the surface of the object to be cleaned during semiconductor device cleaning.

[0009] However, the problems that this application aims to solve are not limited to those mentioned above, and other problems not mentioned should be clearly understandable to an average engineer from the description below. [Means for solving the problem]

[0010] To solve the aforementioned problems, the present invention provides a semiconductor device cleaning solution characterized by containing phenol compounds at a concentration of 10 ppb or less, and having a plasma generation rate of less than 2% per pulse laser irradiation count by a laser-induced breakdown detection method.

[0011] The phenolic compounds may be one or more selected from the group consisting of phenol, methylphenol, ethylphenol, and isopropylphenol.

[0012] The phenolic compounds may be present in a concentration of 0.1 ppb or more and 10 ppb or less.

[0013] The semiconductor device cleaning solution may have a plasma generation rate of less than 1.8% per pulse laser irradiation.

[0014] The semiconductor device cleaning solution may also be hydrogen peroxide.

[0015] The nanoparticles present in the semiconductor device cleaning solution may be one or more selected from the group consisting of silver (Ag), calcium (Ca), nickel (Ni), silicon (Si), molybdenum (Mo), iron (Fe), and oxides of these metal particles.

[0016] The semiconductor device cleaning solution is a semiconductor device cleaning solution manufactured by a manufacturing method including a primary filtering step and a secondary filtering step, wherein the secondary filtering step may be performed using a filter made of one or more materials selected from the group consisting of PTFE and UPE.

[0017] Furthermore, the present invention relates to a method for manufacturing a semiconductor device cleaning solution, comprising a primary filtering step and a secondary filtering step, wherein the secondary filtering step is performed using a filter formed from one or more materials selected from the group consisting of PTFE and UPE. [Effects of the Invention]

[0018] The present invention can provide a high-purity semiconductor device cleaning liquid that can effectively control phenolic compounds inevitably generated in the semiconductor device cleaning liquid manufacturing process and suppress the generation of residues on the surface of the object to be cleaned during semiconductor device cleaning.

[0019] Moreover, the present invention can provide a method for manufacturing the semiconductor device cleaning liquid.

Embodiments for Carrying Out the Invention

[0020] The present invention relates to a semiconductor device cleaning liquid containing phenolic compounds at 10 ppb or less and having a ratio of the number of plasma generations per irradiation of a pulsed laser by a laser-induced breakdown detection method of less than 2%, and a method for manufacturing the same. According to the present invention, it is possible to effectively control phenolic compounds inevitably generated in the semiconductor device cleaning liquid manufacturing process and provide a high-purity semiconductor device cleaning liquid that can suppress the generation of residues on the surface of the object to be cleaned during semiconductor device cleaning.

[0021] More specifically, when using the semiconductor device cleaning liquid of the present invention, even after going through a harsh environment during the semiconductor device cleaning process, it is possible to minimize the defect of residues remaining on the surface of the object to be cleaned.

[0022] In the present invention, the semiconductor device is not particularly limited as long as it is an object recognized as a semiconductor device in the industry, but specifically, it may be a wafer and / or a pattern formed thereon.

[0023] In the present invention, the harsh environment may be an environment maintained at a temperature of 60°C to 150°C for 1 hour to 10 hours, but is not limited thereto.

[0024] As used herein, "comprise", "comprising", "include", "including", "have", and / or "having" are used in a sense that does not exclude the presence or addition of one or more other components, steps, operations, and / or devices other than the recited components, steps, operations, and / or devices.

[0025] In this specification, "ppb" means "parts per billion" and "ppt" means "parts per trillion".

[0026] <Semiconductor device cleaning liquid> The semiconductor device cleaning liquid of the present invention contains a phenolic compound at 10 ppb or less, and is characterized in that the ratio (BDP, Break Down Probability) of the number of plasma generations per irradiation of a pulsed laser by a laser-induced breakdown detection method (LIBD, Laser-Induced Breakdown Detection) is less than 2%. Thereby, it is possible to effectively control the phenolic compound inevitably generated in the semiconductor device cleaning liquid manufacturing process, and to provide a high-purity semiconductor device cleaning liquid capable of suppressing the generation of residues on the surface of the cleaning target during semiconductor device cleaning.

[0027] According to one embodiment of the present invention, the semiconductor device cleaning liquid may be hydrogen peroxide, but is not limited thereto.

[0028] Phenolic compounds The semiconductor device cleaning liquid of the present invention contains a phenolic compound at 10 ppb or less, preferably 0.1 ppb or more and 10 ppb or less.

[0029] The aforementioned phenolic compounds refer to the thermolytic compounds of the working solution used in the anthraquinone process as a method for manufacturing semiconductor device cleaning solutions, and / or compounds produced from resins and / or filters used in the process of purifying the manufactured semiconductor device cleaning solution. These compounds promote the aggregation of nanoparticles present in the semiconductor device cleaning solution, which can lead to defects such as the formation of residues on the surface of semiconductor devices cleaned with the cleaning solution.

[0030] The phenolic compounds mentioned above include, but are not limited to, phenol, methylphenol, ethylphenol, and isopropylphenol.

[0031] The semiconductor device cleaning solution of the present invention is preferable from the viewpoint of not generating residue on the surface of the object to be cleaned, because, by controlling the content of the phenol compounds to be within the specified range, it is less likely to form aggregates with the nanoparticles contained in the semiconductor device cleaning solution.

[0032] Laser-induced breakdown detection method The semiconductor device cleaning solution of the present invention is characterized in that the ratio of plasma generation times per pulse laser irradiation count (Break Down Probability, hereinafter referred to as BDP value) determined by a laser-induced breakdown detection method (Laser-Induced Breakdown Detection, hereinafter referred to as the LIBD method) is less than 2%, preferably less than 1.8%.

[0033] The LIBD method of the present invention is based on the principle that when nanoparticles contained in a liquid solution are irradiated with a pulsed laser, the particles undergo a multi-photon absorption effect, causing multiple photons to stimulate a single atom. At this time, the energy level is shifted to an excited state, and the unstable atom returns to the ground state, emitting various energies such as light, shock waves, and sound. At this time, signals such as CCD images of emitted light, shock waves, and sound are detected. Nanoparticles contained in semiconductor device cleaning solutions can be detected using this LIBD method.

[0034] The LIBD method of the present invention can overcome the limitations of existing particle size analysis methods that utilize light-scattering techniques, such as reduced sensitivity to nanoparticle size. In particular, according to the present invention, all solid components up to 2 nm in size can be distinguished from air and detected with great accuracy.

[0035] The aforementioned size includes, but is not limited to, the diameter and radius in the case of spherical particles, and the length in the longest direction in the case of needle-shaped particles.

[0036] On the other hand, the BDP value obtained by the LIBD method indicates the energy release due to the number of pulse laser irradiations, specifically the ratio of times plasma is generated. The BDP value increases as the content of solid components such as nanoparticles in the semiconductor device cleaning solution increases. Furthermore, it is preferable to set a standard for the intensity of the pulse laser, as a higher intensity pulse laser generates more plasma and increases the BDP value.

[0037] According to one embodiment of the present invention, the LIBD method used analytical equipment fabricated with reference to Part.Part.Syst.Charact.22(2005)181-191. The BDP value of the present invention calculated by the LIBD method was based on the pulse laser intensity at which the BDP value of a standard reagent, prepared by adding 20 nm sized polystyrene particles (manufactured by Themo SCIENTIFIC Microgenics Corporation) to ultrapure water at a concentration of 1 ppt, reached 2%.

[0038] According to one embodiment of the present invention, the nanoparticles present in the semiconductor device cleaning solution may be one or more selected from the group consisting of metal particles and oxides of the metal particles. Specifically, the metal particles may be one or more selected from the group consisting of silver (Ag), calcium (Ca), nickel (Ni), silicon (Si), molybdenum (Mo), and iron (Fe), but are not limited thereto.

[0039] According to one embodiment of the present invention, the semiconductor device cleaning solution is a semiconductor device cleaning solution manufactured by a manufacturing method including a primary filtering step and a secondary filtering step, wherein the secondary filtering step may be performed with a filter made of PTFE (Poly Tetra Fluoro Ethylene) and / or UPE (Ultra High Molecular Weight Polyethylene) material. The void size of the filter may be 1 to 3 nm, preferably 1 to 2 nm, most preferably 2 nm, and the number of filtering cycles through the filter may be 1 to 5, preferably 1 to 3.

[0040] <Method for manufacturing semiconductor device cleaning solution> The present invention provides a method for producing the semiconductor device cleaning solution described above. The semiconductor device cleaning solution production method of the present invention is not particularly limited as long as it can produce a semiconductor device cleaning solution containing phenol compounds at a concentration of 10 ppb or less and having a plasma generation rate of less than 2% per pulse laser irradiation count by a laser-induced breakdown detection method.

[0041] According to one embodiment of the present invention, the semiconductor device cleaning solution manufacturing method includes a primary filtering step and a secondary filtering step, wherein the secondary filtering step may be performed with a filter made of PTFE and / or UPE material. The void size of the filter may be 1 to 3 nm, preferably 1 to 2 nm, most preferably 2 nm, and the number of filtering cycles through the filter may be 1 to 5, preferably 1 to 3. More specifically, the semiconductor device cleaning solution manufacturing method is carried out through a purification apparatus including an input pipe, a purification column equipped with a gas injection pipe, and a discharge pipe provided downstream of the purification column, and may include: (a) a step of introducing unpurified hydrogen peroxide water into the purification column via the input pipe and passing it through a mixed ion exchange resin; (b) a step of purifying hydrogen peroxide through a primary filtering step and a secondary filtering step, wherein the secondary filtering step is carried out with a filter made of PTFE and / or UPE material; and (c) a step of discharging hydrogen peroxide water via a discharge pipe connected to the lower end of the purification column and including a liquid level maintenance pipe.

[0042] When producing the semiconductor device cleaning solution through the above method, it is preferable from the viewpoint that the gas generated by the reaction between hydrogen peroxide and the mixed ion exchange resin can be stably discharged to reduce the risk of explosion and improve the safety of the semiconductor device cleaning solution purification process.

[0043] Unpurified hydrogen peroxide contains various impurities, and generally, cation exchange resins are used to remove cationic impurities, and anion exchange resins are used to remove anionic impurities. Furthermore, to remove both cationic and anionic impurities simultaneously and improve process efficiency, a hybrid ion exchange resin, a mixture of cation exchange resins and anion exchange resins, can be used. However, because the specific gravities of cation exchange resins and anion exchange resins differ, conventional stirring methods often fail to prevent layer separation after mixing.

[0044] The semiconductor device cleaning solution manufacturing method of the present invention is characterized by manufacturing a mixed ion exchange resin through a bubbling process in order to prevent layer separation of the mixed ion exchange resin. More specifically, a mixture of a cation exchange resin, anion exchange resin, and water is introduced into the purification column, and then gas is injected through the gas injection pipe to bubble the mixture and manufacture the mixed ion exchange resin.

[0045] This method of producing a hybrid ion exchange resin by bubbling cation exchange resins and anion exchange resins is preferable because it prevents layer separation of the cation exchange resins and anion exchange resins, reduces ion re-elution during the purification process, minimizes the generation of nanoparticles, and controls the generation of phenolic compounds.

[0046] Furthermore, it is preferable to maintain the liquid level of the hydrogen peroxide solution in the purification column at or above the height of the mixed ion exchange resin so that a portion of the mixed ion exchange resin in the purification column does not become exposed and dry out without being submerged in the hydrogen peroxide solution.

[0047] To this end, the discharge piping includes a liquid level maintenance pipe, which allows the liquid level of the hydrogen peroxide solution to be maintained above the height of the mixed ion exchange resin.

[0048] The liquid level maintenance pipe refers to a part of the discharge piping that includes a U-shaped bend, and the ends of the liquid level maintenance pipe may be bent so that they face the same direction, and the intermediate portion protrudes in a different direction from the ends, and the shape of the bend is not limited to a U shape, but may include, and is not limited to, a modified U shape, a V shape, and a modified V shape.

[0049] The liquid level maintenance pipe is preferably 50 to 100 mm in diameter from the viewpoint of reducing piping pressure loss, and is preferably located within 20 m of the purification column, taking into consideration piping costs and pressure loss.

[0050] Furthermore, it is preferable that the liquid level maintenance pipe be made of the same material as the purification column.

[0051] The aforementioned U-shaped bend is directed upwards rather than towards the ground, and its uppermost point represents the maximum height of the liquid level maintenance pipe. The purified hydrogen peroxide solution transported through the liquid level maintenance pipe passes through a section where it is transported in the opposite direction to gravity before passing through the U-shaped bend, which is the highest point.

[0052] As a result, if the liquid level of hydrogen peroxide in the purification column is higher than or equal to the maximum height of the liquid level maintenance pipe, the purified hydrogen peroxide discharged from the purification column can pass through the liquid level maintenance pipe. Conversely, if the liquid level of hydrogen peroxide in the purification column is lower than the maximum height of the liquid level maintenance pipe, the purified hydrogen peroxide discharged from the purification column will not reach the maximum height of the liquid level maintenance pipe and will not be able to pass through it.

[0053] Therefore, if the maximum height of the liquid level maintenance pipe is greater than or equal to the height of the mixed ion exchange resin in the purification column, the level of the hydrogen peroxide solution in the purification column can also be maintained at or above the height of the mixed ion exchange resin. This effectively prevents a portion of the mixed ion exchange resin in the purification column from being exposed and drying out without being submerged in the hydrogen peroxide solution.

[0054] Maintaining the height of the hydrogen peroxide solution in the purification column above the height of the mixed ion exchange resin through the liquid level maintenance tube in this manner is preferable from the viewpoint of ensuring sufficient time for the hydrogen peroxide solution to pass through the mixed ion exchange resin, thereby minimizing the generation of nanoparticles and controlling the generation of phenolic compounds.

[0055] In particular, in the semiconductor device cleaning solution manufacturing method of the present invention, from the viewpoint of controlling phenol compounds to 10 ppb or less, it is preferable that the hydrogen peroxide solution in step (a) is passed from above to below the mixed ion exchange resin, and in step (c), the maximum height of the liquid level maintenance pipe is greater than or equal to the height of the mixed ion exchange resin in the purification column; and the mixed ion exchange resin through which the hydrogen peroxide solution in step (a) is passed is manufactured by injecting gas into a mixture of a cation exchange resin, anion exchange resin, and water and bubbling it; and that the semiconductor device cleaning solution manufacturing method of the present invention includes both of the above features. From the viewpoint of the problem that it is difficult to control phenol compounds generated during the manufacturing process to 10 ppb or less when the semiconductor device cleaning solution manufacturing method does not include both of the above features, it is preferable that the semiconductor device cleaning solution manufacturing method of the present invention includes both of the above features.

[0056] The following describes specific embodiments for carrying out the present invention. However, the present invention is not limited to the embodiments disclosed below and can be realized in a variety of different forms, provided that these embodiments are provided to complete the disclosure of the present invention and to fully inform those with ordinary skill in the art to which the present invention pertains, and the present invention is defined only by the scope of the claims.

[0057] <Examples and Comparative Examples> Example 1 A mixture of cation exchange resin (functional group: sulfonic acid group; ion exchange capacity: 2.0 eq / L; effective acidity: pH 0-14), anion exchange resin (functional group: quaternary ammonium group; ion exchange capacity: 1.0 eq / L; effective acidity: pH 1-14), and water (resistivity 18.2 MΩ·cm) is introduced into a purification column with an inner diameter of 700 mm and an internal height of 3600 mm. Air that has passed through a filtration device (filtration grade 0.05 μm) is then injected at a rate of 1.0 kgf / cm² via a gas injection valve connected to the lower end of the purification column. 2 The mixture was injected at a pressure of 24 hours and bubbling was performed to produce a mixed ion exchange resin, which filled the purification column to 33.3% (1200 mm) of its internal height. Then, unpurified hydrogen peroxide solution (31%, impurity level 10 ppb) was introduced through the input pipe at the top of the purification column, and the temperature was maintained below 15°C. After the hydrogen peroxide solution was allowed to pass through the mixed ion exchange resin, a primary filtering process was performed twice using a filter with a void size of 50 nm, and a secondary filtering process was performed three times using a filter with a void size of 2 nm.

[0058] The purified hydrogen peroxide solution was produced by discharging it at a flow rate of 1650 L / hr through a discharge pipe, which included a liquid level maintenance pipe connected to the lower end of the purification column and having a maximum height of 1400 mm.

[0059] Examples 2 to 3 In the above-described Example 1, the semiconductor device cleaning solution was manufactured using the same method as described above, except that the void size and the number of filtering cycles in the primary and secondary filtering steps were adjusted as shown in Table 1 below.

[0060] Comparative Example 1 In the above-described Example 1, the semiconductor device cleaning solution was manufactured using the same method as described above, except that the primary filtering step involved filtering three times with a filter having a void size of 50 nm, the secondary filtering step was omitted, and the maximum height of the liquid level maintenance pipe connected to the lower end of the purification column was 1000 mm.

[0061] Comparative Example 2 In the above-described Example 1, the semiconductor device cleaning solution was manufactured using the same method as described above, except that a primary filtering step was performed using a filter with a void size of 50 nm, and a secondary filtering step was not performed.

[0062] Comparative Example 3 In Example 1 described above, the void size and number of filtration cycles were adjusted in the primary and secondary filtration steps as shown in Table 1 below, and the semiconductor device cleaning solution was manufactured using the same method as described above, except that the cation exchange resin and anion exchange resin were mixed by mechanical stirring without a bubbling step during the process of manufacturing the mixed ion exchange resin.

[0063] [Table 1]

[0064] <Example of experiment> (1) Measurement of the phenolic compound content of semiconductor device cleaning solution The content of phenolic compounds in the semiconductor device cleaning solutions of the above-mentioned examples and comparative examples was analyzed by concentrating the prepared semiconductor device cleaning solutions and using a pyrolysis system and GC-MS equipment. A DB-5MS column (30m × 0.25mm) was used, and the analysis range was m / z 30-700. The peak area of ​​the phenolic standard compound, which had been quantified in advance, was compared with the peak area of ​​the standard compound in the semiconductor device cleaning solution, and the results are shown in Table 2 below according to the following criteria.

[0065] ○: Less than 10 ppb X: Exceeding 10ppb (2) Measurement of BDP value of semiconductor device cleaning solution by LIBD method For the semiconductor device cleaning solutions of the above-mentioned manufactured examples and comparative examples, analytical equipment fabricated with reference to Part.Part.Syst.Charact.22(2005)181-191 was used. A reagent prepared by adding 20 nm-sized polystyrene particles (manufactured by Themo SCIENTIFIC Microgenics Corporation) to ultrapure water at a concentration of 1 ppt was used as the standard reagent. After setting the pulse laser intensity to achieve a BDP value of 2%, the BDP value was measured using the LIBD method, and the results are shown in Table 2 below.

[0066] (3) Measurement of the number of particles of semiconductor device cleaning solution by particle size The total number of nanoparticles 20 nm or larger (ea), 30 nm or larger (ea), and 60 nm or larger (ea) per unit volume (ml) of the semiconductor device cleaning solutions of the above-mentioned manufactured examples and comparative examples was measured using LPC19F (manufactured by RION Corporation), and the results are shown in Table 2 below.

[0067] [Table 2]

[0068] (4) Measurement of the number of particles of different sizes generated under harsh conditions To the semiconductor device cleaning solutions of the above-mentioned examples and comparative examples, nanoparticles were added to a concentration of 5 ppt as shown in Table 3 below. The number of particles of each size was then measured using LPC19F (manufactured by RION) in the same manner as described above. After undergoing a harsh test of stirring at 80°C for 6 hours, the number of particles of each size was measured again, and the results are shown in Table 3 below.

[0069] [Table 3]

[0070] Referring to Table 2 above, it can be confirmed that the semiconductor device cleaning solutions according to Examples 1 to 3 of this application have a low BDP value of 1.8% or less, as measured by the LIBD method. The results of measuring the number of particles of different sizes passing through the LPC also show that the number of nanoparticles 20 nm or larger is measured to be 6 or less per unit volume, confirming that the number of nanoparticles inside the cleaning solution is very small. As a result, it can be confirmed from Table 3 that there is no change in the number of nanoparticles per unit volume even after administering nanoparticles to the semiconductor device cleaning solutions of Examples 1 to 3 and undergoing a harsh test corresponding to the semiconductor device cleaning process.

[0071] In contrast, the semiconductor device cleaning solutions of Comparative Examples 1 and 2 of the present application were manufactured without a secondary filtering process, and the BDP value measured by the LIBD method was a high value of 3.5% or more. The measurement results of the number of particles by size that passed through the LPC also showed that the number of nanoparticles of 20 nm or larger was measured to be 10 or more per unit volume, confirming that the number of nanoparticles inside the cleaning solution was greater than that of the examples. In addition, the semiconductor device cleaning solution of Comparative Example 1 was manufactured through a manufacturing apparatus in which the maximum height of the liquid level maintenance tube was lower than the height of the ion exchange resin during the semiconductor device cleaning solution manufacturing process, and it was confirmed that the amount of phenolic compounds contained in the semiconductor device cleaning solution exceeded 10 ppb. As a result, after administering nanoparticles to the semiconductor device cleaning solutions of Comparative Examples 1 and 2 and undergoing a harsh test corresponding to the semiconductor device cleaning process, a large number of nanoparticles of 20 nm or larger were generated, 27 or more per unit volume, confirming that they had a greater impact on the surface of the semiconductor device compared to the examples.

[0072] The semiconductor device cleaning solution in Comparative Example 3 underwent both a primary and secondary filtering process. However, in the semiconductor device cleaning solution manufacturing process, the filtering process was carried out through a mixed ion exchange resin that did not go through a bubbling process. The solution contained 6 nanoparticles of 20 nm or larger per unit volume. However, it was confirmed that the amount of phenolic compounds contained in the semiconductor device cleaning solution exceeded 10 ppb, and after a harsh test, a large number of nanoparticles of 20 nm or larger were generated, reaching 15 or more per unit volume.

Claims

1. A semiconductor device cleaning solution characterized by containing phenol compounds at a concentration of 10 ppb or less, and having a plasma generation rate of less than 2% per pulse laser irradiation count determined by a laser-induced breakdown detection method.

2. The semiconductor device cleaning solution according to claim 1, wherein the phenol compound is one or more selected from the group consisting of phenol, methylphenol, ethylphenol, and isopropylphenol.

3. The semiconductor device cleaning solution according to claim 1, wherein the phenol compound is contained in an amount of 0.1 ppb or more and 10 ppb or less.

4. The semiconductor device cleaning solution according to claim 1, wherein the ratio of plasma generation cycles per pulse laser irradiation cycle is less than 1.8%.

5. The semiconductor device cleaning solution according to claim 1, wherein the semiconductor device cleaning solution is hydrogen peroxide.

6. The semiconductor device cleaning solution according to claim 1, wherein the nanoparticles present in the semiconductor device cleaning solution are one or more selected from the group consisting of silver (Ag), calcium (Ca), nickel (Ni), silicon (Si), molybdenum (Mo), iron (Fe), and oxides of these metal particles.

7. A semiconductor device cleaning solution manufactured by a manufacturing method including a primary filtering step and a secondary filtering step, The aforementioned secondary filtering step is performed using a filter formed from one or more materials selected from the group consisting of PTFE and UPE, in a semiconductor device cleaning solution.

8. A method for manufacturing a semiconductor device cleaning solution according to any one of claims 1 to 7, A primary filtering step; and a secondary filtering step, A method for manufacturing a semiconductor device cleaning solution, wherein the secondary filtering step is performed using a filter formed from one or more materials selected from the group consisting of PTFE and UPE.

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