Method for producing an etching solution composition

Abstract

To provide a method for manufacturing an etchant composition capable of suppressing liquid dripping at the time of filling in a container.SOLUTION: With a method for manufacturing an etchant composition, the etchant composition etches a metal film formed on a substrate. A step is included of filling a container with the etchant composition using a filling nozzle having a filling port for discharging the etchant composition. A receding contact angle of the etchant with respect to a material of the filling port of the filling nozzle is 60° or more, and a ratio of an advancing contact angle to a receding contact angle (the advancing contact angle / the receding contact angle) is 1.4 or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing an etching solution composition.

Background Art

[0002] In the manufacturing process of semiconductor devices, for example, a step of etching an etching target film containing at least one metal such as tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, rhodium, copper, nickel, cobalt, titanium, titanium nitride, alumina, aluminum, and iridium into a predetermined pattern shape is performed. As the etching solution, an aqueous mixed acid solution containing phosphoric acid, nitric acid, and acetic acid is generally used. In recent years, in the semiconductor field, high integration has been progressing, and the wiring has become more complex and finer. The requirements for pattern processing technology and etching solutions are also increasing, and various etching solution compositions and etching methods have been proposed.

[0003] For example, in Patent Document 1, as an etching solution composition used for etching a Cu / Mo double film, phosphoric acid is about 50 to 80% by weight, nitric acid is about 0.5 to 10% by weight, acetic acid is about 4 to 30% by weight, a chlorine-containing compound is about 0.5 to 6% by weight, and the balance is water. An etching solution composition has been proposed. In Patent Document 2, as an etching method for etching a metal laminated film made of an alloy of copper and molybdenum and / or titanium, an etching method using an etching solution composition prepared by blending 40 to 50% by weight of phosphoric acid, 1.5 to 3.5% by weight of nitric acid, 25 to 40% by weight of acetic acid, and water has been proposed. In Patent Document 3, an etching composition for a thin film transistor liquid crystal display device containing 55 to 70% by weight of phosphoric acid, 3 to 15% by weight of nitric acid, 5 to 20% by weight of acetic acid, 0.5 to 10% by weight of phosphate, 0.1 to 5% by weight of a chlorine-based compound, 0.01 to 4% by weight of an azole-based compound, and the balance is water has been proposed. Patent Document 4 proposes an etching liquid composition for forming a predetermined pattern by etching a metal film having a multilayer structure in which a molybdenum film is laminated on the surface of an aluminum or aluminum alloy film formed on a substrate. The etching liquid composition consists of 40 to 70% by mass of phosphoric acid, 0.5 to 10% by mass of nitric acid, 50 to 15% by mass of acetic acid, and the balance being water. Patent Document 5 proposes an etching composition for a thin-film transistor liquid crystal display device containing 50 to 80% by weight of phosphoric acid, 2 to 15% by weight of nitric acid, 3 to 20% by weight of acetic acid, 0.05 to 3% by weight of a lithium-based compound, 0.1 to 5% by weight of a phosphate-based compound, and the balance of water.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, an etching liquid composition is filled in a container and commercialized. When filling the etching liquid composition into the container, in order to reduce the content of foreign substances (particles) in the etching liquid composition, a filtration process using a filter or the like is performed. Therefore, an etching liquid with excellent filter flowability and a high filtration rate is required. In addition, liquid dripping may occur when filling the etching solution into a container. The more the number of liquid dripping times, the more time is required for wiping, resulting in low productivity. From the perspective of improving productivity, the etching solution is also required to be less likely to drip. Further, the etching solution filled in the container is also required to be less likely to drip when taking out the etching solution in the container.

[0006] Therefore, in one aspect, the present disclosure provides a method for manufacturing an etching solution composition capable of suppressing liquid dripping when filling a container. The present disclosure provides, in one aspect, a method for manufacturing an etching solution composition capable of achieving both suppression of liquid dripping when filling a container and improvement of filtration rate. The present disclosure provides, in one aspect, a container-containing etching solution composition capable of suppressing liquid dripping when taking out the etching solution in the container.

Means for Solving the Problems

[0007] The present disclosure relates to, in one aspect, a method for manufacturing an etching solution composition, wherein the etching solution composition is an etching solution composition for etching a metal film formed on a substrate, and the method includes a step of filling the etching solution composition into a container using a filling nozzle having a filling port for discharging the etching solution composition, and a receding contact angle of the etching solution with respect to the material of the filling port of the filling nozzle is 60° or more and a ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) is 1.4 or less.

[0008] The present disclosure relates to, in one aspect, a mixed acid composition for use in the method for manufacturing the etching solution composition of the present disclosure, the mixed acid composition containing phosphoric acid, nitric acid, and an organic acid.

[0009] In one aspect, the present disclosure relates to an etching liquid composition filled in a container, wherein the etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate, the etching liquid composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, has a viscosity at 25 °C of 11 mPa·s or more and less than 40 mPa·s, and has a receding contact angle of the etching liquid composition with respect to the material of the container of 60° or more and a ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

[0010] In one aspect, the present disclosure relates to the use of a mixed acid composition containing phosphoric acid, nitric acid, and an organic acid in the production method of the etching liquid composition of the present disclosure.

Effects of the Invention

[0011] In one aspect, the present disclosure can provide a method for producing an etching liquid composition that can suppress liquid dripping when filling a container. According to the present disclosure, in one aspect, a method for producing an etching liquid composition that can achieve both suppression of liquid dripping when filling a container and improvement of the filtration rate can be provided. In one aspect, the present disclosure can provide an etching liquid composition filled in a container that can suppress liquid dripping when taking out the etching liquid in the container.

Brief Description of the Drawings

[0012]

Figure 1

Modes for Carrying Out the Invention

[0013] Based on the finding that in one aspect, by setting the contact angle (receding contact angle, advancing contact angle / receding contact angle) of the etching liquid with respect to the material of the filling port within a predetermined range, liquid dripping when filling the container can be suppressed, and furthermore, the filtration rate can be improved.

[0014] That is, in one aspect, the present disclosure relates to a method for manufacturing an etching liquid composition, wherein the etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate (hereinafter also referred to as "the etching liquid composition of the present disclosure"), and includes a step of filling a container with the etching liquid composition using a filling nozzle having a filling port for discharging the etching liquid composition (hereinafter also referred to as "the filling step"), and the receding contact angle of the etching liquid with respect to the material of the filling port of the filling nozzle is 60° or more, and the ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) is 1.4 or less. The present disclosure also relates to a method for manufacturing an etching liquid composition (hereinafter also referred to as "the etching liquid manufacturing method of the present aspect 1"). According to the present aspect 1, in one or more embodiments, dripping during filling into a container can be suppressed. Further, according to the present aspect 1, in one or more embodiments, it is possible to achieve both suppression of dripping during filling into a container and improvement of the filtration rate.

[0015] Although the details of the mechanism for the manifestation of the effects of the present aspect 1 are not clear, it is presumed as follows. For the same liquid, when the receding contact angle is a predetermined value or more, the number of dripping times is suppressed, and when the ratio of the advancing contact angle to the receding contact angle is a predetermined value or less, a balance between the liquid passing property (filtration rate) and dripping suppression is achieved, and productivity is improved. When the receding contact angle is relatively high and the ratio of the advancing contact angle to the receding contact angle falls within a certain range, it is considered that the productivity in the etching process (for example, the process of processing an electronic member by etching, the process of preparing for the etching process) is improved due to the combined effects of both sides. However, the present disclosure should not be construed as being limited to these mechanisms.

[0016] In other aspects, the present disclosure is based on the finding that by using an etching liquid containing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water and having a viscosity within a predetermined range at 25°C, it is possible to achieve both suppression of dripping during filling into a container and improvement of the filtration rate.

[0017] That is, in other aspects, the present disclosure relates to a method for manufacturing an etching liquid composition filled in a container, wherein the etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate (hereinafter, also referred to as "the etching liquid composition of the present disclosure"), the etching liquid composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, has a viscosity at 25 °C of 11 mPa·s or more and less than 40 mPa·s, and includes a step of filling the container with the etching liquid composition (hereinafter, also referred to as "the filling step"), and relates to a method for manufacturing an etching liquid composition (hereinafter, also referred to as "the etching liquid manufacturing method of the present aspect 2"). According to the present aspect 2, in one or more embodiments, it is possible to provide a method for manufacturing an etching liquid composition that can achieve both suppression of liquid dripping during filling into a container and improvement of the filtration rate.

[0018] Although the details of the mechanism for the manifestation of the effects of the present aspect 2 are not clear, it is presumed as follows. Since the etching liquid composition of the present aspect 2 has a viscosity within a predetermined range, it is considered that liquid dripping during filling into a container can be suppressed. Further, since the etching liquid composition of the present aspect 2 contains an organic acid, it is considered that the neutralization of strong acids (phosphoric acid, nitric acid) and the etching inhibitor can be suppressed from proceeding rapidly to form submicron-sized fine particles, the liquid permeability of the filter becomes good, and the filtration rate is improved. However, the present disclosure does not have to be construed as being limited to these mechanisms. In the following description, the etching liquid manufacturing methods of the present aspect 1 and the present aspect 2 are also collectively referred to as "the etching liquid manufacturing method of the present disclosure".

[0019] [Filling Step] The etching liquid manufacturing method of the present disclosure includes a step of filling a container with the etching liquid composition of the present disclosure (filling step). In one or more embodiments, the filling step is a step of filling a container with the etching liquid composition of the present disclosure using a filling nozzle having a filling port for discharging the etching liquid composition. In the filling step, the method of filling the etching liquid composition into the container is not particularly limited, and it can be filled by a conventionally known method depending on the form of the container and the like. As a method of filling the etching liquid composition into the container in the filling step, for example, a method of filling the etching liquid composition into the container using a filling system as shown in FIG. 1 can be mentioned, but it may not be construed as being limited thereto. In one or more embodiments, as shown in FIG. 1, the filling system includes a tank 1 for storing the etching liquid composition, a pump 2 for feeding the etching liquid composition, a filter 3 for filtering the etching liquid composition, an outlet valve 4 for controlling the flow rate of the etching liquid composition discharged from the outlet (filling nozzle) 5, and a pipe P1 connecting the tank 1, the pump 2, the filter 3, the outlet valve 4, and the outlet (filling nozzle) 5. Further, it includes a circulation path P2 branched from the pipe P1 between the filter 3 and the outlet valve 4 and connected to the upstream side of the pump 2. Also, in one or more embodiments, the filling system shown in FIG. 1 further includes a circulation valve 7 for controlling the flow rate of the etching liquid composition circulated through the circulation path P2. In one or more embodiments, the filling system shown in FIG. 1 is configured to feed the etching liquid composition in the tank 1 with the pump 2, filter it with the filter 3, fill the container 6 with the etching liquid composition discharged from the outlet (filling nozzle) 5 by opening the outlet valve 4, and circulate the etching liquid composition through the circulation path P2 by opening the circulation valve 7 whether the outlet valve 4 is open or closed. In one or more embodiments, the pump 2 is a pump for feeding the etching liquid composition in the tank 1 into the pipe P1. The type of the pump may not be particularly limited, and for example, a diaphragm pump or the like can be mentioned. In one or more embodiments, the pump 2 stops when both the circulation valve 7 and the outlet valve 4 are closed. The filter 3 is a filter for filtering the etching liquid composition in one or more embodiments. Examples of the filter 3 include conventionally used membrane filters, pleated filters, depth filters, filters containing filter aids, etc., and these can be used in combination. Examples of the number of stages of the filter 3 include 1 to 5 stages. The outlet 5 is a filling nozzle having a filling port for discharging the etching liquid composition in one or more embodiments. In FIG. 1, the circulation path P2 is configured to connect the downstream side of the filter 3 and the tank 1, but it may not be limited to this as long as the downstream side of the filter 3 and the upstream side of the pump 2 can be connected. For example, the circulation path P2 may be configured to return from the downstream side of the filter 3 to the pipe P1 between the tank 1 and the pump 2. In FIG. 1, the outlet valve 4 and the circulation valve 7 are provided separately, but instead of these two valves, a three-way valve may be provided at the branch point of the pipe P1 and the circulation path P2 to switch the flow path of the etching liquid composition. In addition, the filling system in FIG. 1 is configured to circulate the etching liquid by the circulation path P2 and the circulation valve 7, but a configuration without the circulation path P2 and the circulation valve 7 (that is, a configuration that does not circulate the etching liquid) may also be used.

[0020] [Filling nozzle] The filling nozzle used in the filling step may be any nozzle that can fill the etching liquid, and the shape, size, etc. are not particularly limited. Examples of the outer diameter of the filling port of the filling nozzle include 5 mm to 1000 mm. From the viewpoint of suppressing liquid dripping, at least one selected from polypropylene (PP), PFA (perfluoroalkoxy alkane), and PTFE (polytetrafluoroethylene) is preferable as the material of the filling port of the filling nozzle, and PFA and PTFE are more preferable.

[0021] [Container] Examples of the container filled with the etching liquid composition include containers made of polyethylene resin, polypropylene resin, or fluororesin. Examples of the polyethylene resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, and mixtures thereof. Examples of the fluororesin include PFA (perfluoroalkoxyalkane), PTFE (polytetrafluoroethylene), and mixtures thereof. Among these, from the viewpoint of suppressing liquid leakage, at least one selected from polypropylene (PP), PFA (perfluoroalkoxyalkane), and PTFE (polytetrafluoroethylene) is preferable as the material of the container, and PFA and PTFE are more preferable. In the present disclosure, the "container made of polyethylene resin or polypropylene resin" means a container in which at least the portion in contact with the etching liquid composition is made of polyethylene resin or polypropylene resin. As the resin container in the present disclosure, for example, a container may be used in which a layer of polyethylene resin or polypropylene resin is provided on the inner layer in contact with the etching liquid composition, and a resin of another material or the like is laminated on the outside thereof. Note that, although an antistatic agent such as a surfactant or a metal oxide may generally be added to commercially available containers made of polyethylene resin or polypropylene resin, it is preferable that the etching liquid composition of the present disclosure does not contain an antistatic agent. Further, since the etching liquid composition of the present disclosure contains nitric acid as an essential component, in order to prevent decomposition by sunlight or the like, it is preferable that the outer packaging of the container is colored or light-shielded in gray, blue, etc. rather than a translucent or white container. Examples of the form of the container in the present disclosure include, for example, a resin container with a capacity of 0.1 to 30 L, a composite container combining a resin inner container with a capacity of 0.1 to 30 L and cardboard, a composite container combining a resin inner container with a capacity of 1 to 30 L and a metal can, a resin drum container with a capacity of 20 to 300 L, a composite container combining a resin inner container with a capacity of 20 to 300 L and a metallic drum, a composite container combining a resin content container with a capacity of 500 to 1200 L and a metal container, an ISO container tank of 1000 or more, and the like. The container in the present disclosure only needs to be usable for the purpose of storing or transporting the etching liquid composition, and examples include those manufactured by injection molding, extrusion molding, or rotational molding. In one or more embodiments, when filling the container with the etching liquid composition using a nozzle (filling nozzle), the outlet diameter of the nozzle (outer diameter of the filling port) is, for example, an outer diameter of 14 mm.

[0022] [Etching liquid composition] In one or more embodiments, the etching liquid composition of the present disclosure contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water. In one or more other embodiments, the etching liquid composition of the present disclosure contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, and is an etching liquid composition having a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s.

[0023] (Contact angle of the etching liquid with respect to the material (material) of the filling port of the filling nozzle) From the viewpoint of suppressing liquid dripping, the advancing contact angle of the etching liquid composition of the present disclosure with respect to the material of the filling port of the filling nozzle is preferably 70° or more, more preferably 75° or more, still more preferably 79° or more, and from the viewpoint of productivity, preferably 120° or less, more preferably 100° or less, still more preferably 95° or less. From the same viewpoint, the advancing contact angle is preferably 70° or more and 120° or less, more preferably 75° or more and 100° or less, still more preferably 79° or more and 100° or less. The receding contact angle of the etching liquid composition of the present disclosure with respect to the material of the filling port of the filling nozzle is 60° or more, preferably 66° or more, more preferably 70° or more, from the viewpoint of suppressing liquid dripping, and from the viewpoint of productivity, 100° or less is preferable, 92° or less is more preferable, and 85° or less is even more preferable. From the same viewpoint, the receding contact angle is preferably 60° or more and 100° or less, more preferably 66° or more and 92° or less, and even more preferably 70° or more and 85° or less. The ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) of the etching liquid composition of the present disclosure with respect to the material of the filling port of the filling nozzle is 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less, from the viewpoint of suppressing liquid dripping. In the present disclosure, the contact angle (advancing contact angle, receding contact angle) of the etching liquid with respect to the material of the filling port of the filling nozzle can be measured using a contact angle measuring device (for example, K-100 manufactured by KRUSS) in an environment of 25°C. Specifically, it can be measured by the method described in the examples.

[0024] (Phosphoric acid) The blending amount of phosphoric acid in the etching liquid composition of the present disclosure is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, from the viewpoint of reducing etching unevenness, and from the viewpoint of reducing etching unevenness, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is even more preferable. More specifically, the blending amount of phosphoric acid in the etching liquid composition of the present disclosure is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% by mass or less, and even more preferably 20% by mass or more and 70% by mass or less.

[0025] (Nitric acid) From the viewpoint of improving the etching rate, the content of nitric acid in the etching solution composition of the present disclosure is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 4% by mass or more. From the viewpoint of reducing etching unevenness, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, still more preferably 6% by mass or less. More specifically, the content of nitric acid in the etching solution composition of the present disclosure is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, still more preferably 2% by mass or more and 7% by mass or less, still more preferably 3% by mass or more and 6% by mass or less, still more preferably 4% by mass or more and 6% by mass or less.

[0026] (Organic acid) Examples of the organic acid contained in the etching solution composition of the present disclosure include, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid, and glutamic acid. From the viewpoint of achieving both suppression of liquid dripping during filling into the container and improvement of the filtration rate, as the organic acid, a monovalent organic acid having 1 to 10 carbon atoms is preferable, a monovalent carboxylic acid having 1 to 10 carbon atoms is more preferable, and those containing acetic acid are still more preferable. The organic acid may be used alone or in combination of two or more.

[0027] From the viewpoint of reducing etching unevenness, the content of the organic acid in the etching solution composition of the present disclosure is preferably 11% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. From the viewpoint of improving the filtration rate, it is preferably 59% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. More specifically, the content of the organic acid in the etching solution composition of the present disclosure is preferably 11% by mass or more and 59% by mass or less, more preferably 15% by mass or more and 50% by mass or less, still more preferably 20% by mass or more and 40% by mass or less. When the organic acid is a combination of two or more, the content of the organic acid is the total content thereof.

[0028] From the perspective of reducing etching unevenness, the total blending amount of phosphoric acid, nitric acid, and organic acid in the etching solution composition of the present disclosure is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, and from the same perspective, preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less. The total blending amount of phosphoric acid, nitric acid, and organic acid in the etching solution composition of the present disclosure is preferably 70% by mass or more and 99.9% by mass or less, more preferably 75% by mass or more and 99% by mass or less, still more preferably 80% by mass or more and 98% by mass or less.

[0029] In one or more embodiments, the acid contained in the etching solution composition of the present disclosure is an acid containing phosphoric acid, nitric acid, and organic acid. From the perspective of achieving both suppression of liquid leakage during filling into the container and improvement of the filtration rate, it is preferably an acid containing phosphoric acid, nitric acid, and acetic acid, and more preferably a mixed acid composed of phosphoric acid, nitric acid, and acetic acid. When the acid contained in the etching solution composition of the present disclosure is a mixed acid composed of phosphoric acid, nitric acid, and acetic acid, from the perspective of reducing etching unevenness, the blending amount of phosphoric acid in the mixed acid is preferably 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 93% by mass or less, still more preferably 30% by mass or more and 90% by mass or less. From the same perspective, the blending amount of nitric acid in the mixed acid is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, still more preferably 1.5% by mass or more and 10% by mass or less. From the same perspective, the blending amount of acetic acid in the mixed acid is preferably 2% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, still more preferably 15% by mass or more and 60% by mass or less. The mass ratio of phosphoric acid, nitric acid, and acetic acid (phosphoric acid / nitric acid / acetic acid) can be set as appropriate. For example, it can be 57 / 6 / 37. In the present disclosure, in one or more embodiments, the blending amount of each component in the mixed acid can be regarded as the content of each component in the mixed acid.

[0030] (Etching inhibitor) The etching inhibitor contained in the etching solution composition of the present disclosure may be used alone or in combination of two or more. In one or more embodiments, examples of the etching inhibitor in the present disclosure include at least one nitrogen-containing compound selected from polyalkyleneimine and polyalkylene polyamine. Examples of the polyalkyleneimine include polyethyleneimine (PEI). Examples of the polyalkylene polyamine include pentaethylenehexamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like.

[0031] When the etching inhibitor is polyalkyleneimine, the number average molecular weight of the etching inhibitor is preferably 300 or more, more preferably 600 or more, still more preferably 1,200 or more, from the viewpoints of reducing etching non-uniformity, storage stability, and improving filtration rate, and preferably 100,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, from the viewpoint of viscosity. More specifically, the number average molecular weight of the etching inhibitor is preferably 300 or more and 100,000 or less, more preferably 600 or more and 5,000 or less, still more preferably 1,200 or more and 3,000 or less. When the etching inhibitor is polyalkylene polyamine, the number average molecular weight or molecular weight of the etching inhibitor is preferably 50 or more, more preferably 80 or more, still more preferably 100 or more, from the viewpoints of reducing etching non-uniformity, storage stability, and improving filtration rate, and preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less, from the same viewpoints. More specifically, the number average molecular weight or molecular weight of the etching inhibitor is preferably 50 or more and 1,000 or less, more preferably 80 or more and 500 or less, still more preferably 100 or more and 300 or less.

[0032] In the present disclosure, the average molecular weight can be measured by gel permeation chromatography (GPC). Examples of the method for measuring the average molecular weight of the etching inhibitor of the present disclosure are shown below. <GPC conditions (for polyalkyleneimine)> Sample solution: Adjusted to a concentration of 0.1 wt% Apparatus / detector: HLC-8320GPC (integrated GPC) manufactured by Tosoh Corporation Column: α-M + α-M (manufactured by Tosoh Corporation) Eluent: 0.15 mol / L Na2SO4, 1% CH3COOH / water Column temperature: 40 °C Flow rate: 1.0 mL / min Sample solution injection volume: 100 μL Standard polymer: Pullulan with known molecular weight (Shodex P-5, P-50, P-200, P-800)

[0033] From the perspective of reducing etching non-uniformity, the compounding amount of the etching inhibitor in the etching liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and from the same perspective, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less. More specifically, the compounding amount of the etching inhibitor in the etching liquid composition of the present disclosure is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, still more preferably 0.5% by mass or more and 3% by mass or less. When the etching inhibitor is a combination of two or more kinds, the compounding amount of the etching inhibitor is the total compounding amount thereof.

[0034] (Water) In one or more embodiments, the etching liquid composition of the present disclosure contains water. Examples of the water contained in the etching liquid of the present disclosure include distilled water, ion-exchanged water, pure water, and ultrapure water. From the perspective of reducing etching non-uniformity, the compounding amount of water in the etching liquid composition of the present disclosure is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and from the same perspective, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less. More specifically, the compounding amount of water in the etching liquid composition of the present disclosure is preferably 2% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, still more preferably 7% by mass or more and 20% by mass or less.

[0035] (Other components) The etching liquid composition of the present disclosure may further contain other components as long as the effects of the present disclosure are not impaired. Examples of the other components include inorganic acids other than phosphoric acid and nitric acid, chelating agents, surfactants, solubilizing agents, preservatives, rust preventives, bactericides, antibacterial agents, antioxidants, and the like.

[0036] From the viewpoint of reducing etching unevenness, the etching liquid composition of the present disclosure preferably does not contain an azole compound. Here, "not containing an azole compound" includes, in one or more embodiments, not containing an azole compound, substantially not containing an azole compound, or not containing an amount of an azole compound that affects the etching result. The blending amount of the azole compound in the specific etching liquid composition of the present disclosure is not particularly limited, but is preferably less than 0.01% by mass, more preferably 0.001% by mass or less, and still more preferably 0% by mass (that is, not containing).

[0037] From the viewpoint of reducing etching unevenness, the etching liquid composition of the present disclosure preferably does not contain a chlorine-containing compound. Here, "not containing a chlorine-containing compound" includes, in one or more embodiments, not containing a chlorine-containing compound, substantially not containing a chlorine-containing compound, or not containing an amount of a chlorine-containing compound that affects the etching result. The blending amount of the chlorine-containing compound in the specific etching liquid composition of the present disclosure is not particularly limited, but is preferably less than 0.1% by mass, more preferably 0.001% by mass or less, and still more preferably 0% by mass (that is, not containing).

[0038] From the perspective of reducing etching non-uniformity, the etching solution composition of the present disclosure preferably does not contain or is not formulated with a phosphate-based compound. Here, "not containing or not being formulated with a phosphate-based compound" means, in one or more embodiments, not containing or not being formulated with a phosphate-based compound, substantially not containing or not being formulated with a phosphate-based compound, or not containing or not being formulated with an amount of a phosphate-based compound that affects the etching result. The amount of the phosphate-based compound formulated in the specific etching solution composition of the present disclosure is not particularly limited, but is preferably less than 0.1% by mass, more preferably 0.001% by mass or less, and still more preferably 0% by mass (i.e., not containing or not being formulated).

[0039] From the perspective of reducing etching non-uniformity, the etching solution composition of the present disclosure preferably does not contain hydrogen peroxide. Here, "not containing hydrogen peroxide" means, in one or more embodiments, not containing hydrogen peroxide, substantially not containing hydrogen peroxide, or not containing an amount of hydrogen peroxide that affects the etching result. The amount of hydrogen peroxide formulated in the specific etching solution composition of the present disclosure is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, still more preferably 0.001% by mass or less, and still more preferably 0% by mass (i.e., not containing).

[0040] From the perspective of reducing etching non-uniformity, the etching solution composition of the present disclosure preferably does not contain a fluorine compound. Here, "not containing a fluorine compound" means, in one or more embodiments, not containing a fluorine compound, substantially not containing a fluorine compound, or not containing an amount of a fluorine compound that affects the etching result. The amount of the fluorine compound formulated in the specific etching solution composition of the present disclosure is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, still more preferably 0.001% by mass or less, and still more preferably 0% by mass (i.e., not containing).

[0041] In one or more embodiments, the etching liquid composition of the present disclosure can be obtained by mixing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, water, and optionally any of the above-mentioned optional components in a known manner. Therefore, in one or more embodiments, the method for manufacturing the etching liquid of the present disclosure can include at least the step of mixing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water. In the present disclosure, "mixing at least phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water" means, in one or more embodiments, mixing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, water, and optionally any of the above-mentioned optional components simultaneously or in sequence. The mixing order may not be particularly limited. The mixing can be performed using a mixer such as a propeller-type stirrer, liquid circulation stirring by a pump, a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill. In the method for manufacturing the etching liquid of the present disclosure, the preferred blending amounts of the respective components can be the same as the preferred blending amounts of the respective components in the etching liquid composition of the present disclosure described above.

[0042] In the present disclosure, the "blending amount of each component in the etching liquid composition" means, in one or more embodiments, the blending amount of each component in the etching liquid composition at the time when it is used in the etching process, that is, at the time when the use for the etching treatment is started (at the time of use). In one or more embodiments, the blending amount of each component in the etching liquid composition of the present disclosure can be regarded as the content of each component in the etching liquid composition of the present disclosure. However, when affected by neutralization, the blending amount and the content may be different.

[0043] In one or more embodiments, the etching solution composition of the present disclosure can be obtained by blending a mixed acid composition containing phosphoric acid, nitric acid, and an organic acid with an etching inhibitor. Accordingly, in one or more embodiments, the method for manufacturing the etching solution of the present disclosure can include a step of blending a mixed acid composition containing phosphoric acid, nitric acid, and an organic acid with an etching inhibitor to obtain the etching solution composition. The mixed acid composition may contain water and, if necessary, the other components described above. The blending of the mixed acid composition and the etching inhibitor can be performed using the mixer described above. From the viewpoint of reducing etching unevenness, the blending amount of phosphoric acid in the mixed acid composition is preferably 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 93% by mass or less, and still more preferably 30% by mass or more and 90% by mass or less. From the same viewpoint, the blending amount of nitric acid in the mixed acid composition is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 1.5% by mass or more and 10% by mass or less. From the same viewpoint, the blending amount of the organic acid in the mixed acid composition is preferably 2% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and still more preferably 15% by mass or more and 60% by mass or less. The mass ratio (phosphoric acid / nitric acid / organic acid) of phosphoric acid, nitric acid, and organic acid in the mixed acid composition is preferably 10 - 95 / 0.5 - 20 / 2 - 80, more preferably 20 - 93 / 1 - 15 / 5 - 70, and still more preferably 30 - 80 / 1.5 - 10 / 15 - 60. From the viewpoint of etching characteristics, the blending amount of water in the mixed acid composition is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and still more preferably 5% by mass or more and 20% by mass or less. In one or more embodiments, the mixed acid composition is used in the production of the etching liquid composition of the present disclosure. Accordingly, in one aspect, the present disclosure relates to a mixed acid composition for use in a method for producing the etching liquid composition of the present disclosure, the mixed acid composition containing phosphoric acid, nitric acid, and an organic acid. Further, in one aspect, the present disclosure relates to the use of a mixed acid composition containing phosphoric acid, nitric acid, and an organic acid in the method for producing the etching liquid of the present disclosure.

[0044] Embodiments of the etching liquid composition of the present disclosure may be of a so-called one-component type in which all components are supplied to the market in a pre-mixed state, or may be of a so-called two-component type in which they are mixed at the time of use. As the two-component type etching liquid composition, water is divided into a first liquid and a second liquid, and phosphoric acid, nitric acid, an organic acid, and an etching inhibitor are each contained in either one or both of the first liquid and the second liquid, and the first liquid and the second liquid are mixed at the time of use. The first liquid and the second liquid may each contain any of the above-described optional components as required.

[0045] From the viewpoint of reducing etching unevenness, the pH of the etching liquid composition of the present disclosure is preferably 1 or less, more preferably 0 or less, still more preferably less than 0, and still more preferably about -1. Note that the pH of the etching liquid composition of the present disclosure can preferably be -5 or more, more preferably -3 or more. In the present disclosure, the pH of the etching liquid composition is the value at 25°C and can be measured using a pH meter, specifically, by the method described in the examples.

[0046] The viscosity of the etching liquid composition of the present disclosure at 25°C is preferably 11 mPa·s or more, more preferably 13 mPa·s or more, still more preferably 20 mPa·s or more, from the viewpoint of suppressing liquid dripping, and preferably less than 40 mPa·s, more preferably 39 mPa·s or less, still more preferably 38 mPa·s or less, from the viewpoint of improving the filtration rate. More specifically, the viscosity of the etching liquid composition of the present disclosure at 25°C is preferably 11 mPa·s or more and less than 40 mPa·s, more preferably 13 mPa·s or more and 39 mPa·s or less, still more preferably 20 mPa·s or more and 38 mPa·s or less. In the present disclosure, the viscosity of the etching liquid composition can be measured using a general-purpose viscometer such as a B-type viscometer or an Ubbelohde viscometer, and specifically, it can be measured by the method described in the examples. The viscosity of the etching liquid composition at 25°C can be adjusted, for example, with water or an organic solvent.

[0047] The etching liquid composition of the present disclosure may be stored and supplied in a concentrated state as long as its storage stability is not impaired. In this case, it is preferable in terms of reducing the manufacturing and transportation costs. And this concentrated liquid can be appropriately diluted with water or an aqueous acid solution as needed and used in the etching process. The dilution ratio can be, for example, 3 to 100 times.

[0048] [Etching target film] The etching target film to be etched using the etching liquid composition of the present disclosure is a metal film formed on a substrate (hereinafter, also referred to as "etching target metal film"). The substrate is, in one or more embodiments, at least one substrate selected from a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a plasma display, a substrate for a FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, and a substrate for a solar cell. The metal film to be etched is, in one or more embodiments, a metal film containing at least one kind of metal. The metal film to be etched is not particularly limited as long as the effects of the present disclosure can be achieved. For example, it includes metal films containing at least one kind of metal selected from tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, rhodium, copper, nickel, cobalt, titanium, titanium nitride, alumina, aluminum, and iridium. The metal film to be etched does not contain copper and aluminum in one or more embodiments. In one or more embodiments, the etching liquid composition of the present disclosure is preferably used for etching a metal film (excluding copper and aluminum) containing at least one kind of metal selected from tungsten, tantalum, zirconium, molybdenum, niobium, and nickel. In one or more embodiments, the etching liquid composition of the present disclosure is preferably used for etching a tungsten film, a molybdenum film, or a nickel film. That is, as the film to be etched, in one or more embodiments, a tungsten film, a molybdenum film, or a nickel film is included.

[0049] [Kit] In one aspect, the present disclosure relates to a kit for manufacturing the etching liquid composition of the present disclosure (hereinafter, also referred to as "the kit of the present disclosure"). In one or more embodiments, the kit of the present disclosure includes a first liquid and a second liquid in a state where they are not mixed with each other, and phosphoric acid, nitric acid, an organic acid, and an etching inhibitor are each included in either one or both of the first liquid and the second liquid, and a kit (two-component etching liquid) in which the first liquid and the second liquid are mixed during use. After the first liquid and the second liquid are mixed, they may be diluted with water or an aqueous acid solution as necessary. The first liquid or the second liquid may contain all or part of the total amount of water used for preparing the etching liquid. The first liquid and the second liquid may each contain the above-mentioned optional components as necessary. In one or more embodiments, the kit of the present disclosure includes a mixed acid composition (first liquid a) containing phosphoric acid, nitric acid, and an organic acid and a solution containing an etching inhibitor (second liquid a) without being mixed with each other, and the kit (two-component etching solution) in which these are mixed during use is mentioned. After the first liquid a and the second liquid a are mixed, they may be diluted with water or an aqueous acid solution as necessary. The first liquid a or the second liquid a may contain all or part of the total amount of water used for preparing the etching solution. The acid contained in the first liquid a may be the total amount or a part of the total amount of acid used for preparing the etching solution. The second liquid a may contain an acid. The first liquid a and the second liquid a may each contain any of the above-described optional components as necessary. According to the kit of the present disclosure, an etching solution capable of achieving both suppression of liquid dripping during filling into a container and improvement in filtration rate can be obtained.

[0050] In one or more embodiments, the etching solution composition of the present disclosure can be used for etching a metal in the manufacturing process of an electronic device, particularly a semiconductor wafer. In one or more embodiments, the etching solution composition of the present disclosure can be suitably used for producing at least one substrate selected from a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a plasma display, a substrate for a FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, and a substrate for a solar cell. In one or more embodiments, the etching solution composition of the present disclosure can be used for etching an electrode in the manufacturing process of an electronic device, particularly a semiconductor memory such as a non-volatile memory including a NAND type flash memory. In one or more embodiments, the etching solution composition of the present disclosure can be suitably used for producing a pattern having a three-dimensional structure. Thereby, an advanced device such as a memory with increased capacity can be obtained. The etching solution composition of the present disclosure can be used, for example, in an etching method as disclosed in JP-A-2020-145412.

[0051] [Etching liquid composition in a container] In one aspect, the present disclosure is based on the finding that an etching liquid composition filled in a container contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, has a viscosity within a predetermined range at 25° C., and has a contact angle (advancing contact angle, advancing contact angle / receding contact angle) with respect to the material of the container within a predetermined range, thereby suppressing liquid dripping when taking out the etching liquid in the container.

[0052] That is, in one aspect, the present disclosure relates to an etching liquid composition filled in a container, wherein the etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate, the etching liquid composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, has a viscosity at 25° C. of 11 mPa·s or more and less than 40 mPa·s, and the receding contact angle of the etching liquid composition with respect to the material of the container is 60° or more and the ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) is 1.4 or less (hereinafter, also referred to as "the etching liquid composition in a container of the present disclosure"). According to the present disclosure, in one or more embodiments, liquid dripping when taking out the etching liquid in the container can be suppressed.

[0053] In the etching liquid composition in a container of the present disclosure, examples of the etching liquid composition filled in the container include the etching liquid composition of the present disclosure described above in one or more embodiments. In the etching liquid composition in a container of the present disclosure, examples of the container include a container filled with the etching liquid composition of the present disclosure described above. In one or more embodiments, the etching liquid composition in a container of the present disclosure can be obtained by using the etching liquid production method of the present disclosure. For example, the etching liquid composition in a container of the present disclosure can be obtained by filling the etching liquid composition of the present disclosure into a container 6 using a filling system as shown in FIG. 1. The details of the filling system shown in FIG. 1 are as described above.

[0054] (Contact angle of the etching solution with respect to the material of the container) In the etching solution composition contained in the container of the present disclosure, the etching solution composition filled in the container has a receding contact angle of 60° or more with respect to the material of the container and a ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less from the viewpoint of suppressing liquid dripping. The preferable values of the advancing contact angle, the receding contact angle, and the ratio (advancing contact angle / receding contact angle) with respect to the material of the container can be the same as the preferable values of the advancing contact angle, the receding contact angle, and the ratio (advancing contact angle / receding contact angle) with respect to the material of the filling port of the above-described filling nozzle. In the present disclosure, the contact angle of the etching solution composition with respect to the material of the container can be measured using the same method as the method for measuring the contact angle of the etching solution composition with respect to the material of the filling port of the above-described filling nozzle.

Examples

[0055] Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples in any way.

[0056] 1. Preparation of etching solution (Examples 1 to 12, Comparative Examples 1 to 6) Phosphoric acid, nitric acid, organic acids shown in Tables 1 to 2, etching inhibitors shown in Tables 1 to 2, and water were blended to obtain the etching solutions (pH: -2 to 0) of Examples 1 to 12 and Comparative Examples 1 to 6. The blending amounts (mass%, active ingredient) of the respective components in the prepared etching solutions are shown in Tables 1 to 2. Note that the blending amount of water in Tables 1 to 2 also includes the blending amount of water contained in acid aqueous solutions and the like.

[0057] The following components were used for the preparation of the etching solution. Phosphoric acid [manufactured by Phosphorus Chemical Industry Co., Ltd., concentration 85%] Nitric acid [manufactured by Fujifilm Wako Pure Chemical Corporation, concentration 70%] (Organic acid) Acetic acid [manufactured by Fujifilm Wako Pure Chemical Corporation, concentration 100%] (Etching inhibitor) Polyethyleneimine [number average molecular weight 1,800, "Epomin SP-018" manufactured by Nippon Shokubai Co., Ltd.] Diethylenetriamine [molecular weight 103, "DETA" of Tosoh Corporation] (Water) Water [ultrapure water produced using a continuous ultrapure water production device (Pureconty PC-2000VRL type) and subsystem (Mac Ace KC-05H type) manufactured by Kurita Water Industries, Ltd.]

[0058] 2. Measurement method of parameters [pH of the etching solution] The pH value of the etching solution at 25°C is the value measured using a pH meter (manufactured by TOA-DKK Corporation), and it is the value after 1 minute of immersing the electrode of the pH meter into the etching solution.

[0059] [Viscosity of the etching solution] The viscosity of the etching solution was measured using the following viscometer under the following conditions. Device name: TVB-10 type viscometer (with thermostat) manufactured by Toki Sangyo Co., Ltd. Rotor: Spindle No. M1, Cord No. 20 Rotation speed: 100 rpm, measure the viscosity value after 60 seconds Measurement temperature: 25°C

[0060] [Advancing contact angle, receding contact angle, advancing contact angle / receding contact angle of the etching solution composition with respect to the material of the filling port of the filling nozzle] The advancing contact angle and receding contact angle of the etching solution composition with respect to the material of the filling port of the filling nozzle were measured using the following measuring device under the following conditions. Device name: K-100 manufactured by KRUSS Size of the sample plate: 20 (mm) × 50 (mm) × 2 (mm) Material of the sample plate (material): Materials shown in Tables 1 - 2 [PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxyalkane), PP (polypropylene), PE (polyethylene), PVC (polyvinyl chloride)] Immersion liquid: Etching solution composition <Measurement conditions> Temperature: 25°C Measurement speed: 1 mm / min Maximum immersion depth: 5 mm Minimum immersion depth: 1 mm Number of measurements: 3 times Data acquisition step: 0.2 mm <Analysis method> Calculated from the slope when the measurement result of the third time was plotted as immersion depth - Force <Operation method> The contact angle (advancing contact angle) of the tip was measured during the process of gradually immersing the sample plate into the etching liquid composition. Also, the contact angle (receding contact angle) of the trailing edge was measured during the process of gradually pulling up the sample plate immersed in the etching liquid composition. Then, the ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) was calculated. The results are shown in Tables 1 - 2.

[0061] 3. Evaluation of the etching liquid The prepared etching liquid composition was filled into a container under the following conditions using the filling system shown in Fig. 1 to obtain the etching liquid compositions in containers of Examples 1 - 12 and Comparative Examples 1 - 6. Then, the following evaluations were carried out and the results are shown in Tables 1 - 2. Here, the filling system shown in Fig. 1 includes a tank 1 for storing the etching liquid composition, a pump 2 for feeding the etching liquid composition, a filter 3 for filtering the etching liquid composition, an outlet valve 4 for controlling the flow rate of the etching liquid composition discharged from the outlet (filling nozzle) 5, and a pipe P1 connecting the tank 1, the pump 2, the filter 3, the outlet valve 4, and the outlet (filling nozzle) 5. Further, it includes a circulation path P2 branched from the pipe P1 between the filter 3 and the outlet valve 4 and connected to the upstream side of the pump 2. Also, the filling system shown in Fig. 1 further includes a circulation valve 7 for controlling the flow rate of the etching liquid composition circulating through the circulation path P2. First, the prepared etching liquid composition is accommodated in the tank 1. Then, the etching liquid composition in the tank 1 is fed by the pump 2, filtered by the filter 3, and the filtered etching liquid composition is discharged from the filling port of the outlet (filling nozzle) 5 and filled into the container 6 through the opening of the container 6. <Filling system> Pump 2: Diaphragm pump DP-10BPT (manufactured by Yamada Corporation) Pipes P1 and P2: Corrugated flexible hose 15A (manufactured by Fluor Chemical Co., Ltd.) Filter 3: Membrane filter Outlet 5 (filling nozzle): Outer diameter 14 mm, material of the filling port of the filling nozzle: PTFE Container 6: 20 L resin container <Condition> Filtration temperature: 25 °C Filtration pressure: 0.3 MPa Filtration flow rate: 0.1 - 20 kg / (m 2 ·min) Scale: 300 kg of etching solution composition Filling flow rate: 0.1 - 20 kg / (m 2 ·min) Circulation flow rate: 0.1 - 20 kg / (m 2 ·min)

[0062] [Number of liquid drips during filling] After filling a predetermined amount of the etching solution composition into container 6 under the above conditions using the filling system shown in Fig. 1, in order to fill the next empty filling container, when outlet 5 (filling nozzle) was pulled up from the opening of container 6, the frequency of liquid dripping occurring around the opening and on the wall surface of container 6 was evaluated. The occurrence frequency (number of liquid drips) when the above operation was performed 10 times is shown in Tables 1 - 2. The fewer the number of liquid drips, the more it can be judged that liquid dripping is suppressed.

[0063] [Evaluation of liquid permeability] The prepared unfiltered etching solution composition was passed through a predetermined filter (manufactured by Advantec, hydrophilic PTFE 0.20 (pore diameter) μm filter, model: 25HP020AN) under a constant pressure of a liquid temperature of 25 °C and an air pressure of 0.30 MPa, and the liquid passing amount (g / min) passed through the filter in the initial 1 minute was determined and shown in Table 1. Incidentally, the liquid passing amount through the 0.20 μm filter under these conditions can be used as an index of the filtration rate when filling the etching solution composition into the container. That is, the higher the liquid passing amount, the more it can be evaluated that the etching solution composition can be filtered at high speed.

[0064] [Evaluation of Productivity] The productivity of the etching solution composition can be evaluated by the sum of the filtration rate, i.e., the filtration fluid permeability, and the frequency of liquid dripping during filling. For example, those with good filtration fluid permeability and extremely low frequency of liquid dripping during filling have very high productivity, which can be evaluated as "A" because there is little wiping work around the opening and on the wall surface of the container. On the other hand, those with good filtration fluid permeability and extremely high frequency of liquid dripping during filling have very low productivity, which can be evaluated as "D" because there is a lot of wiping work around the opening and on the wall surface of the container. Then, the evaluation criteria were set in four levels as follows, and the results are shown in Table 1. [Evaluation Criteria] A: The filtration fluid permeability is good, and there is almost no wiping work, so the productivity is very high. B: The filtration fluid permeability is good, and there is little wiping work, so it is very high. C: There is almost no wiping work. Since the filtration fluid permeability is poor, the productivity is inferior. D: The filtration fluid permeability is good, but there is a lot of wiping work and the number of interruptions increases, so the productivity is very low.

[0065] [Table 1]

[0066] [Table 2]

[0067] As shown in Table 1, Examples 1 to 9 that satisfy the conditions that the receding contact angle of the etching solution with respect to the material of the filling port of the filling nozzle is 60° or more and (advancing contact angle / receding contact angle) is 1.4 or less had a small number of liquid dripping times when filling the container, and liquid dripping was suppressed. In addition, the etching solutions of Examples 1 to 7 containing phosphoric acid, nitric acid, organic acid, and an etching inhibitor and having a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s, compared with Examples 8 to 9 containing phosphoric acid, nitric acid, organic acid, and an etching inhibitor and having a viscosity at 25°C of 40 mPa·s or more, and Comparative Example 1 containing phosphoric acid, nitric acid, organic acid, and an etching inhibitor and having a viscosity at 25°C of less than 11 mPa·s, can achieve both suppression of liquid dripping during filling into the container and improvement of the filtration rate, indicating that the productivity is improved. As shown in Table 2, Examples 1, 10 to 11, 7, and 12 that satisfy the condition that the receding contact angle of the etching solution with respect to the material of the filling port of the filling nozzle is 60° or more and (advancing contact angle / receding contact angle) is 1.4 or less have fewer liquid dripping times when filling the container compared with Comparative Examples 2 to 6 that do not satisfy the condition that the receding contact angle of the etching solution with respect to the material of the filling port of the filling nozzle is 60° or more and (advancing contact angle / receding contact angle) is 1.4 or less, indicating that liquid dripping can be suppressed.

Industrial Applicability

[0068] The etching solution composition of the present disclosure is useful for etching metal films on substrates such as semiconductor wafers, substrates for liquid crystal display devices, substrates for plasma displays, substrates for FED (Field Emission Display), substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

Explanation of Symbols

[0069] 1: Tank, 2: Pump, 3: Filter, 4: Outlet valve, 5: Outlet (filling nozzle), 6: Container, 7: Circulation valve, P1: Pipe, P2: Circulation path

Claims

1. A method for producing an etching solution composition, comprising: The etching solution composition is an etching solution composition for etching a metal film formed on a substrate, The method includes a step of filling a container with the etching solution composition using a filling nozzle having a filling port for discharging the etching solution composition, The advancing contact angle and the receding contact angle of the etching solution composition with respect to the material of the filling port of the filling nozzle are The advancing contact angle is 70° or more and 95° or less, The receding contact angle is 60° or more and 85° or less, and A method for producing an etching solution composition, in which the ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) is 1.4 or less.

2. The method for producing an etching solution composition according to claim 1 , wherein the etching solution composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water.

3. The method for producing an etching solution composition according to claim 2 , wherein the organic acid includes acetic acid.

4. The method for producing an etching solution composition according to claim 2 , wherein the organic acid is present in an amount of 11% by mass or more and 59% by mass or less.

5. The method for producing the etching solution composition according to claim 2 , comprising the step of blending a mixed acid composition containing phosphoric acid, nitric acid and an organic acid with an etching inhibitor to obtain the etching solution composition.

6. The method for producing an etching solution composition according to claim 2, wherein the etching inhibitor is at least one nitrogen-containing compound selected from the group consisting of polyalkyleneimines and polyalkylenepolyamines.

7. The method for producing an etching solution composition according to claim 1 or 2, wherein the etching solution composition does not contain an azole compound.

8. The method for producing an etching solution composition according to claim 1 or 2, wherein the etching solution composition does not contain hydrogen peroxide.

9. The method for producing an etching solution composition according to claim 1 or 2, wherein the etching solution composition does not contain a fluorine compound.

10. The method for producing an etching solution composition according to claim 1 or 2, wherein the etching solution composition has a pH of 1 or less.

11. 3. The method for producing an etching solution composition according to claim 1, wherein the metal film is a metal film containing at least one metal selected from the group consisting of tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, rhodium, copper, nickel, cobalt, titanium, titanium nitride, alumina, aluminum, and iridium.

12. 3. The method for producing an etching solution composition according to claim 1, wherein the substrate is at least one type of substrate selected from the group consisting of a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a plasma display, a substrate for an FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, and a substrate for a solar cell.

13. The method for producing an etching liquid composition according to claim 1 or 2, wherein the container is made of a polyethylene resin, a polypropylene resin or a fluororesin.

14. The method for producing an etching solution composition according to claim 1 or 2, wherein the material of the container is at least one selected from the group consisting of polypropylene, perfluoroalkoxyalkane, and polytetrafluoroethylene.

15. A mixed acid composition for use in the method for producing the etching solution composition according to claim 5, A mixed acid composition comprising phosphoric acid, nitric acid and an organic acid.

16. An etching solution composition filled in a container, The etching solution composition is an etching solution composition for etching a metal film formed on a substrate, The etching solution composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, The advancing contact angle and the receding contact angle of the etching solution composition with respect to the material of the container are The advancing contact angle is 70° or more and 95° or less, The receding contact angle is 60° or more and 85° or less, and A containerized etching solution composition having a ratio of advancing contact angle to receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

17. 17. The container-packed etching solution composition according to claim 16, wherein the container is made of a polyethylene resin, a polypropylene resin, or a fluororesin.

18. 18. The container-packed etching solution composition according to claim 16, wherein the container is made of at least one material selected from the group consisting of polypropylene, perfluoroalkoxyalkane, and polytetrafluoroethylene.

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