Method for producing etching liquid composition

Abstract

In one embodiment, the present invention provides a method for manufacturing an etching liquid composition capable of suppressing liquid dropping when filling a container. In one embodiment, the present invention relates to a method for manufacturing an etchant composition for etching a metal film formed on a substrate, the etchant composition being a method for manufacturing an etchant composition for etching a metal film formed on a substrate. The manufacturing method of the etching liquid composition comprises a step of filling the etching liquid composition into a container by using a filling nozzle with a filling port for discharging the etching liquid composition, and the receding contact angle of the etching liquid to the material of the filling port of the filling nozzle is more than 60 degrees. And the ratio of the forward contact angle to the backward contact angle (forward contact angle / backward contact angle) is 1.4 or less.

Description

Technical Field

[0001] The invention relates to a method for preparing an etching liquid composition. Background Art

[0002] In the manufacturing process of semiconductor devices, for example, a process is performed in which a target 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, aluminum oxide, aluminum, and iridium is etched into a predetermined pattern. A mixed acid aqueous solution containing phosphoric acid, nitric acid, and acetic acid is generally used as the etching solution.

[0003] In recent years, in the semiconductor field, high integration has been advancing, and wiring has become more complex and miniaturized. This has led to increasing demands for pattern processing technology and etching solutions, and various etching solution compositions and etching methods have been proposed.

[0004] For example, Japanese Patent Application Laid-Open No. 2014-27274 (Patent Document 1) proposes an etching solution composition for etching a Cu / Mo bilayer film, comprising approximately 50 to 80 wt % of phosphoric acid, approximately 0.5 to 10 wt % of nitric acid, approximately 4 to 30 wt % of acetic acid, approximately 0.5 to 6 wt % of a chlorine-containing compound, and the remainder being water.

[0005] Japanese Patent Application Publication No. 2012-156248 (Patent Document 2) proposes an etching method for etching a metal laminate film comprising an alloy of copper, molybdenum, and / or titanium, using an etching solution composition comprising 40 to 50 wt % of phosphoric acid, 1.5 to 3.5 wt % of nitric acid, 25 to 40 wt % of acetic acid, and water.

[0006] Japanese Patent Application Publication No. 2009-218601 (Patent Document 3) proposes an etching composition for a thin-film transistor liquid crystal display device, which comprises: 55 to 70 weight percent phosphoric acid, 3 to 15 weight percent nitric acid, 5 to 20 weight percent acetic acid, 0.5 to 10 weight percent phosphate, 0.1 to 5 weight percent chlorine-based compound, 0.01 to 4 weight percent azole-based compound, and the remainder water.

[0007] Japanese Patent Application Laid-Open No. 2008-244205 (Patent Document 4) proposes an etching solution composition for etching a metal film having a multilayer structure formed by laminating a molybdenum film on the surface of an aluminum or aluminum alloy film formed on a substrate to form a predetermined pattern. The etching solution composition comprises: phosphoric acid at a concentration of 40 to 70% by mass, nitric acid at a concentration of 0.5 to 10% by mass, acetic acid at a concentration of 50 to 15% by mass, and the remainder being water.

[0008] Japanese Patent Application Publication No. 2007-305996 (Patent Document 5) proposes an etching composition for a thin-film transistor liquid crystal display device, which comprises: 50 to 80 weight percent phosphoric acid, 2 to 15 weight percent nitric acid, 3 to 20 weight percent acetic acid, 0.05 to 3 weight percent lithium compound, 0.1 to 5 weight percent phosphate compound, and the remainder water. Summary of the Invention

[0009] In one embodiment, the present invention relates to a method for producing an etching liquid composition, wherein the etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate, the method comprising the step of filling the etching liquid composition into a container using a filling nozzle having a filling port for discharging the etching liquid composition, wherein the etching liquid has a receding contact angle of 60° or greater with respect to a material at the filling port of the filling nozzle, and a ratio of an advancing contact angle to a receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

[0010] In one embodiment, the present invention relates to a mixed acid composition used in the method for producing the etching solution composition of the present invention, wherein the mixed acid composition comprises phosphoric acid, nitric acid, and an organic acid.

[0011] In one embodiment, the present invention relates to an etching liquid composition contained in a container, wherein the etching liquid composition is filled in the container and is used 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, and has a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s. The etching liquid composition 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.

[0012] In one embodiment, the present invention relates to use of a mixed acid composition comprising phosphoric acid, nitric acid, and an organic acid in the method for producing the etching solution composition of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is a schematic diagram showing one embodiment of a filling system. DETAILED DESCRIPTION

[0014] Typically, an etching solution composition is filled into a container and commercialized. When the etching solution composition is filled into the container, a filtration process using a filter or the like is performed to reduce the content of foreign matter (particles) in the etching solution composition. Therefore, an etching solution having excellent filter permeability and a high filtration rate is desired.

[0015] Furthermore, the etching liquid may drip when filling the container. The more drips occur, the longer the wiping process takes, which reduces productivity. To improve productivity, the etching liquid must be less likely to drip. Furthermore, the etching liquid must be less likely to drip when removing the etching liquid from the container.

[0016] Therefore, in one embodiment, the present invention provides a method for producing an etching liquid composition that can suppress dripping when filling a container. In another embodiment, the present invention provides a method for producing an etching liquid composition that can achieve both suppression of dripping when filling a container and improvement of the filtration rate. In another embodiment, the present invention provides a container-contained etching liquid composition that can suppress dripping when removing the etching liquid from the container.

[0017] In one embodiment, the present invention provides a method for producing an etching liquid composition that can suppress dripping during filling of a container. In one embodiment, the present invention provides a method for producing an etching liquid composition that can achieve both suppression of dripping during filling of a container and improvement of the filtration rate. In one embodiment, the present invention provides a container-contained etching liquid composition that can suppress dripping during removal of the etching liquid from the container.

[0018] In one embodiment, the present invention is based on the finding that by setting the contact angle (receding contact angle, advancing contact angle / receding contact angle) of the etching solution with respect to the material of the filling port within a predetermined range, dripping during filling into the container can be suppressed and the filtration speed can be increased.

[0019] That is, in one embodiment, the present invention relates to a method for producing an etching liquid composition (hereinafter also referred to as the “etching liquid production method of the present embodiment 1”), 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 invention”), the method for producing the etching liquid composition including a step of filling the etching liquid composition into a container using a filling nozzle having a filling port for discharging the etching liquid composition (hereinafter also referred to as the “filling step”), wherein the etching liquid has a receding contact angle of 60° or greater with respect to the material at the filling port of the filling nozzle, and a ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

[0020] According to the first aspect, in one or more embodiments, dripping during filling of a container can be suppressed. Also, according to the first aspect, in one or more embodiments, both the suppression of dripping during filling of a container and the improvement of the filtration speed can be achieved.

[0021] The details of the mechanism by which the effects of Method 1 are expressed are not yet clear, but the following is speculated.

[0022] For the same liquid, by keeping the receding contact angle above a specified value, the number of drips can be reduced. By keeping the ratio of the advancing contact angle to the receding contact angle below a specified value, a balance can be achieved between liquid permeability (filtration speed) and drip suppression, thereby improving productivity. When the receding contact angle is high enough and the ratio of the advancing contact angle to the receding contact angle is within a certain range, it is believed that these two effects will improve productivity in etching processes (for example, processes for etching electronic components and processes preparing for etching).

[0023] However, the present invention should not be construed as being limited to these mechanisms.

[0024] In another aspect, the present invention is based on the finding that by using an etching solution 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 of a container and improvement of the filtration rate.

[0025] That is, in another embodiment, the present invention relates to a method for producing an etching solution composition (hereinafter also referred to as the “etching solution production method of embodiment 2”), which is a method for producing an etching solution composition filled in a container, wherein the etching solution composition is an etching solution composition for etching a metal film formed on a substrate (hereinafter also referred to as the “etching solution composition of the present invention”), the etching solution composition contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, and has a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s, and the method for producing the etching solution composition includes a step of filling the container with the etching solution composition (hereinafter also referred to as the “filling step”).

[0026] According to the second aspect, in one or more embodiments, a method for producing an etching liquid composition capable of achieving both suppression of dripping during filling into a container and improvement of the filtration rate can be provided.

[0027] The details of the mechanism by which the effects of this method 2 are expressed are not yet clear, but the following is speculated.

[0028] The etching solution composition of Embodiment 2 is believed to have a viscosity within a predetermined range, thereby suppressing dripping when filling a container. Furthermore, the etching solution composition of Embodiment 2 is believed to contain an organic acid, which rapidly promotes neutralization of the strong acid (phosphoric acid, nitric acid) and the etching inhibitor, thereby suppressing the formation of submicron-sized particles, improving the liquid permeability of the filter, and increasing the filtration rate.

[0029] However, the present invention should not be construed as being limited to these mechanisms.

[0030] In the following description, the etching solution manufacturing methods of the present embodiment 1 and the present embodiment 2 are also collectively referred to as “the etching solution manufacturing method of the present invention”.

[0031] [Filling process]

[0032] The method for producing an etching solution of the present invention includes a step of filling the etching solution composition of the present invention into a container (filling step). In one or more embodiments, the filling step is a step of filling the etching solution composition of the present invention into the container using a filling nozzle having a filling port for discharging the etching solution composition.

[0033] In the filling step, the method for filling the container with the etching liquid composition is not particularly limited, and the container can be filled by a conventionally known method depending on the form of the container.

[0034] As a method of filling the container with the etching liquid composition in the filling step, for example, the following can be mentioned: Figure 1 The method of filling the etching liquid composition into the container by the filling system shown may also be interpreted in a non-limiting manner.

[0035] In one or more embodiments, Figure 1 As shown, the filling system includes: a tank 1 that stores the etching liquid composition; a pump 2 that transports the etching liquid composition; a filter 3 that filters the etching liquid composition; an outlet valve 4 that controls the flow rate of the etching liquid composition discharged from the outlet (filling nozzle) 5; and a pipe P1 that connects the tank 1, the pump 2, the filter 3, the outlet valve 4, and the outlet (filling nozzle) 5; the filling system further includes a circulation path P2 that branches from the pipe P1 between the filter 3 and the outlet valve 4 and is connected to the upstream side of the pump 2. In addition, in one or more embodiments, Figure 1 The shown filling system further includes a circulation valve 7 that controls the flow rate of the etching liquid composition circulating in the circulation path P2.

[0036] In one or more embodiments, Figure 1 The filling system shown is configured as follows: the etching liquid composition in the tank 1 is fed by a pump 2, filtered by a filter 3, the outlet valve 4 is opened to discharge the etching liquid composition from an outlet (filling nozzle) 5, and the discharged etching liquid composition is filled into a container 6. The circulation valve 7 is opened both when the outlet valve 4 is open and when it is closed, so that the etching liquid composition circulates in the circulation path P2.

[0037] In one or more embodiments, pump 2 is a pump that transports the etching liquid composition within tank 1 to pipe P1. The type of pump is not particularly limited; examples include diaphragm pumps. In one or more embodiments, pump 2 is stopped when both circulation valve 7 and outlet valve 4 are closed.

[0038] In one or more embodiments, filter 3 is a filter for filtering the etching solution composition. Examples of filter 3 include conventional membrane filters, pleated filters, depth filters, and filters containing filter aids, and combinations thereof may be used. Examples of filter 3 include 1 to 5 stages.

[0039] In one or more embodiments, the outlet 5 is a filling nozzle having a filling port for discharging the etching liquid composition.

[0040] It should be noted that in Figure 1 In the embodiment, the circulation path P2 is configured to connect the downstream side of the filter 3 to the tank 1. However, the present invention is not limited thereto, and any configuration is acceptable as long as the downstream side of the filter 3 can be connected to the upstream side of the pump 2. 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.

[0041] In addition, Figure 1 In the embodiment, the outlet valve 4 and the circulation valve 7 are separately provided. However, instead of these two valves, a three-way valve may be provided at the branch point between the pipe P1 and the circulation path P2 to switch the flow path of the etching liquid composition.

[0042] in addition, Figure 1 The filling system in FIG. 1 is configured to circulate the etching liquid through the circulation path P2 and the circulation valve 7 , but may be configured without the circulation path P2 and the circulation valve 7 (ie, a configuration that does not circulate the etching liquid).

[0043] [Filling nozzle]

[0044] The filling nozzle used in the filling step may be any one that can be filled with the etching liquid, and the shape, size, etc. are not particularly limited.

[0045] Examples of the outer diameter of the filling port of the filling nozzle include 5 mm to 1000 mm.

[0046] From the viewpoint of suppressing dripping, the material of the filling port of the filling nozzle is preferably at least one selected from polypropylene (PP), PFA (perfluoroalkoxyalkane), and PTFE (polytetrafluoroethylene), and more preferably PFA and PTFE.

[0047] [container]

[0048] Examples of containers filled with the etching liquid composition include those 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 fluororesins include PFA (perfluoroalkoxyalkane), PTFE (polytetrafluoroethylene), and mixtures thereof. Among these, the container material (material) is preferably at least one selected from polypropylene (PP), PFA (perfluoroalkoxyalkane), and PTFE (polytetrafluoroethylene) from the perspective of preventing dripping, with PFA and PTFE being more preferred.

[0049] In the present invention, a "polyethylene resin or polypropylene resin container" refers to a container in which at least the portion of the container that contacts the etching solution composition is made of polyethylene resin or polypropylene resin. As the resin container of the present invention, for example, a container having a polyethylene resin or polypropylene resin layer provided as an inner layer in contact with the etching solution composition, and a resin of another material laminated on the outer layer thereof can be used.

[0050] Generally, antistatic agents such as surfactants and metal oxides are added to commercially available polyethylene resin or polypropylene resin containers. However, the etching solution composition of the present invention preferably does not contain an antistatic agent.

[0051] Furthermore, since the etching solution composition of the present invention contains nitric acid as an essential component, to prevent decomposition by sunlight, etc., it is preferable to use a container that is colored or light-shielding, such as gray or blue, rather than a translucent or white container.

[0052] Examples of the container of the present invention include resin containers with a capacity of 0.1 to 30 L, composite containers comprising a combination of a resin inner container with a capacity of 0.1 to 30 L and cardboard, composite containers comprising a combination of a resin inner container with a capacity of 1 to 30 L and a metal can, resin canister containers with a capacity of 20 to 300 L, composite containers comprising a combination of a resin inner container with a capacity of 20 to 300 L and a metal canister, composite containers comprising a combination of a resin inner container with a capacity of 500 to 1200 L and a metal receptacle, and ISO storage tanks of 1000 or greater.

[0053] The container in the present invention may be any container that can be used to store or transport the etching solution composition, and examples thereof include containers produced by injection molding, extrusion molding, or rotational molding.

[0054] In one or more embodiments, when the etching liquid composition is filled into the container using a nozzle (filling nozzle), the outlet diameter of the nozzle (outer diameter of the filling port) may be, for example, 14 mm in outer diameter.

[0055] [Etching liquid composition]

[0056] In one or more embodiments, the etching solution composition of the present invention comprises phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water. In another or more embodiments, the etching solution composition of the present invention comprises phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, and has a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s.

[0057] (Contact angle of the etching liquid on the material (material) of the filling port of the filling nozzle)

[0058] From the perspective of suppressing dripping, the advancing contact angle of the etching solution composition of the present invention with respect to the material filling the filling port of the nozzle is preferably 70° or greater, more preferably 75° or greater, and even more preferably 79° or greater. Furthermore, from the perspective of productivity, it is preferably 120° or less, more preferably 100° or less, and even more preferably 95° or less. From the same perspective, the advancing contact angle is preferably 70° or greater and 120° or less, more preferably 75° or greater and 100° or less, and even more preferably 79° or greater and 100° or less.

[0059] From the perspective of suppressing dripping, the receding contact angle of the etching solution composition of the present invention with respect to the material filling the filling port of the nozzle is 60° or greater, preferably 66° or greater, and more preferably 70° or greater. Furthermore, from the perspective of productivity, it is preferably 100° or less, more preferably 92° or less, and even more preferably 85° or less. From the same perspective, the receding contact angle is preferably 60° or greater and 100° or less, more preferably 66° or greater and 92° or less, and even more preferably 70° or greater and 85° or less.

[0060] From the viewpoint of suppressing dripping, the etching solution composition of the present invention has a ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less, preferably 1.3 or less, and more preferably 1.2 or less, with respect to the material filling the filling port of the nozzle.

[0061] In the present invention, the contact angles (advancing contact angle, receding contact angle) of the etching solution filling the nozzle with respect to the material of the filling port can be measured at 25°C using a contact angle measuring device (e.g., K-100 manufactured by KRUSS). Specifically, the measurement can be performed using the method described in the Examples.

[0062] (Phosphoric acid)

[0063] From the perspective of reducing etching unevenness, the amount of phosphoric acid incorporated into the etching solution composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Furthermore, from the perspective of reducing etching unevenness, the amount of phosphoric acid incorporated into the etching solution composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. More specifically, the amount of phosphoric acid incorporated into the etching solution composition of the present invention 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.

[0064] (nitric acid)

[0065] From the perspective of increasing the etching rate, the amount of nitric acid incorporated into the etching solution composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 4% by mass or more. Furthermore, from the perspective of reducing etching unevenness, it is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 6% by mass or less. More specifically, the amount of nitric acid incorporated into the etching solution composition of the present invention 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, even more preferably 2% by mass or more and 7% by mass or less, even more preferably 3% by mass or more and 6% by mass or less, and particularly preferably 4% by mass or more and 6% by mass or less.

[0066] (Organic acid)

[0067] Examples of the organic acid contained in the etching solution composition of the present invention include at least one selected from 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, glycolic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid, and glutamic acid. From the perspective of achieving both suppression of dripping during container filling and improvement of filtration speed, the organic acid is preferably a monobasic organic acid having 1 to 10 carbon atoms, more preferably a monocarboxylic acid having 1 to 10 carbon atoms, and even more preferably acetic acid. The organic acid may be used alone or in combination of two or more.

[0068] From the perspective of reducing uneven etching, the amount of the organic acid in the etching solution composition of the present invention is preferably 11% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. From the perspective of increasing the filtration rate, it is preferably 59% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. More specifically, the amount of the organic acid in the etching solution composition of the present invention 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, and even 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 amount of the organic acid is the total amount of these acids.

[0069] From the perspective of reducing uneven etching, the total amount of phosphoric acid, nitric acid, and the organic acid in the etching solution composition of the present invention is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. From the same perspective, it is preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. The total amount of phosphoric acid, nitric acid, and the organic acid in the etching solution composition of the present invention 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, and even more preferably 80% by mass or more and 98% by mass or less.

[0070] In one or more embodiments, the acid contained in the etching solution composition of the present invention is an acid comprising phosphoric acid, nitric acid, and an organic acid. From the perspective of achieving both suppression of dripping during filling into a container and improvement in filtration rate, an acid comprising phosphoric acid, nitric acid, and acetic acid is preferred, and a mixed acid comprising phosphoric acid, nitric acid, and acetic acid is more preferred.

[0071] When the acid contained in the etching solution composition of the present invention is a mixed acid containing phosphoric acid, nitric acid, and acetic acid, from the perspective of reducing etching unevenness, the 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, and even more preferably 30% by mass or more and 90% by mass or less. From the same perspective, the 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, and even more preferably 1.5% by mass or more and 10% by mass or less. From the same perspective, the 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, and even 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 appropriately set, for example, it can be set to 57 / 6 / 37. In the present invention, in one or more embodiments, the amount of each component in the mixed acid can be regarded as the content of each component in the mixed acid.

[0072] (Etching Inhibitor)

[0073] The etching inhibitor contained in the etching solution composition of the present invention may be used alone or in combination of two or more.

[0074] In one or more embodiments of the present invention, the etching inhibitor may include at least one nitrogen-containing compound selected from polyalkyleneimines and polyalkylenepolyamines. Examples of the polyalkyleneimines include polyethyleneimine (PEI). Examples of the polyalkylenepolyamines include pentaethylenehexamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0075] When the etching inhibitor is a polyalkyleneimine, from the viewpoint of reducing uneven etching and improving storage stability and filtration speed, the number average molecular weight of the etching inhibitor is preferably 300 or more, more preferably 600 or more, and even more preferably 1200 or more. Furthermore, from the viewpoint of viscosity, the number average molecular weight is preferably 100,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. 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, and even more preferably 1,200 or more and 3,000 or less.

[0076] When the etching inhibitor is a polyalkylene polyamine, from the viewpoint of reducing uneven etching and improving storage stability and filtration speed, the number average molecular weight or molecular weight of the etching inhibitor is preferably 50 or more, more preferably 80 or more, and even more preferably 100 or more. From the same viewpoint, it is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less. More specifically, the number average molecular weight or molecular weight of the etching inhibitor is preferably 50 or more and 1000 or less, more preferably 80 or more and 500 or less, and even more preferably 100 or more and 300 or less.

[0077] In the present invention, the average molecular weight can be measured by gel permeation chromatography (GPC).

[0078] An example of a method for measuring the average molecular weight of the etching inhibitor of the present invention is shown below.

[0079] <GPC conditions (polyalkylene imine)>

[0080] Test solution: adjusted to a concentration of 0.1 wt%

[0081] Device / Detector: HLC-8320GPC (integrated GPC) manufactured by Tosoh Corporation

[0082] Column: α-M + α-M (manufactured by Tosoh Corporation)

[0083] Eluent: 0.15 mol / L Na2SO4, 1% CH3COOH / water

[0084] Column temperature: 40°C

[0085] Flow rate: 1.0 mL / min

[0086] Test solution injection volume: 100 μL

[0087] Standard polymer: Pullulan with known molecular weight (P-5, P-50, P-200, P-800 from Shodex)

[0088] From the perspective of reducing uneven etching, the amount of the etching inhibitor in the etching solution composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. From the same perspective, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. More specifically, the amount of the etching inhibitor in the etching solution composition of the present invention 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, and even more preferably 0.5% by mass or more and 3% by mass or less. When two or more etching inhibitors are used in combination, the amount of the etching inhibitors used is the total amount of these.

[0089] (water)

[0090] In one or more embodiments, the etching solution composition of the present invention contains water. Examples of the water contained in the etching solution of the present invention include distilled water, ion-exchanged water, pure water, and ultrapure water.

[0091] From the perspective of reducing uneven etching, the amount of water in the etching solution composition of the present invention is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. From the same perspective, it is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. More specifically, the amount of water in the etching solution composition of the present invention 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, and even more preferably 7% by mass or more and 20% by mass or less.

[0092] (Other ingredients)

[0093] The etching solution composition of the present invention may further contain other ingredients, as long as the effects of the present invention are not impaired. Examples of such other ingredients include inorganic acids other than phosphoric acid and nitric acid, chelating agents, surfactants, solubilizers, preservatives, rust inhibitors, bactericides, antimicrobial agents, and antioxidants.

[0094] From the perspective of reducing uneven etching, the etching solution composition of the present invention preferably does not contain azole compounds. In one or more embodiments, "does not contain azole compounds" includes: no azole compounds; substantially no azole compounds; or no azole compounds in an amount that would affect the etching results. The specific amount of azole compounds in the etching solution composition of the present invention is not particularly limited, but is preferably less than 0.01% by mass, more preferably 0.001% by mass or less, and even more preferably 0% by mass (i.e., no azole compounds).

[0095] From the perspective of reducing uneven etching, the etching solution composition of the present invention preferably does not contain chlorine-containing compounds. Here, in one or more embodiments, "does not contain chlorine-containing compounds" includes: no chlorine-containing compounds; substantially no chlorine-containing compounds; or no chlorine-containing compounds in an amount that would affect the etching results. The specific amount of chlorine-containing compounds in the etching solution composition of the present invention is not particularly limited, but is preferably less than 0.1% by mass, more preferably 0.001% by mass or less, and even more preferably 0% by mass (i.e., no chlorine-containing compounds).

[0096] From the perspective of reducing uneven etching, the etching solution composition of the present invention preferably does not contain or is not mixed with a phosphate compound. Here, in one or more embodiments, "does not contain or is not mixed with a phosphate compound" includes: not containing or not mixing a phosphate compound; substantially not containing or not mixing a phosphate compound; or not containing or not mixing a phosphate compound in an amount that would affect the etching results. The specific amount of phosphate compound in the etching solution composition of the present invention is not particularly limited, but is preferably less than 0.1% by mass, more preferably 0.001% by mass or less, and even more preferably 0% by mass (i.e., not containing or not mixing).

[0097] From the perspective of reducing uneven etching, the etching solution composition of the present invention preferably does not contain hydrogen peroxide. Here, in one or more embodiments, "does not contain hydrogen peroxide" includes: no hydrogen peroxide; substantially no hydrogen peroxide; or no hydrogen peroxide in an amount that would affect the etching results. The specific amount of hydrogen peroxide in the etching solution composition of the present invention is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, particularly preferably 0.001% by mass or less, and even more preferably 0% by mass (i.e., no hydrogen peroxide).

[0098] From the perspective of reducing uneven etching, the etching solution composition of the present invention preferably does not contain fluorine compounds. Here, in one or more embodiments, "does not contain fluorine compounds" includes: no fluorine compounds; substantially no fluorine compounds; or no fluorine compounds in an amount that would affect the etching results. The specific amount of fluorine compounds in the etching solution composition of the present invention is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, particularly preferably 0.001% by mass or less, and even more preferably 0% by mass (i.e., no fluorine compounds).

[0099] In one or more embodiments, the etching solution composition of the present invention can be obtained by combining phosphoric acid, nitric acid, an organic acid, an etching inhibitor, water, and, if desired, the aforementioned optional components using known methods. Therefore, in one or more embodiments, the etching solution production method of the present invention can include a step of combining at least phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water.

[0100] In one or more embodiments of the present invention, "combining at least phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water" includes simultaneously or sequentially mixing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, water, and, if necessary, the aforementioned optional components. The order of mixing is not particularly limited. This mixing can be performed using, for example, a propeller stirrer, liquid circulation stirring using a pump, a homogenizer, a homogenizer, an ultrasonic disperser, or a wet ball mill.

[0101] In the method for producing an etching solution of the present invention, the preferred blending amount of each component may be the same as the preferred blending amount of each component in the etching solution composition of the present invention described above.

[0102] In one or more embodiments of the present invention, the "amount of each component in the etching solution composition" refers to the amount of each component in the etching solution composition used in the etching step, that is, at the time of starting the etching process (at the time of use).

[0103] In one or more embodiments, the amount of each component in the etching solution composition of the present invention can be regarded as the content of each component in the etching solution composition of the present invention. However, under the influence of neutralization, the amount of each component may be different from the content.

[0104] In one or more embodiments, the etching solution composition of the present invention can be obtained by combining a mixed acid composition comprising phosphoric acid, nitric acid, and an organic acid, and an etching inhibitor. Therefore, in one or more embodiments, the etching solution manufacturing method of the present invention may include a step of combining a mixed acid composition comprising phosphoric acid, nitric acid, and an organic acid, and an etching inhibitor to obtain the etching solution composition. The mixed acid composition may also contain water and, as required, the other components described above. The mixing of the mixed acid composition and the etching inhibitor can be performed using the mixer described above.

[0105] From the viewpoint of reducing etching unevenness, the content of phosphoric acid in the mixed acid composition is preferably 10% by mass to 95% by mass, more preferably 20% by mass to 93% by mass, and even more preferably 30% by mass to 90% by mass.

[0106] From the same viewpoint, the amount of nitric acid in the mixed acid composition is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1.5% by mass to 10% by mass.

[0107] From the same viewpoint, the content 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 even more preferably 15% by mass or more and 60% by mass or less.

[0108] The mass ratio of phosphoric acid, nitric acid and organic acid (phosphoric acid / nitric acid / 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 even more preferably 30-80 / 1.5-10 / 15-60.

[0109] From the viewpoint of etching properties, the amount of water in the mixed acid composition is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and even more preferably 5% by mass to 20% by mass.

[0110] In one or more embodiments, the mixed acid composition is used in the manufacture of the etching solution composition of the present invention. Therefore, in one embodiment, the present invention relates to a mixed acid composition for use in the method for manufacturing the etching solution composition of the present invention, wherein the mixed acid composition comprises phosphoric acid, nitric acid, and an organic acid. Furthermore, in one embodiment, the present invention relates to the use of a mixed acid composition comprising phosphoric acid, nitric acid, and an organic acid in the method for manufacturing the etching solution of the present invention.

[0111] The etching liquid composition of the present invention can be supplied to the market in a premixed state, known as a one-part type, or a two-part type, where all components are mixed upon use. Examples of two-part etching liquid compositions include those in which water is separated into a first liquid and a second liquid, and phosphoric acid, nitric acid, an organic acid, and an etching inhibitor are contained in either or both of the first and second liquids, with the first and second liquids being mixed upon use. Each of the first and second liquids may also contain the aforementioned optional components as needed.

[0112] From the perspective of reducing uneven etching, the pH of the etching solution composition of the present invention is preferably 1 or less, more preferably 0 or less, even more preferably less than 0, and even more preferably around -1. The pH of the etching solution composition of the present invention can be preferably set to -5 or higher, and more preferably -3 or higher. In the present invention, the pH of the etching solution composition is the value at 25°C and can be measured using a pH meter. Specifically, it can be measured by the method described in the Examples.

[0113] From the perspective of dripping suppression, the viscosity of the etching solution composition of the present invention at 25°C is preferably 11 mPa·s or greater, more preferably 13 mPa·s or greater, and even more preferably 20 mPa·s or greater. Furthermore, from the perspective of improving filtration speed, it is preferably less than 40 mPa·s, more preferably 39 mPa·s or less, and even more preferably 38 mPa·s or less. More specifically, the viscosity of the etching solution composition of the present invention at 25°C is preferably 11 mPa·s or greater and less than 40 mPa·s, more preferably 13 mPa·s or greater and 39 mPa·s or less, and even more preferably 20 mPa·s or greater and 38 mPa·s or less. In the present invention, the viscosity of the etching solution composition can be measured using a general-purpose viscometer such as a B-type viscometer or an Ubbelohde viscometer. Specifically, it can be measured by the method described in the Examples. The viscosity of the etching solution composition at 25°C can be adjusted using, for example, water or an organic solvent.

[0114] The etching solution composition of the present invention can be stored and supplied in a concentrated state, as long as its storage stability is not compromised. This is preferred because it reduces production and transportation costs. Furthermore, the concentrated solution can be diluted with water or an aqueous acid solution as needed before use in the etching process. The dilution ratio can be, for example, 3 to 100 times.

[0115] [Etched film]

[0116] The film to be etched by the etching liquid composition of the present invention is a metal film formed on a substrate (hereinafter also referred to as "metal film to be etched").

[0117] In one or more embodiments, the substrate is 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 an FED (Field Emission Display), a substrate for an optical disc, a substrate for a magnetic disk, a substrate for a magneto-optical disc, a substrate for a photomask, a ceramic substrate, and a substrate for a solar cell.

[0118] In one or more embodiments, the etched metal film is a metal film containing at least one metal. The etched metal film is not particularly limited as long as it can exhibit the effects of the present invention. Examples include metal films containing at least one metal selected from tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, rhodium, copper, nickel, cobalt, titanium, titanium nitride, aluminum oxide, aluminum, and iridium. In one or more embodiments, the etched metal film does not contain copper or aluminum.

[0119] In one or more embodiments, the etching solution composition of the present invention is preferably used for etching a metal film (excluding copper and aluminum) comprising at least one metal selected from tungsten, tantalum, zirconium, molybdenum, niobium, and nickel. In one or more embodiments, the etching solution composition of the present invention is suitable for etching tungsten films, molybdenum films, or nickel films. Specifically, in one or more embodiments, the film to be etched may include a tungsten film, a molybdenum film, or a nickel film.

[0120] [Set]

[0121] In one embodiment, the present invention relates to a kit for producing the etching solution composition of the present invention (hereinafter also referred to as "the kit of the present invention").

[0122] As a kit of the present invention, in one or more embodiments, a kit (two-liquid etching solution) can be exemplified, wherein the kit comprises a first liquid and a second liquid in an unmixed state, wherein phosphoric acid, nitric acid, an organic acid, and an etching inhibitor are contained in either or both of the first and second liquids, and the first and second liquids are mixed during use. After the first and second liquids are mixed, they can be diluted with water or an aqueous acid solution as needed. The first or second liquid can also contain all or a portion of the water used to prepare the etching solution. Each of the first and second liquids can also contain the aforementioned optional components as needed.

[0123] In one or more embodiments, the kit of the present invention may include a kit (two-liquid etching solution) comprising a mixed acid composition (liquid 1a) comprising phosphoric acid, nitric acid, and an organic acid and a solution (liquid 2a) comprising an etching inhibitor in an unmixed state, and these are mixed when used. Liquid 1a and liquid 2a may be mixed and then diluted with water or an acid aqueous solution as needed. Liquid 1a or liquid 2a may contain all or part of the water used to prepare the etching solution. The acid contained in liquid 1a may be all or part of the acid used to prepare the etching solution. Liquid 2a may also contain an acid. Liquid 1a and liquid 2a may each contain the above-mentioned optional components as needed.

[0124] According to the kit of the present invention, it is possible to obtain an etching solution that can achieve both suppression of dripping during filling of a container and improvement of the filtration speed.

[0125] In one or more embodiments, the etching solution composition of the present invention can be used to etch metals in the manufacturing process of electronic devices, especially semiconductor wafers.

[0126] In one or more embodiments, the etching solution composition of the present invention can be suitably used for the production of at least one substrate selected from the group consisting of semiconductor wafers, substrates for liquid crystal displays, substrates for plasma displays, substrates for FEDs (field emission displays), substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

[0127] In one or more embodiments, the etching solution composition of the present invention can be used to etch electrodes in the manufacturing process of electronic devices, especially semiconductor memories such as non-volatile memories including NAND flash memories.

[0128] In one or more embodiments, the etching solution composition of the present invention can be suitably used to produce patterns having three-dimensional structures, thereby enabling the production of advanced devices such as high-capacity memories.

[0129] The etching liquid composition of the present invention can be used in the etching method disclosed in, for example, JP-A-2020-145412.

[0130] [Etching liquid composition contained in container]

[0131] In one embodiment, the present invention is based on the finding that by ensuring that an etching solution composition filled in a container contains phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, and having a viscosity at 25° C. within a predetermined range and a contact angle (advancing contact angle, advancing contact angle / receding contact angle) with respect to the material of the container within a predetermined range, dripping of the etching solution when the container is removed can be suppressed.

[0132] That is, in one embodiment, the present invention relates to a container-containing etching solution composition (hereinafter also referred to as “the container-containing etching solution composition of the present invention”), which is an etching solution composition filled in a container, the etching solution composition being an etching solution composition for etching a metal film formed on a substrate, the etching solution composition containing phosphoric acid, nitric acid, an organic acid, an etching inhibitor, and water, and having a viscosity at 25°C of 11 mPa·s or more and less than 40 mPa·s, the etching solution composition having 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.

[0133] According to the present invention, in one or more embodiments, dripping of the etching liquid in the container can be suppressed when the etching liquid is taken out.

[0134] In the container-containing etching liquid composition of the present invention, as the etching liquid composition filled in the container, in one or more embodiments, the etching liquid composition of the present invention described above can be mentioned.

[0135] In the etching liquid composition contained in a container of the present invention, examples of the container include the above-mentioned container filled with the etching liquid composition of the present invention.

[0136] In one or more embodiments, the etching solution composition contained in the container of the present invention can be obtained using the etching solution manufacturing method of the present invention. For example, the etching solution composition contained in the container of the present invention can be obtained by using Figure 1 The filling system shown is obtained by filling the etching liquid composition of the present invention into a container 6 . Figure 1 Details of the filling system shown are as described above.

[0137] (Contact angle of the etching solution to the container material)

[0138] From the viewpoint of suppressing dripping, in the etching liquid composition contained in the container of the present invention, the etching liquid composition filled in the container has a receding contact angle 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 / recoiling contact angle) of 1.4 or less. The preferred values ​​of the advancing contact angle, receding contact angle, and ratio (advancing contact angle / recoiling contact angle) with respect to the material of the container can be set to the same as the preferred values ​​of the advancing contact angle, receding contact angle, and ratio (advancing contact angle / recoiling contact angle) with respect to the material of the filling port of the filling nozzle described above.

[0139] In the present invention, the contact angle of the etching solution composition with respect to the material of the container can be measured by the same method as the above-mentioned method for measuring the contact angle of the etching solution composition with respect to the material of the filling port of the filling nozzle.

[0140] Example

[0141] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples at all.

[0142] 1. Preparation of Etching Solution (Examples 1 to 12, Comparative Examples 1 to 6)

[0143] Phosphoric acid, nitric acid, the organic acids listed in Tables 1-2, the etching inhibitors listed in Tables 1-2, and water were blended to obtain etching solutions (pH: -2 to 0) for Examples 1-12 and Comparative Examples 1-6. The amounts of each component (mass %, active ingredient) in the prepared etching solutions are shown in Tables 1-2. The water content in Tables 1-2 also includes the amount of water contained in acid aqueous solutions, etc.

[0144] The following components were used to prepare the etching solution.

[0145] Phosphoric acid [manufactured by RIN KAGAKU KOGYO Co., Ltd., concentration 85%]

[0146] Nitric acid [Fujifilm Wako Pure Chemical Industries, Ltd., concentration 70%]

[0147] (Organic acid)

[0148] Acetic acid [Fujifilm Wako Pure Chemical Industries, Ltd., 100% concentration]

[0149] (Etching Inhibitor)

[0150] Polyethyleneimine [number average molecular weight 1800, "EPOMIN SP-018" manufactured by Nippon Shokubai Co., Ltd.]

[0151] Diethylenetriamine [Molecular weight 103, "DETA" from Tosoh Corporation]

[0152] (water)

[0153] Water [Ultrapure water produced using a continuous pure water production system (Pureconti PC-2000VRL) and a subsystem (Makuace KC-05H) manufactured by Kurita Industry Co., Ltd.]

[0154] 2. Parameter determination method

[0155] [pH of etching solution]

[0156] The pH of the etching solution at 25° C. is a value measured using a pH meter (manufactured by DKK Toa Co., Ltd.), and is a value obtained by immersing the electrode of the pH meter in the etching solution for 1 minute.

[0157] [Viscosity of etching solution]

[0158] The viscosity of the etching solution was measured using the following viscometer under the following conditions.

[0159] Device name: TVB-10 viscometer (with constant temperature bath) manufactured by Toki Sangyo Co., Ltd.

[0160] Rotor: Spindle (shaft) No. M1, Cord (wire) No. 20

[0161] Speed: Measure the viscosity value after 60 seconds at 100 rpm

[0162] Measurement temperature: 25°C

[0163] [Advancing contact angle, receding contact angle, and advancing contact angle / receding contact angle of the etching liquid composition with respect to the material filling the filling port of the nozzle]

[0164] The advancing contact angle and receding contact angle of the etching solution composition with respect to the material filling the filling port of the nozzle were measured using the following measuring apparatus under the following conditions.

[0165] Device name: K-100 manufactured by KRUSS

[0166] Sample plate size: 20 (mm) × 50 (mm) × 2 (mm)

[0167] Sample plate materials: Materials listed in Tables 1 and 2 [PTFE (polytetrafluoroethylene), PFA (perfluoroalkane), PP (polypropylene), PE (polyethylene), polyvinyl chloride]

[0168] Immersing liquid: Etching liquid composition

[0169] <Measurement conditions>

[0170] Temperature: 25℃

[0171] Measuring speed: 1 mm / min

[0172] Maximum immersion depth: 5 mm

[0173] Minimum immersion depth: 1 mm

[0174] Number of measurements: 3 times

[0175] Data acquisition step: 0.2 mm

[0176] <Analysis Method>

[0177] Calculated based on the slope of the plot of immersion depth-force for the third measurement result

[0178] How to use

[0179] The contact angle at the front end of the sample plate (advancing contact angle) was measured while the sample plate was slowly immersed in the etching solution composition. Furthermore, the contact angle at the very end of the sample plate (receding contact angle) was measured while the sample plate was slowly lifted out of the etching solution composition. The ratio of the advancing contact angle to the receding contact angle (advancing contact angle / receding contact angle) was then calculated. The results are shown in Tables 1 and 2.

[0180] 3. Evaluation of etching solution

[0181] use Figure 1 The prepared etching liquid compositions were filled into containers using the filling system shown below under the following conditions to obtain container-filled etching liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 6. The following evaluations were then performed, and the results are shown in Tables 1 and 2.

[0182] Here, Figure 1The filling system shown includes: a tank 1 that stores the etching liquid composition; a pump 2 that transports the etching liquid composition; a filter 3 that filters the etching liquid composition; an outlet valve 4 that controls the flow rate of the etching liquid composition discharged from the outlet (filling nozzle) 5; and a pipe P1 that connects the tank 1, pump 2, filter 3, outlet valve 4 and outlet (filling nozzle 5); and a circulation path P2 that branches from the pipe P1 between the filter 3 and the outlet valve 4 and is connected to the upstream side of the pump 2. In addition, Figure 1 The shown filling system further includes a circulation valve 7 that controls the flow rate of the etching liquid composition circulating in the circulation path P2.

[0183] First, the prepared etching liquid composition is placed in a tank 1. The etching liquid composition in the tank 1 is then fed by a pump 2 and filtered through a filter 3. The filtered etching liquid composition is discharged from a filling port of an outlet (filling nozzle) 5 and filled into a container 6 through its opening.

[0184] <Filling system>

[0185] Pump 2: Diaphragm pump DP-10BPT (manufactured by Yamada Corporation)

[0186] Pipes P1, P2: Corrugated hose 15A (manufactured by Flon Chemical)

[0187] Filter 3: Membrane filter

[0188] Outlet 5 (filling nozzle): outer diameter 14 mm, filling port material of the filling nozzle: PTFE

[0189] Container 6: 20 L resin container

[0190] <Conditions>

[0191] Filtration temperature: 25℃

[0192] Filtration pressure: 0.3 MPa

[0193] Filtration flow rate: 0.1~20 kg / (m 2 ·minute)

[0194] Scale: Etching liquid composition 300 kg

[0195] Filling flow rate: 0.1~20 kg / (m 2 ·minute)

[0196] Circulation flow rate: 0.1~20 kg / (m 2 ·minute)

[0197] [Number of drops when filling]

[0198] use Figure 1 In the filling system shown, after filling a container 6 with a predetermined amount of etching liquid composition under the above conditions, the outlet 5 (filling nozzle) was lifted from the opening of the container 6 to fill the next empty filling container. The frequency of dripping around the opening and on the wall of the container 6 during this lifting was evaluated. The frequency (number of dripping) after performing this operation 10 times is shown in Tables 1 and 2. The lower the number of dripping, the more effectively dripping is suppressed.

[0199] [Evaluation of liquid permeability]

[0200] The prepared, unfiltered etching solution composition was passed through a specified filter (Advantech, hydrophilic PTFE 0.20 μm (pore size) filter, model: 25HP020AN) at a liquid temperature of 25°C and a constant air pressure of 0.30 MPa. The flow rate (g / min) through the filter during the initial one minute was determined and shown in Table 1. The flow rate through the 0.20 μm filter under these conditions can be used as an indicator of the filtration rate of the etching solution composition when it is filled into a container. In other words, the higher the flow rate, the more likely the etching solution composition is to be filtered at a high rate.

[0201] [Productivity Evaluation]

[0202] The productivity of the etching solution composition can be evaluated by comprehensively considering the filtration rate, i.e., the permeability, and the dripping frequency during filling. For example, a composition with good permeability and extremely low dripping frequency during filling can be evaluated as having very high productivity (A) due to minimal wiping work around the container opening and walls. On the other hand, a composition with good permeability and extremely high dripping frequency during filling can be evaluated as having very poor productivity (D) due to the increased wiping work around the container opening and walls. The evaluation criteria were set on a four-level scale as described below, and the results are shown in Table 1.

[0203] <Evaluation Criteria>

[0204] A: The filtration fluid permeability is good and there is almost no wiping work, so the productivity is very high.

[0205] B: Good filtration and liquid permeability, less wiping work, so high productivity

[0206] C: There is almost no wiping work. The filtration fluid permeability is poor, so the productivity is poor.

[0207] D: The filtration permeability is good, but the wiping work is more and the number of interruptions increases, so the productivity is very low

[0208] [Table 1]

[0209]

[0210] [Table 2]

[0211]

[0212] As shown in Table 1, Examples 1 to 9 satisfying the conditions of a receding contact angle of the etching liquid with respect to the material at the filling port of the filling nozzle being 60° or greater and (advancing contact angle / receding contact angle) being 1.4 or less, have a small number of dripping times during filling into the container, and dripping is suppressed.

[0213] Furthermore, it can be seen that the etching solutions of Examples 1 to 7, which contain phosphoric acid, nitric acid, an organic acid, and an etching inhibitor and have a viscosity of 11 mPa·s or more and less than 40 mPa·s at 25°C, can achieve both suppression of dripping during filling into a container and improvement in filtration speed, as compared to Examples 8 to 9, which contain phosphoric acid, nitric acid, an organic acid, and an etching inhibitor and have a viscosity of less than 11 mPa·s at 25°C, and Comparative Example 1, which contains phosphoric acid, nitric acid, an organic acid, and an etching inhibitor and has a viscosity of less than 11 mPa·s at 25°C, thereby improving productivity.

[0214] As shown in Table 2, it can be seen that compared with Comparative Examples 2 to 6, which do not satisfy the conditions that the receding contact angle of the etching liquid with respect to the material of the filling port of the filling nozzle is 60° or greater and the (advancing contact angle / receding contact angle) is 1.4 or less, Examples 1, 10 to 11, 7, and 12, which satisfy the conditions that the receding contact angle of the etching liquid with respect to the material of the filling port of the filling nozzle is 60° or greater and the (advancing contact angle / receding contact angle) is 1.4 or less, the number of drippings during filling into the container is reduced, and dripping can be suppressed.

[0215] Industrial applicability

[0216] The etching liquid composition of the present invention is useful for etching metal films on substrates such as semiconductor wafers, substrates for liquid crystal displays, substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

[0217] Description of Reference Numerals

[0218] 1: Tank; 2: Pump; 3: Filter; 4: Outlet valve; 5: Outlet (filling nozzle); 6: Container; 7: Circulation valve; P1: Piping; P2: Circulation path.

Claims

1. A method for producing an etching solution composition, wherein: The etching liquid composition is an etching liquid composition for etching a metal film formed on a substrate. The method for producing the etching liquid composition comprises the step of filling the etching liquid composition into a container using a filling nozzle having a filling port for discharging the etching liquid composition. The etching liquid has a receding contact angle of 60° or more with respect to the material of the filling port of the filling nozzle, and a ratio of an advancing contact angle to a receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

2. The method for producing an etching solution composition according to claim 1, wherein: The viscosity of the etching solution composition at 25° C. is greater than or equal to 11 mPa·s and less than 40 mPa·s.

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

4. The method for producing an etching solution composition according to claim 3, wherein: The organic acid comprises acetic acid.

5. The method for producing an etching solution composition according to claim 3 or 4, wherein: The blending amount of the organic acid is 11 mass % or more and 59 mass % or less. 6 . The method for producing an etching solution composition according to claim 3 , comprising the step of preparing the etching solution composition by mixing a mixed acid composition and an etching inhibitor, wherein the mixed acid composition comprises phosphoric acid, nitric acid and an organic acid.

7. The method for producing an etching solution composition according to any one of claims 3 to 6, wherein: The etching inhibitor is at least one nitrogen-containing compound selected from polyalkylene imine and polyalkylene polyamine.

8. The method for producing an etching solution composition according to any one of claims 1 to 7, wherein: The etching solution composition does not contain azole compounds.

9. The method for producing an etching solution composition according to any one of claims 1 to 8, wherein: The etching solution composition does not contain hydrogen peroxide.

10. The method for producing an etching solution composition according to any one of claims 1 to 9, wherein: The etching solution composition does not contain fluorine compounds.

11. The method for producing an etching solution composition according to any one of claims 1 to 10, wherein: The pH of the etching solution composition is 1 or less.

12. The method for producing an etching solution composition according to any one of claims 1 to 11, wherein: The metal film is a metal film including at least one metal selected from tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, rhodium, copper, nickel, cobalt, titanium, titanium nitride, aluminum oxide, aluminum and iridium.

13. The method for producing an etching solution composition according to any one of claims 1 to 12, wherein: The substrate is at least one substrate selected from semiconductor wafers, substrates for liquid crystal display devices, substrates for plasma displays, substrates for FEDs, i.e., substrates for field emission displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

14. A mixed acid composition, which is used in the method for producing the etching solution composition according to any one of claims 6 to 13, The mixed acid composition comprises phosphoric acid, nitric acid and an organic acid.

15. An etching liquid composition contained in a container, which is an etching liquid composition filled in a container, The etching liquid composition is an etching liquid 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, and has a viscosity of 11 mPa·s or more and less than 40 mPa·s at 25° C., The etching solution composition has a receding contact angle of 60° or more with respect to the material of the container, and a ratio of an advancing contact angle to a receding contact angle (advancing contact angle / receding contact angle) of 1.4 or less.

16. Use of a mixed acid composition comprising phosphoric acid, nitric acid and an organic acid in the method for producing an etching solution composition according to any one of claims 6 to 13.

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