Adjusted water manufacturing device and adjusted water manufacturing method

Abstract

Provided is an apparatus for producing adjusted water in which the concentration of a dopant element is adjusted, the adjusted water being used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, and in which dissolution of the metal component into the adjusted water is suppressed during the application. [Solution] An apparatus for producing adjusted water, comprising: a dopant element concentration adjustment device that adds a concentration adjustment agent containing a dopant component to the water to be treated by controlling the amount added; a pH adjustment device that adjusts the pH of the water to be treated to which the concentration adjustment agent may be added; and an oxidation-reduction potential adjustment device that adjusts the oxidation-reduction potential of the water to be treated to which the concentration adjustment agent may be added.

Description

[Technical Field]

[0001] The present disclosure relates to an apparatus for producing conditioned water and a method for producing conditioned water. [Background technology]

[0002] Substrates used in semiconductor devices such as transistors, diodes, and solar cells are manufactured by diffusing a dopant element such as phosphorus or boron into a semiconductor substrate. A dry processing method such as ion implantation is used as a method for diffusing a dopant element into a semiconductor substrate (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2023-118399 Summary of the Invention [Problem to be solved by the invention]

[0004] It tends to be difficult to apply dry processing methods to semiconductor substrates having complex structures. Therefore, the present inventors have investigated a method of applying an aqueous solution containing a dopant element to the surface of a semiconductor substrate as a wet processing method that is thought to be easily applicable to semiconductor substrates having complex structures. The present inventors have found that in this case, metal components exposed on the surface of the semiconductor substrate may unintentionally dissolve in the aqueous solution.

[0005] The present disclosure aims to provide an apparatus for producing adjusted water having an adjusted concentration of a dopant element, which is used to apply to a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process, and in which dissolution of the metal components into the adjusted water is suppressed during the application. [Means for solving the problem]

[0006] One aspect of the adjusted water manufacturing apparatus of the present disclosure is an apparatus for manufacturing adjusted water in which the concentration of a dopant element is adjusted, and which is used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process.The manufacturing apparatus comprises a dopant element concentration adjusting device that adds a concentration adjuster containing a dopant component to the water to be treated by controlling the amount of the concentration adjuster added, and at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of the water to be treated to which the concentration adjuster may have been added, and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the water to be treated to which the concentration adjuster may have been added. [Effects of the Invention]

[0007] The manufacturing apparatus disclosed herein can produce adjusted water having an adjusted concentration of a dopant element, which is used to apply to a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process, and in which dissolution of the metal components into the adjusted water is suppressed during the application. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a block diagram that schematically illustrates one embodiment of an apparatus for producing conditioned water. [Figure 2] FIG. 2 is a block diagram that schematically illustrates one embodiment of an apparatus for producing conditioned water. [Figure 3] FIG. 3 is a block diagram that schematically illustrates one embodiment of an apparatus for producing conditioned water. [Figure 4] FIG. 4 is a block diagram that schematically illustrates one embodiment of an apparatus for producing conditioned water. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, the numerical range N1 to N2 means N1 or more and N2 or less. In this specification, when the units of the numerical values ​​written before and after "~" indicating a numerical range are the same, the unit of the numerical value written before "~" may be omitted.

[0010] The manufacturing apparatus of the present disclosure produces the target adjusted water by treating raw water such as ultrapure water with a concentration adjuster, etc., as described below. In this specification, raw water such as ultrapure water and an aqueous solution obtained by adding a concentration adjuster, etc., to raw water are also collectively referred to as "water to be treated."

[0011] [Adjusted water manufacturing equipment] The manufacturing apparatus disclosed herein is an apparatus for producing adjusted water having an adjusted concentration of dopant elements, which is used to apply to a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process.

[0012] The manufacturing apparatus of the present disclosure includes: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to the water to be treated by controlling the amount of the agent added; at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of the treatment target water to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the treatment target water to which the concentration adjusting agent may be added; Equipped with.

[0013] The manufacturing apparatus of the present disclosure may further include a water quality monitoring device that measures the concentration of the dopant element in the treatment target water or adjusted water to which the concentration adjuster has been added.

[0014] The manufacturing apparatus of the present disclosure may be equipped with an impurity component removal device that selectively removes at least a portion of unintended impurity components, which are different from the desired dopant components, from the water to be treated or the concentration adjuster to which the above-mentioned concentration adjuster may be added.

[0015] The manufacturing apparatus of the present disclosure can produce adjusted water from water such as ultrapure water, which contains the desired dopant element or dopant component (e.g., a metal element or ion) in a wide concentration range, and in one embodiment, has undesired impurity components (e.g., a metal element or ion) removed or their concentrations reduced.

[0016] The dopant component is, for example, a component containing a dopant element to be doped into a semiconductor substrate having a metal component exposed on its surface during a semiconductor or semiconductor device manufacturing process. By using such adjusted water, the semiconductor substrate can be doped by a wet processing method. For example, by applying an appropriate amount of adjusted water obtained by the manufacturing apparatus of the present disclosure to appropriate locations on the semiconductor substrate surface during a doping process in a semiconductor or semiconductor device manufacturing process, the dopant element constituting the dopant component can be doped in an appropriate amount at appropriate locations. Furthermore, either or both of the pH and the oxidation-reduction potential of the adjusted water are adjusted to an appropriate range. Therefore, dissolution of the metal component into the adjusted water during application can be suppressed.

[0017] The metal component preferably contains at least one metal element selected from the group consisting of Groups 3, 4, 5, 8, 9, 10, 11, and 13 of the periodic table. Specific examples of metal elements include copper, cobalt, lanthanum, rhodium, indium, gallium, aluminum, nickel, and ruthenium. The metal component may be one type, two or more types, or an alloy of two or more types. The semiconductor substrate may have a compound containing the metal component on its surface. Examples of compounds containing the metal component include compound semiconductors such as InP and InGaAs.

[0018] Ultrapure water is produced, for example, by removing ionic substances, organic matter, dissolved gases, and particulates from raw water. Examples of raw water include city water, well water, river water, lake water, and industrial water. Ultrapure water preferably has a resistivity of 18.1 MΩ·cm or more, particulates with a particle size of 50 nm or more and 1000 particles / L or less, viable bacteria of 1 particle / L or less, TOC (Total Organic Carbon) of 1 μg / L or less, total silicon of 0.1 μg / L or less, metals of 1 ng / L or less, ions of 10 ng / L or less, hydrogen peroxide of 30 μg / L or less, and a water temperature of 25±2°C, but is not particularly limited thereto.

[0019] The conditioned water produced using the manufacturing apparatus of the present disclosure is transported to a point of use (UP). Examples of the UP include a doping treatment apparatus for applying the conditioned water to a semiconductor substrate having exposed metal components on its surface in a semiconductor or semiconductor device manufacturing process. Examples of semiconductor devices include transistors, diodes, and solar cells.

[0020] <Dopant element concentration adjustment device> The manufacturing apparatus of the present disclosure includes a dopant element concentration adjustment device. The concentration adjustment device is a device for adding a concentration adjuster containing a dopant component to water to be treated, such as ultrapure water, while controlling the amount of the agent added; for example, a device for adding an aqueous solution containing a dopant component to the water to be treated.

[0021] The concentration adjuster contains a dopant component. The dopant component contains a dopant element (hereinafter also simply referred to as "dopant") as a constituent element, and is a component for containing the target dopant element in the concentration adjuster and the adjusted water to be produced. One type of dopant component may be used, or two or more types may be used. The concentration adjuster is, for example, an aqueous solution containing the dopant component.

[0022] The dopant component is not particularly limited as long as it is a component conventionally used for doping semiconductor substrates, and may be, for example, a compound containing an n-type dopant or a compound containing a p-type dopant. The aqueous solution is, for example, an aqueous solution containing at least one compound selected from the group consisting of compounds containing an n-type dopant and compounds containing a p-type dopant.

[0023] Examples of n-type dopants include phosphorus, arsenic, sulfur, tin, and antimony. Examples of p-type dopants include boron, zinc, magnesium, gallium, indium, and aluminum. Examples of the dopant component include phosphorus compounds, arsenic compounds, and boron compounds.

[0024] Examples of phosphorus compounds include phosphoric acid, phosphorous acid, diphosphorous acid, polyphosphoric acid, and diphosphorus pentoxide, as well as phosphite esters such as trimethyl phosphite and triethyl phosphite, phosphate esters such as trimethyl phosphate and triethyl phosphate, tris(trialkylsilyl) phosphites such as tris(trimethylsilyl) phosphite, and tris(trialkylsilyl) phosphates such as tris(trimethylsilyl) phosphate.

[0025] Examples of arsenic compounds include arsenic trioxide-sodium sulfate, arsenic acid, arsenous acid, and trialkyl arsenates such as triethoxyarsenic and tri-n-butoxyarsenic.

[0026] Boron compounds include boric acid, metaboric acid, boronic acid, perboric acid, hypoboric acid, diboron trioxide, trialkyl borates, tetrahydroxydiborane, monoalkoxytrihydroxydiborane, dialkoxydihydroxydiborane, trialkoxymonohydroxydiborane, and tetraalkoxydiborane.

[0027] The concentration of the dopant element in the adjusted water obtained by the manufacturing apparatus of the present disclosure is set appropriately depending on the application of the adjusted water and is not particularly limited. The concentration of the dopant element in the adjusted water is preferably 100,000 mg / L or less, more preferably 0.1 to 50,000 mg / L, even more preferably 0.5 to 20,000 mg / L, and particularly preferably 1 to 13,000 mg / L. The concentration adjusting apparatus, for example, adds a concentration adjuster to the water to be treated so that the concentration of the dopant element in the adjusted water falls within the above range.

[0028] The concentration adjusting device is, for example, a device that measures and supplies a concentration adjusting agent to a transfer line for water to be treated, such as ultrapure water. The concentration adjusting device includes, for example, a tank that stores the concentration adjusting agent and a supply line that supplies the concentration adjusting agent from the tank to the transfer line, and may further include a pump that adjusts the supply rate of the concentration adjusting agent, as desired. As will be described later, in one embodiment, the concentration adjusting device may further include a device for removing impurities. The concentration adjusting device may include, for example, a tank containing a concentration adjusting agent, the remover, and a supply line that supplies the concentration adjusting agent from the tank to the transfer line through the remover. The concentration adjusting device may include two or more tanks according to the type of concentration adjusting agent.

[0029] The tank containing the concentration adjuster may be equipped with at least one selected from the group consisting of a device for purging the inside of the tank with an inert gas (e.g., N2 gas) and a degassing membrane for removing dissolved gas (e.g., dissolved oxygen) in the concentration adjuster in the tank.

[0030] The pump may be, for example, a diaphragm pump. Alternatively, a pressure extrusion pump may be used, in which the concentration adjuster is placed in a tank together with an inert gas (e.g., N2 gas) and the pressure of the inert gas is used to extrude the concentration adjuster.

[0031] <Impurity component removal device> In one embodiment, the manufacturing apparatus of the present disclosure includes an impurity component removal device. The removal device selectively removes at least a portion of impurity components (e.g., at least one selected from the group consisting of metal elements and ions) other than the dopant component from the treatment target water to which the concentration adjuster may be added or from the concentration adjuster. The impurity components here are components that are undesirable to be contained in the adjusted water to be produced. In one embodiment, the removal device allows the dopant components to pass through and selectively removes the impurity components, such as metal elements and ions, such as Al, Ca, Fe, Mg, Na, Ni, and Zn, as well as undesired dopant components.

[0032] The removal device preferably has a removal section according to the type of impurity component to be removed. The removal device preferably has at least one selected from the group consisting of ion exchange resins, ion exchange membranes, nanofiltration membranes, and reverse osmosis membranes. Among these, ion exchange resins are preferred. Examples of ion exchange resins include cation exchange resins and anion exchange resins, and cation exchange resins are preferred from the viewpoint of removing cationic metal ion impurities in the water to be treated or the concentration adjuster.

[0033] Examples of cation exchange resins include strongly acidic cation exchange resins such as sulfonic acid type and weakly acidic cation exchange resins such as carboxylic acid type. Examples of anion exchange resins include strongly basic anion exchange resins such as quaternary amine type and weakly basic anion exchange resins such as primary, secondary, or tertiary amine type.

[0034] The ion exchange resin may be, for example, a mixed resin of a cation exchange resin and an anion exchange resin, which allows, for example, an impurity component removal device to selectively remove undesired dopant components (e.g., boron compounds) depending on the types of the desired dopant components and undesired dopant components (e.g., dopant components other than boron compounds).

[0035] The ion exchange resin may be, for example, a gel-type resin.

[0036] The above removal device may include an ion exchange resin column. The ion exchange resin column may be in one stage or two or more stages.

[0037] The above removal device is, for example, a device that removes impurity components such that the concentration of impurity components in the water to be treated or the concentration adjusting agent is preferably 1 μg / L or less, more preferably 0.1 μg / L or less, still more preferably 0.01 μg / L or less, and particularly preferably 0.001 μg / L or less.

[0038] In one embodiment, the above removal device is located upstream or downstream of the dopant element concentration adjusting device on the transfer line of the water to be treated, and is preferably located downstream. Thereby, the concentration of impurity components (for example, metal elements, ions) in the water to be treated can be reduced.

[0039] In one embodiment, the above removal device is included in the dopant element concentration adjusting device. That is, in one embodiment, the above concentration adjusting device may further include the above removal device. Thereby, for example, impurity components in the concentration adjusting agent containing the dopant component added to the water to be treated can be removed or the concentration thereof can be reduced, and as a result, impurity components in the water to be treated can be removed or the concentration thereof can be reduced.

[0040] <pH Adjusting Device and Redox Potential Adjusting Device> The manufacturing device of the present disclosure further includes at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of water to be treated such as ultrapure water, and a redox potential adjusting device (hereinafter also referred to as "ORP adjusting device") that adjusts the redox potential (hereinafter also referred to as "ORP") of water to be treated such as ultrapure water. The adjusted water whose pH and / or ORP is adjusted in addition to the concentration of the dopant element can suppress the dissolution of the above metal components into the adjusted water during the above coating. The pH adjuster is a device that adjusts the pH of the water to be treated by measuring and supplying a pH adjuster to a transfer line for the water to be treated. The pH adjuster includes, for example, a tank containing the pH adjuster and a supply line for supplying the pH adjuster from the tank to the transfer line, and may optionally further include a pump for adjusting the supply rate of the pH adjuster. The ORP adjuster is preferably located downstream of the pH adjuster and upstream of the degassing device on the transfer line, so that the ORP of the water to be treated may be adjusted by the ORP adjuster.

[0041] The ORP adjuster is a device that adjusts the ORP of the water to be treated by measuring and supplying an oxidation-reduction potential adjuster (hereinafter also referred to as "ORP adjuster") to the transfer line. The ORP adjuster includes, for example, a tank that stores the ORP adjuster and a supply line that supplies the ORP adjuster from the tank to the transfer line, and may further include a pump that adjusts the supply rate of the ORP adjuster, if desired.

[0042] pH-adjusted water, obtained by adding a pH adjuster to ultrapure water, has a higher electrical conductivity than ultrapure water. This reduces the buildup of static electricity in the pipes and the liquid flowing through them, and prevents particles from being mixed into the water being treated.

[0043] The tank may include at least one selected from the group consisting of a device for purging the tank with an inert gas (e.g., N2 gas) and a degassing membrane for removing dissolved gas (e.g., dissolved oxygen) from the pH adjuster or ORP adjuster in the tank.

[0044] The pump may be, for example, a diaphragm pump. Alternatively, a pressure extrusion pump may be used, in which the pH adjuster or ORP adjuster is placed in a tank together with an inert gas (e.g., N2 gas) and the pressure of the inert gas is used to extrude the pH adjuster or ORP adjuster.

[0045] When the pH adjuster or ORP adjuster is a gas, a direct gas-liquid contact device such as a gas permeable membrane module or an ejector may be used as the pH adjuster or ORP adjuster.

[0046] Examples of pH adjusters that can be used to adjust the pH of the water to be treated or the adjusted water to 7 or higher include aqueous solutions of alkaline compounds and gaseous alkaline compounds. The alkaline compound is the active ingredient of the pH adjuster. Examples of alkaline compounds include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. Examples of gaseous alkaline compounds include ammonia gas. One type of alkaline compound may be used, or two or more types may be used.

[0047] Among these, an aqueous ammonia solution or ammonia gas is preferred, and an aqueous ammonia solution is more preferred. By dissolving a small amount of ammonia in ultrapure water, for example, the effect of suppressing dissolution and charging of semiconductor materials can be obtained.

[0048] In one embodiment, the pH adjuster adjusts the pH of the water to be treated to preferably 7 to 11, more preferably 8 to 11. In one embodiment, the pH adjuster adjusts the pH of the water to be treated so that the pH of the adjusted water is preferably 7 to 11, more preferably 8 to 11. A pH of 7 or higher or 8 or higher tends to suppress the generation of static electricity in various devices located downstream of the pH adjuster. A pH of 11 or lower tends to suppress corrosion of semiconductor substrates and deterioration of membranes, etc., included in degassing devices or gas dissolved film devices.

[0049] When adjusting the pH of the water to be treated or the adjusted water to less than 7, examples of pH adjusters include aqueous solutions of acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, and citric acid, as well as gases such as CO2 gas. The acidic compounds and carbon dioxide gas (CO2 gas) are active ingredients of the pH adjuster. One or more types of acidic compounds may be used. The pH is a value measured at 23°C using a known pH meter.

[0050] The pH adjuster is preferably a liquid, more preferably an aqueous solution of an alkaline compound, and even more preferably an aqueous ammonia solution.

[0051] Examples of ORP adjusters for adjusting the oxidation-reduction potential of the water to be treated or the adjusted water to a higher (+ side) include aqueous solutions such as hydrogen peroxide solution, and gases such as ozone gas and oxygen gas. Examples of ORP adjusters for adjusting the oxidation-reduction potential of the water to be treated or the adjusted water to a lower side include aqueous solutions of compounds such as oxalic acid, hydrogen sulfide, and potassium iodide, and gases such as hydrogen gas. One or more of the above compounds may be used. One or more of the above gases may be used.

[0052] The ORP adjusting device preferably adjusts the oxidation-reduction potential (ORP) of the water to be treated to fall within the following range, or adjusts the ORP of the adjusted water to fall within the following range. The ORP is preferably 0 mV or higher, more preferably 50 mV or higher, even more preferably 100 mV or higher, even more preferably 200 mV or higher, particularly preferably 300 mV or higher, and particularly preferably 400 mV or higher. The ORP is preferably 3000 mV or lower, more preferably 2500 mV or lower, even more preferably 2000 mV or lower, even more preferably 1500 mV or lower, and particularly preferably 1000 mV or lower. The ORP is, for example, 0 to 3000 mV. The ORP is a value measured at 23°C using a known ORP meter. An ORP equal to or higher than the lower limit tends to further suppress dissolution of the metal component into the adjusted water during application, and also tends to enhance diffusibility of the dopant element into the semiconductor substrate.

[0053] <Hydrogen peroxide removal device> The manufacturing apparatus of the present disclosure may further include a hydrogen peroxide removal device. For example, it is preferable that at least a portion of the hydrogen peroxide has been removed from the water to be treated to which the ORP adjuster is supplied. Therefore, the hydrogen peroxide remover is preferably located upstream of the ORP adjuster on the transfer line, and more preferably upstream of the pH adjuster and the ORP adjuster. By providing the hydrogen peroxide remover, the ORP adjuster can accurately control the ORP of the adjusted water.

[0054] The hydrogen peroxide removal device includes, for example, a platinum group metal-supported resin column. The platinum group metal-supported resin column includes a resin (hereinafter also referred to as a "carrier resin") and a platinum group metal supported on the resin. In the platinum group metal-supported resin column, the catalytic action of the platinum group metal decomposes and removes hydrogen peroxide from the water to be treated, such as ultrapure water.

[0055] Examples of carrier resins include ion exchange resins. Among ion exchange resins, anion exchange resins are preferred. Platinum group metals are negatively charged, so they are stably supported on anion exchange resins and are less likely to fall off. The exchange groups of the anion exchange resins are preferably in the OH form. The OH-type anion exchange resins have an alkaline resin surface, which promotes the decomposition of hydrogen peroxide.

[0056] Examples of platinum group metals include ruthenium, rhodium, palladium, osmium, iridium, and platinum. Platinum group metals may be used alone, two or more, or as an alloy of two or more, or purified products of naturally occurring mixtures may be used without separating them into individual elements. Among these, platinum, palladium, platinum / palladium alloys, or mixtures of two or more of these, are preferably used because of their strong catalytic activity. Nano-sized particles of these metals can also be preferably used.

[0057] <Pump> The manufacturing apparatus of the present disclosure may further include a pump. Use of the pump makes it easy to increase the flow rate and water pressure. The pump is preferably a pump that can control the amount of pressure applied. Examples of pumps include a rotary positive displacement pump that continuously sucks and discharges by changing the volume, a reciprocating positive displacement pump that repeatedly sucks and discharges by changing the volume, and a centrifugal pump that discharges liquid by centrifugal force or thrust generated by the rotation of an impeller or propeller inside the pump.

[0058] <Degassing device> The manufacturing apparatus of the present disclosure may further include a degassing device that degasses the water to be treated. The degassing device removes at least a portion of the dissolved gases in the water to be treated, reducing the amount of dissolved gases, such as dissolved oxygen and dissolved nitrogen.

[0059] The degassing device is preferably located downstream of the pH adjuster or downstream of the pH adjuster and ORP adjuster on the transfer line. Although this type of manufacturing apparatus is equipped with a degassing device, it can suppress static electricity and prevent fine particles from accumulating on the gas-permeable membrane surface. This prevents fine particles from being mixed into the adjusted water.

[0060] As the degassing device, a membrane degassing device is preferred, and a membrane degassing device equipped with a gas-permeable membrane is more preferred. In one embodiment, the membrane degassing device passes the water to be treated through one side (liquid phase chamber) of the gas-permeable membrane, and reduces the pressure on the other side (gas phase chamber) with a vacuum pump, thereby causing at least a portion of the dissolved gas to permeate through the gas-permeable membrane and migrate to the gas phase chamber for removal. The degassing device, for example, reduces the dissolved oxygen concentration in the water to be treated supplied to the gas-dissolved membrane device to 0.1 mg / L or less.

[0061] By post-degassing the water to be treated without directly degassing the concentration adjuster, pH adjuster, and ORP adjuster, the risk of chemical leakage during vacuum degassing of these chemicals can be reduced.

[0062] The gas-permeable membrane may be any membrane that allows gases such as oxygen, nitrogen, and steam to pass through but does not allow water to pass through. Examples of materials constituting the gas-permeable membrane include polymeric materials such as silicone rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyolefins (e.g., polypropylene), and polyurethane. One or more polymeric materials may be used. Among these, at least one selected from the group consisting of polypropylene and polyvinylidene fluoride is preferred.

[0063] <Gas-dissolved film type device> The manufacturing apparatus of the present disclosure may further include a gas dissolved film type apparatus. The gas-dissolved membrane device is preferably located downstream of the degassing device on the transfer line. The gas-dissolved membrane device is a device that dissolves an inert gas in, for example, degassed water to be treated via a gas-permeable membrane. This stabilizes the properties of the water to be treated.

[0064] Inert gases include, for example, nitrogen gas, argon, and helium.

[0065] In one embodiment, the gas-dissolved membrane type device flows degassed water to be treated on one side (liquid phase chamber) of a gas-permeable membrane and supplies an inert gas to the other side (gas phase chamber), allowing the inert gas to permeate the gas-permeable membrane, migrate to the liquid phase side, and dissolve in the water to be treated.

[0066] Examples of materials constituting the gas-permeable membrane are as described above, and will not be repeated here. Among the above materials, at least one selected from the group consisting of polypropylene and polyvinylidene fluoride is preferred.

[0067] The gas-permeable membrane may be, for example, a hollow fiber membrane. In this case, the gas-dissolved membrane device includes a hollow fiber membrane unit containing a hollow fiber membrane therein. Connected to the interior of the hollow fiber membrane unit are a liquid supply pipe for supplying the degassed water to be treated to the hollow fiber membrane unit, a gas supply pipe for supplying an inert gas to the hollow fiber membrane unit, and a drain pipe for discharging the conditioned water with the inert gas dissolved therein.

[0068] <Water quality monitoring device> The manufacturing apparatus of the present disclosure preferably further includes a water quality monitoring device for measuring the quality (e.g., concentration of a dopant element) of the water to be treated or the conditioned water.

[0069] The water quality monitoring device is preferably located downstream of the dopant element concentration adjustment device on the transfer line for the water to be treated. The water quality monitoring device measures the concentration of the dopant element in the water to be treated or the adjusted water, and monitors whether the concentration of the dopant element is at a desired value.

[0070] The water quality monitoring device is preferably located downstream of the concentration adjusting device on the transfer line for the water to be treated, and upstream or downstream of the device for removing impurity components.

[0071] The water quality monitoring device is preferably located downstream of the gas dissolved film device on the transfer line. The water quality monitoring device may, for example, measure at least one selected from the group consisting of the concentration of the active ingredient of a pH adjuster, the concentration of the active ingredient of an ORP adjuster, pH, and oxidation-reduction potential (ORP) in the water to be treated or the adjusted water, or may measure the concentration of an inert gas and monitor whether the concentration of the active ingredient, pH, ORP, or the concentration of the inert gas is at a desired value. These measurements may be performed by the water quality monitoring device that measures the concentration of the dopant element, or by a water quality monitoring device different from the water quality monitoring device that measures the concentration of the dopant element.

[0072] The concentration of dopant elements in the water to be treated or the adjusted water can be measured using a known pH meter or conductivity meter, or a metal element or ion detection device. The pH, ORP, and inert gas concentration of the water to be treated or the adjusted water can be measured using a known pH meter, a known ORP meter, and a known gas concentration meter, respectively. The concentration of the above-mentioned active ingredients can be measured using a known conductivity meter.

[0073] <Control device> The manufacturing apparatus of the present disclosure preferably further includes a control device in addition to the water quality monitoring device. The control device is, for example, a computer. The water quality monitoring device may be connected, for example, electrically or wirelessly, to the control device. The control device may be connected, for example, electrically or wirelessly, to at least one device selected from the group consisting of the concentration adjusting device, pH adjusting device, and ORP adjusting device, and, if necessary, to the gas dissolved film type device.

[0074] The control device is a device that controls the amount of addition or supply rate of a concentration adjuster containing a dopant component in a dopant element concentration adjustment device based on the water quality (e.g., dopant element concentration, pH, or conductivity) of the water to be treated or the adjusted water measured by a water quality monitoring device.

[0075] The control device can control the adjusted water to have a set concentration of the dopant element. The control of the concentration by such a control device can be performed by feedback control such as PI control or PID control, or by other well-known methods.

[0076] The control device can transmit a signal to a dopant element concentration adjustment device based on the water quality (e.g., dopant element concentration, pH, or conductivity) measured by a water quality monitoring device, and control the amount of addition or supply rate of the concentration adjustment agent in the device using a pump or the like.

[0077] The control device may be, for example, a device that controls at least one selected from the group consisting of the amount or supply rate of a pH adjuster in a pH adjuster device and the amount or supply rate of an ORP adjuster in an ORP adjuster device, based on the water quality of the water to be treated or the adjusted water measured by a water quality monitoring device, and, if necessary, the amount or supply rate of an inert gas in a gas-dissolved film type device.

[0078] The control device can control the adjusted water to have at least one selected from the group consisting of a set concentration of the active ingredient, a set pH value, and a set ORP value, or a set concentration of the inert gas. The control of the active ingredient concentration, at least one selected from the group consisting of pH and ORP, or the inert gas concentration by such a control device can be controlled by a known method, for example, feedback control such as PI control or PID control.

[0079] The control device can transmit a signal to the pH adjustment device based on the water quality (e.g., the concentration of the active ingredient of the pH adjuster or pH) measured by the water quality monitoring device, and control the amount of pH adjuster added or the supply rate in the pH adjustment device using a pump or the like. The control device can transmit a signal to the ORP adjustment device based on the water quality (e.g., the concentration of the active ingredient in the ORP adjuster or the ORP) measured by the water quality monitoring device, and control the amount of ORP adjuster added or the supply rate in the ORP adjustment device using a pump or the like. The control device can transmit a signal to an inert gas mass flow controller based on the water quality (e.g., the concentration of the inert gas) measured by a water quality monitoring device, and control the amount of inert gas added or the supply rate of the inert gas supplied from the inert gas supply device using the mass flow controller, etc.

[0080] <Temperature control device> The manufacturing apparatus of the present disclosure may further include a temperature control device. The location where the temperature control device is installed in the manufacturing apparatus of the present disclosure is not particularly limited. Examples of the temperature control device include a heat exchanger.

[0081] <Coating equipment> The manufacturing apparatus of the present disclosure may further include an application device for applying the produced conditioned water to an object at a point of use of the produced conditioned water, such as a semiconductor substrate having a metal component exposed on its surface, used in a semiconductor or semiconductor device manufacturing process. Any known coating device can be used, including, for example, a dip coater, a slit coater, a spin coater, a spray coater, and an inkjet coating device.

[0082] <Flow path> In the manufacturing apparatus of the present disclosure, the flow paths (e.g., transfer lines or supply lines) through which the water to be treated, such as ultrapure water, adjusted water, concentration adjusters, pH adjusters, ORP adjusters, and inert gases, flow are made up of, for example, piping. The flow paths may be provided with equipment such as tanks, pumps, joints, and valves.

[0083] Examples of materials for piping include polymeric materials such as polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and polypropylene (PP), as well as fiber-reinforced plastics (FRP) and stainless steel. Among these, PFA is preferred.

[0084] <Example of Manufacturing Device> Hereinafter, an embodiment of the manufacturing apparatus of the present disclosure will be described in detail with reference to the drawings. 1 to 4 are block diagrams that schematically show a manufacturing apparatus according to the present disclosure.

[0085] 1 includes a transfer line L1 for water W to be treated, such as ultrapure water, a concentration adjuster 10 for a dopant element, an ORP adjuster 60, an impurity component remover 20, and a water quality monitor 30. The transfer line L1 connects the concentration adjuster 10 and the ORP adjuster 60, connects the ORP adjuster 60 and the remover 20, and connects the remover 20 and the monitor 30. The production apparatus 1 in Figure 1 includes, from upstream to downstream of a transfer line L1 through which the water to be treated W flows, a concentration adjuster 10, an ORP adjuster 60, a removal device 20, and a monitoring device 30, in this order. The produced adjusted water is sent to a point of use (UP) via a transfer line L2. A variation of the production apparatus 1 in Figure 1 is a production apparatus that includes, from upstream to downstream of the transfer line L1, a concentration adjuster 10, a removal device 20, an ORP adjuster 60, and a monitoring device 30, in this order.

[0086] 2 includes a transfer line L1 for water W to be treated, such as ultrapure water, a concentration adjuster 10 for a dopant element, an ORP adjuster 60, a water quality monitor 30, and an impurity component remover 20. The transfer line L1 connects the concentration adjuster 10 and the ORP adjuster 60, connects the ORP adjuster 60 and the water quality monitor 30, and connects the water quality monitor 30 and the remover 20. The production apparatus 1 in Figure 2 includes, from upstream to downstream of a transfer line L1 through which the water to be treated W flows, a concentration adjuster 10, an ORP adjuster 60, a water quality monitoring device 30, and a removal device 20, in this order. The produced adjusted water is sent to a point of use (UP) via a transfer line L2. A variation of the production apparatus 1 in Figure 2 is a production apparatus that includes, from upstream to downstream of the transfer line L1, a concentration adjuster 10, a water quality monitoring device 30, a removal device 20, and an ORP adjuster 60, in this order.

[0087] The dopant element concentration adjusting device 10 in Figures 1 and 2 includes a tank 12 containing a concentration adjusting agent containing a dopant component, a supply line 14L connecting the tank 12 to a transfer line L1, and may further include a pump (not shown) located on the supply line 14L.

[0088] 3 includes a transfer line L1 for water W to be treated, such as ultrapure water, a concentration adjuster 10 for a dopant element, an ORP adjuster 60, and a water quality monitor 30. The transfer line L1 connects the concentration adjuster 10 and the ORP adjuster 60, and also connects the ORP adjuster 60 and the water quality monitor 30. 3 includes, from upstream to downstream of a transfer line L1 through which the water to be treated W flows, a concentration adjuster 10, an ORP adjuster 60, and a water quality monitor 30. The adjusted water thus produced is sent to a point of use (UP) via a transfer line L2.

[0089] The dopant element concentration adjusting device 10 in Figure 3 includes a tank 12 containing a concentration adjusting agent containing a dopant component, an impurity component removing device 16, and a supply line 14L connecting the tank 12, the removing device 16, and the transfer line L1. The manufacturing apparatus 1 in FIGS. 1 to 3 and the above-described modified examples may be provided with a pH adjusting device 50 instead of the ORP adjusting device 60 or in addition to the ORP adjusting device 60.

[0090] The manufacturing apparatus 1 in Figure 4 is equipped with a hydrogen peroxide removal device 90, a pH adjustment device 50, an ORP adjustment device 60, a degassing device 70, and a gas dissolved film device 80, arranged in this order on the transfer line L1. Ultrapure water, serving as raw water flowing through the transfer line L1, passes through the hydrogen peroxide removal device 90 to remove hydrogen peroxide, passes through the pH adjustment device 50 to become pH-adjusted water, passes through the ORP adjustment device 60 to adjust the ORP, passes through the degassing device 70 to be degassed, and the degassed pH-adjusted water passes through the gas dissolved film device 80 to become adjusted water. In the manufacturing apparatus 1 in Figure 4, the location of the water quality monitoring device 30 that measures the concentration of the dopant element is not particularly limited, as long as it is downstream of the concentration adjustment device 10.

[0091] The manufacturing apparatus 1 in Figure 4 may be equipped with a concentration adjustment device 10 at position A and a removal device 20 at position B, C, D, E or F; may be equipped with a concentration adjustment device 10 at position A or B and a removal device 20 at position C, D, E or F; may be equipped with a concentration adjustment device 10 at position A, B or C and a removal device 20 at position D, E or F; may be equipped with a concentration adjustment device 10 at position A, B, C or D and a removal device 20 at position E or F; or may be equipped with a concentration adjustment device 10 at position A, B, C, D or E and a removal device 20 at position F. The manufacturing apparatus 1 in FIG. 4 may be provided with a dopant element concentration adjusting device 10 equipped with an impurity component removing device 16 at position A, B, C, D, E or F.

[0092] The manufacturing apparatus 1 in FIG. 4 may not include at least one device selected from the group consisting of the hydrogen peroxide removal device 90, the degassing device 70, and the gas-dissolved film type device 80, and may not include either the pH adjustment device 50 or the ORP adjustment device 60.

[0093] 1 to 4 controls the amount or supply rate of the concentration adjuster in the concentration adjuster 10, the amount or supply rate of the pH adjuster in the pH adjuster 50, and the ORP adjuster in the ORP adjuster 60 based on the water quality obtained by the water quality monitoring device 30 (e.g., concentration of the dopant element, concentration of the active ingredient in the pH adjuster, pH, concentration of the active ingredient in the ORP adjuster, ORP). The control device 40 in FIG. 4 controls the amount or supply rate of the inert gas in the gas dissolved film type device 80 based on the water quality obtained by the water quality monitoring device 30.

[0094] The above describes the adjusted water manufacturing apparatus of the present disclosure based on the above embodiment with reference to the attached drawings, but the adjusted water manufacturing apparatus of the present disclosure is not limited to the above embodiment and can be modified in various ways.

[0095] [Method of producing adjusted water] The method for producing conditioned water according to the present disclosure includes: a step of adding a concentration adjuster containing a dopant component to the water to be treated while controlling the amount of the agent added (hereinafter also referred to as the "addition step"); at least one step selected from the group consisting of a pH adjustment step of adjusting the pH of the water to be treated, to which the concentration adjuster may be added, and an oxidation-reduction potential (ORP) adjustment step of adjusting the oxidation-reduction potential (ORP) of the water to be treated, to which the concentration adjuster may be added; It has.

[0096] The method for producing adjusted water of the present disclosure may further include a step of measuring the concentration of the dopant element in the treated water or adjusted water to which the concentration adjuster has been added (hereinafter also referred to as the "water quality monitoring step"). In one embodiment, the manufacturing method further includes a step of selectively removing at least a part of impurity components different from the dopant component from the water to be treated in which the concentration adjuster may be added (hereinafter also referred to as the "removing step"), or The addition step further includes a step of selectively removing at least a part of impurity components different from the dopant component from the concentration adjuster (removing step).

[0097] By the above manufacturing method, the concentration of the dopant element can be adjusted, and in one embodiment, adjusted water with a reduced content of impurity components can be produced. The adjusted water can be used for coating a semiconductor substrate having a metal component exposed on the surface in the manufacturing process of a semiconductor or a semiconductor device.

[0098] In the addition step, a concentration adjuster containing a dopant component is added to water to be treated such as ultrapure water. Here, it is desirable to add the concentration adjuster so that the concentration of the dopant element in the adjusted water is preferably 100,000 mg / L or less, more preferably 0.1 to 50,000 mg / L, still more preferably 0.5 to 20,000 mg / L, and particularly preferably 1 to 13,000 mg / L. In the pH adjustment step, for example, a pH adjuster is added to the water to be treated. The pH of the water to be treated or the adjusted water is adjusted to the range described in the <pH adjustment device and redox potential adjustment device> column in one embodiment. In the ORP adjustment step, for example, an ORP adjuster is added to the water to be treated. The ORP of the water to be treated or the adjusted water is adjusted to the range described in the <pH adjustment device and redox potential adjustment device> column in one embodiment.

[0099] In the removal step, at least a portion of impurity components other than the dopant component is selectively removed from the water to be treated, to which a concentration adjuster may be added, or from the concentration adjuster. Here, it is desirable to remove the impurity components so that the concentration of the impurity components in the water to be treated or the concentration adjuster is preferably 1 μg / L or less, more preferably 0.1 μg / L or less, even more preferably 0.01 μg / L or less, and particularly preferably 0.001 μg / L or less.

[0100] In the water quality monitoring step, the water quality (e.g., the concentration of the dopant element) of the treatment water to which the concentration adjuster has been added or the obtained adjusted water is measured to monitor whether the adjusted water has the desired water quality. A control device is used to control the amount of concentration adjuster added or the supply rate in the addition step so that the adjusted water has the desired water quality.

[0101] The above-mentioned manufacturing method may further include at least one step selected from the group consisting of a hydrogen peroxide removal step for removing hydrogen peroxide from the water to be treated, a degassing step for degassing the water to be treated, and a gas dissolution step for dissolving an inert gas in the water to be treated.

[0102] Regarding the details of the above manufacturing method and the conditions of each step, the conditions described in the above [Apparatus for manufacturing adjusted water] section can be applied, and description here will be omitted. The manufacturing method of the present disclosure can be carried out using, for example, the above-described manufacturing apparatus.

[0103] [Uses of adjusted water] The adjusted water produced by the manufacturing apparatus or method of the present disclosure is used, for example, to be applied to a semiconductor substrate in the manufacturing process of a semiconductor or semiconductor device, specifically, to perform a liquid doping treatment on the semiconductor substrate. For example, the adjusted water is applied to the surface of the semiconductor substrate, and then the substrate is heated to diffuse the dopant contained in the adjusted water into the semiconductor substrate. Examples of application methods include dip coating, slit coating, spin coating, spray coating, and inkjet coating. The temperature of the applied adjusted water is preferably 10 to 90°C, more preferably 20 to 45°C. In the case of dip coating, in which the semiconductor substrate is immersed in the adjusted water, the immersion time is preferably 0.5 to 60 minutes, more preferably 1 to 45 minutes. From the viewpoints of the diffusibility of the dopant element and the thermal budget, the heating temperature in the heat treatment is preferably 200 to 1000°C, more preferably 300 to 900°C, and even more preferably 400 to 800°C. From the above viewpoints, the heating time is preferably 1 minute to 10 hours, more preferably 3 minutes to 5 hours, and even more preferably 5 minutes to 60 minutes.

[0104] As the semiconductor substrate, various substrates conventionally used as targets for dopant diffusion can be used without particular limitation. For example, a silicon substrate such as a silicon wafer can be used as the semiconductor substrate. The material of the surface of the semiconductor substrate to which the adjusted water is applied is not particularly limited, but examples include Si, SiO2, SiCN, SiN, and SiC. The metal component is exposed on the surface of the semiconductor substrate. For example, a portion of the surface of the semiconductor substrate is a wiring pattern containing the metal component. The wiring pattern may contain a compound containing the metal component. Specific examples of these are as described above.

[0105] [Example of situation] The present disclosure relates to, for example, the following [1] to

[17] . [1] An apparatus for producing adjusted water in which the concentration of a dopant element is adjusted, which is used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, the apparatus comprising: a dopant element concentration adjuster that adds a concentration adjuster containing a dopant component to the water to be treated by controlling the amount of the concentration adjuster added; a pH adjuster that adjusts the pH of the water to be treated to which the concentration adjuster may be added; and an oxidation-reduction potential adjuster that adjusts the oxidation-reduction potential of the water to be treated to which the concentration adjuster may be added. [2] The apparatus for producing conditioned water according to [1], wherein a part of the surface of the semiconductor substrate is a wiring pattern containing the metal component. [3] The apparatus for producing conditioned water according to [1] or [2], wherein the metal component comprises at least one metal element of a group selected from the group consisting of Groups 3, 4, 5, 8, 9, 10, 11, and 13 of the periodic table. [4] An apparatus for producing adjusted water according to any one of [1] to [3], comprising an impurity component removal device that selectively removes at least a portion of impurity components other than the dopant components from the water to be treated or the concentration adjuster, to which the concentration adjuster may be added. [5] The apparatus for producing conditioned water according to [4], wherein the removal device has at least one selected from the group consisting of an ion exchange resin, an ion exchange membrane, a nanofiltration membrane, and a reverse osmosis membrane. [6] The apparatus for producing adjusted water according to [4] or [5], wherein the removal device is located upstream or downstream of the concentration adjustment device for the dopant element on the transfer line for the water to be treated. [7] The apparatus for producing conditioned water according to any one of [4] to [6], wherein the concentration adjusting device has the removing device. [8] The apparatus for producing adjusted water described in any one of [4] to [7], wherein the removal device removes the impurity components so that the concentration of the impurity components in the water to be treated or the concentration adjuster is 1 μg / L or less. [9] The apparatus for producing adjusted water described in any one of [1] to [8], wherein the concentration adjusting device adds the concentration adjusting agent to the water to be treated so that the concentration of the dopant element constituting the dopant component in the adjusted water is 100,000 mg / L or less.

[10] The apparatus for producing adjusted water described in any of [1] to [9] above, further comprising: a water quality monitoring device that measures the concentration of the dopant element in the water to be treated or the adjusted water to which the concentration adjuster has been added; and a control device that controls the amount of concentration adjuster added in the concentration adjustment device based on the concentration of the dopant element measured by the water quality monitoring device.

[11] The apparatus for producing conditioned water according to any one of [1] to

[10] , wherein the concentration adjusting device adds an aqueous solution containing the dopant component as the concentration adjusting agent to the water to be treated.

[12] The apparatus for producing adjusted water according to

[11] , wherein the aqueous solution contains at least one compound selected from the group consisting of a compound containing an n-type dopant and a compound containing a p-type dopant.

[13] The apparatus for producing conditioned water according to any one of [1] to

[12] above, further comprising a degassing device for removing at least a portion of the dissolved gas in the water to be treated.

[14] The apparatus for producing adjusted water according to any one of [1] to

[13] above, further comprising a gas-dissolving membrane type device that dissolves an inert gas in the water to be treated via a gas-permeable membrane.

[15] An apparatus for producing adjusted water according to any one of [1] to

[14] above, which is an apparatus for producing adjusted water having an adjusted concentration of dopant elements, used for doping a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process.

[16] A method for producing adjusted water having an adjusted concentration of a dopant element, which is used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, the method comprising at least one step selected from the group consisting of an addition step of adding a concentration adjuster containing a dopant component to water to be treated by controlling the amount of addition, a pH adjustment step of adjusting the pH of the water to be treated to which the concentration adjuster may have been added, and an oxidation-reduction potential adjustment step of adjusting the oxidation-reduction potential of the water to be treated to which the concentration adjuster may have been added.

[17] A method for producing adjusted water described in

[16] , wherein the production method further includes a step of selectively removing at least a portion of impurity components other than the dopant component from the water to be treated, to which the concentration adjuster may be added, or the addition step further includes a step of selectively removing at least a portion of impurity components other than the dopant component from the concentration adjuster. [Example]

[0106] The conditioned water manufacturing device of the present disclosure will be described based on examples and application examples. The conditioned water manufacturing device of the present disclosure is not limited to the following examples and application examples.

[0107] A boric acid aqueous solution with a concentration of 4% by mass, an arsenic trioxide aqueous solution with a concentration of 4% by mass, and a phosphoric acid aqueous solution with a concentration of 50% by mass were prepared. In the following examples, the manufacturing apparatus 1 shown in FIG. 1, which further includes a pH adjusting device (not shown), was used. The dopant element concentration adjusting device 10 includes a tank containing a boric acid aqueous solution, a tank containing an arsenic trioxide aqueous solution, and a tank containing a phosphoric acid aqueous solution. The impurity component removing device 20 includes a cation exchange resin (product name KR-FC, manufactured by Kurita Water Industries, Ltd.).

[0108] [Example 1] The following adjusted water was produced using the above-described production apparatus 1 as follows. A mixed solution was prepared by adding an aqueous solution of boric acid, an aqueous solution of arsenic acid, and an aqueous solution of phosphoric acid to ultrapure water in the concentration adjusting device 10 in amounts such that the concentrations of boric acid, arsenic acid, and phosphoric acid in the adjusted water were the values ​​shown in Table 1. Next, a pH adjuster (aqueous ammonia solution) was added in the pH adjusting device to adjust the pH. Next, an ORP adjuster (water-based H2O2) was added in the OPR adjusting device 60 to adjust the ORP. The mixed solution after ORP adjustment was then passed through a removal device 20 equipped with a cation exchange resin (product name: KR-FC). In this way, adjusted water 1 was prepared, each of which had a concentration of 1% by mass (10,000 ppm) of boric acid, arsenic acid, and phosphoric acid.

[0109] [Examples 2 to 4] Adjusted waters 2 to 4 were prepared in the same manner as in Example 1, except that the amounts of boric acid aqueous solution and the like added were adjusted and the concentrations of each component in the adjusted water were changed as shown in Table 1.

[0110] [Example 5] The following adjusted water was produced using the above-mentioned production apparatus 1 (but without the removal apparatus 20) as follows: To ultrapure water, an aqueous phosphoric acid solution was added in a concentration adjusting apparatus 10 in an amount such that the phosphoric acid concentration in the adjusted water would be the value shown in Table 1, then a pH adjuster (aqueous ammonia solution) was added in a pH adjusting apparatus to adjust the pH, and then an ORP adjuster (water H2O2) was added in an OPR adjusting apparatus 60 to adjust the ORP, thereby preparing adjusted water 5.

[0111] [Comparative Example 1] The above-mentioned manufacturing apparatus 1 (excluding the removal apparatus 20, pH adjuster, and ORP adjuster 60) was used to manufacture the following adjusted water as follows: Adjusted water 6 was prepared by adding an amount of phosphoric acid aqueous solution to ultrapure water in the concentration adjuster 10 so that the phosphoric acid concentration in the adjusted water would be the value shown in Table 1.

[0112] [Application example] The pH of the adjusted water was measured using a pH meter (manufactured by Horiba). The ORP of the adjusted water was measured using an ORP meter (manufactured by Horiba). The results are shown in Table 1.

[0113] The amounts of dopants (amounts of P element, B element, and As element) in the adjusted water were measured using an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Agilent). Evaluation criteria for the amount of dopant in the adjusted water Small: The content of P, B, and As elements is less than 1 mg / L. Medium: The content of P, B, and As elements is 1 to 10,000 mg / L. Large: The content of P, B, and As elements exceeds 10,000 mg / L. The evaluation of the content is an evaluation of each of the elements.

[0114] The amount of metal elements in the adjusted water was measured using an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Agilent). Evaluation criteria for metal element content in adjusted water Small: The content of Na, Ca, and Fe elements is less than 1 ng / L. Medium: The content of Na, Ca, and Fe elements is 1 to 1000 ng / L. Large: The content of Na, Ca, and Fe elements exceeds 1000ng / L. The evaluation of the content is an evaluation of each of the elements.

[0115] A batch tank was filled with the adjusted water obtained in each of the examples or comparative examples, and a silicon wafer on which a pattern containing the wiring material listed in Table 1 had been formed was immersed in the adjusted water at 25°C for 10 minutes. The silicon wafer was then removed from the adjusted water. The content of each element (Cu, Co, La, Ru, etc.) in the immersion liquid (the adjusted water after the silicon wafer was removed) was analyzed using an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Agilent). Based on the content of each element in the immersion liquid, the amount of dissolution of the pattern (based on thickness) was calculated, and the dissolution rate (nm / min) of the target material was calculated. Elution rate = [content after immersion - 0 (content before immersion)] / immersion time Dissolution rate evaluation criteria ○ Less than 0.1 nm / min × 0.1nm / min or more

[0116] The immersed silicon wafer was subjected to annealing treatment for 20 minutes at 800° C. The diffusion depth of each element in the silicon wafer after the annealing treatment was measured by secondary ion mass spectrometry (SIMS analysis, manufactured by Cameca). Diffusion depth evaluation criteria 〇:50nm or more △: Over 5nm and under 50nm ×: 5nm or less

[0117] [Table 1] [Explanation of symbols]

[0118] 1. Adjusted water production equipment 10...Dopant element concentration adjustment device 12...Tank containing concentration adjuster 14L…supply line 16, 20 ... Impurity component removal device 30…Water quality monitoring device 40...Control device 50...pH adjustment device 60…ORP adjustment device 70... Degassing device 80...Gas-dissolved film type device 90...Hydrogen peroxide removal device W: Ultrapure water or other water to be treated L1, L2 ... Transfer lines UP...Use points

Claims

1. An apparatus for producing adjusted water having an adjusted concentration of a dopant element, which is used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, The manufacturing apparatus includes: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to the water to be treated by controlling the amount of the agent added; at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of the treatment target water to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the treatment target water to which the concentration adjusting agent may be added; Equipped with a part of the surface of the semiconductor substrate is a wiring pattern containing the metal component; Equipment for producing conditioned water.

2. 2. The apparatus for producing conditioned water according to claim 1, wherein the metal component comprises at least one metal element of a group selected from the group consisting of Groups 3, 4, 5, 8, 9, 10, 11, and 13 of the periodic table.

3. The adjusted water manufacturing apparatus of claim 1, further comprising an impurity component removal device that selectively removes at least a portion of impurity components other than the dopant components from the water to be treated or the concentration adjuster, to which the concentration adjuster may be added.

4. The apparatus for producing conditioned water according to claim 3, wherein the removal device comprises at least one selected from the group consisting of an ion exchange resin, an ion exchange membrane, a nanofiltration membrane, and a reverse osmosis membrane.

5. 4. The apparatus for producing conditioned water according to claim 3, wherein the removal device is located upstream or downstream of the device for adjusting the concentration of the dopant element on a transfer line for the water to be treated.

6. The apparatus for producing conditioned water according to claim 3 , wherein the concentration adjusting device has the removing device.

7. 4. The apparatus for producing conditioned water according to claim 3, wherein the removal device removes the impurity components so that the concentration of the impurity components in the treatment target water or the concentration adjuster is 1 μg / L or less.

8. The adjusted water manufacturing apparatus according to claim 1, wherein the concentration adjusting device adds the concentration adjusting agent to the water to be treated so that the concentration of the dopant element constituting the dopant component in the adjusted water is 100,000 mg / L or less.

9. The apparatus for producing conditioned water according to claim 1 , wherein the concentration adjuster adds an aqueous solution containing the dopant component as the concentration adjuster to the water to be treated.

10. 10. The apparatus for producing conditioned water according to claim 9, wherein the aqueous solution contains at least one compound selected from the group consisting of a compound containing an n-type dopant and a compound containing a p-type dopant.

11. The apparatus for producing conditioned water according to claim 1 , further comprising a degassing device for removing at least a portion of dissolved gases in the water to be treated.

12. An apparatus for producing adjusted water in which the concentration of a dopant element is adjusted, the adjusted water being used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, The manufacturing apparatus includes: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to the water to be treated by controlling the amount of the agent added; at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of the treatment target water to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the treatment target water to which the concentration adjusting agent may be added; a water quality monitoring device that measures the concentration of the dopant element in the treatment target water or the adjusted water to which the concentration adjuster has been added; a control device that controls the amount of the concentration adjuster added in the concentration adjuster based on the concentration of the dopant element measured by the water quality monitoring device; An apparatus for producing adjusted water comprising:

13. An apparatus for producing adjusted water in which the concentration of a dopant element is adjusted, the adjusted water being used to apply to a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, The manufacturing apparatus includes: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to the water to be treated by controlling the amount of the agent added; at least one adjusting device selected from the group consisting of a pH adjusting device that adjusts the pH of the treatment target water to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the treatment target water to which the concentration adjusting agent may be added; a gas-dissolving membrane type device that dissolves an inert gas in the water to be treated via a gas-permeable membrane; An apparatus for producing adjusted water comprising:

14. The apparatus for producing adjusted water according to any one of claims 1 to 13, which is an apparatus for producing adjusted water having an adjusted concentration of dopant elements, used for doping a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process.

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