Apparatus for producing adjusted water and method for producing adjusted water

Abstract

The present invention provides an apparatus for producing adjusted water in which the concentration of dopant elements is adjusted, which is used for coating a semiconductor substrate having exposed metal components on its surface in the manufacturing process of semiconductors or semiconductor devices, and in which the dissolution of the metal components into the adjusted water is suppressed during the coating process. [Solution] A device for producing adjusted water, comprising: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to water to be treated while controlling the amount added; a pH adjusting device that adjusts the pH of water to be treated to which the concentration adjusting agent may be added; and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of water to which the concentration adjusting 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 Art

[0002] Substrates used in semiconductor devices such as transistors, diodes, and solar cells are manufactured by diffusing dopant elements such as phosphorus or boron into the semiconductor substrate. As a method of diffusing dopant elements into a semiconductor substrate, for example, a dry process method such as an ion implantation method is used (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Applying a dry process method to a semiconductor substrate having a complex structure tends to be difficult. Therefore, the inventor has considered a method of applying an aqueous solution containing a dopant element to the surface of a semiconductor substrate as a wet process method that is considered to be easy to apply to a semiconductor substrate having a complex structure. The inventor has found that, in this case, the metal components exposed on the surface of the semiconductor substrate may unintentionally dissolve in the aqueous solution.

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

Means for Solving the Problems

[0006] One embodiment of the apparatus for producing adjusted water according to the present disclosure is an apparatus for producing adjusted water with an adjusted concentration of dopant elements, used for coating a semiconductor substrate having exposed metal components on its surface in a semiconductor or semiconductor device manufacturing process, and the apparatus comprises: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to water to be treated, with control over the amount added; a pH adjusting device that adjusts the pH of water to be treated to which the concentration adjusting agent may be added; and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of water to which the concentration adjusting agent may be added. [Effects of the Invention]

[0007] The manufacturing apparatus of the present disclosure is capable of producing adjusted water with an adjusted concentration of dopant elements, which is used for coating a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process, and in which the dissolution of the metal components into the adjusted water is suppressed during coating. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a block diagram schematically showing one embodiment of a water conditioning production apparatus. [Figure 2] Figure 2 is a block diagram schematically showing one embodiment of a water conditioning production apparatus. [Figure 3] Figure 3 is a block diagram schematically showing one embodiment of a water conditioning production apparatus. [Figure 4] Figure 4 is a block diagram schematically showing one embodiment of a water conditioning production apparatus. [Modes for carrying out the invention]

[0009] In this specification, the numerical range N1 to N2 means N1 or greater and N2 or less. In this specification, if the units of the numbers before and after the "~" indicating a numerical range are the same, the unit of the number before the "~" may be omitted.

[0010] The manufacturing apparatus disclosed herein produces the desired adjusted water by processing raw water, such as ultrapure water, by adding concentration adjusting agents, etc., as described below. In this specification, raw water such as ultrapure water, and aqueous solutions obtained by adding concentration adjusting agents, etc., to raw water, are collectively referred to as "water to be treated."

[0011] [Water preparation equipment] The manufacturing apparatus of the present disclosure is an apparatus for producing adjusted water with a controlled concentration of dopant elements, which is used for coating a semiconductor substrate having exposed metal components on its surface in a semiconductor or semiconductor device manufacturing process.

[0012] The manufacturing apparatus disclosed herein is A dopant element concentration adjustment device that adds a concentration adjusting agent containing a dopant component to the water to be treated, while controlling the amount added, At least one adjustment device selected from the group consisting of a pH adjustment device for adjusting the pH of the water to be treated to which the above concentration adjusting agent may be added, and an oxidation-reduction potential adjustment device for adjusting the oxidation-reduction potential of the water to be treated to which the above concentration adjusting agent may be added, It is equipped with.

[0013] The manufacturing apparatus of this disclosure may further include a water quality monitoring device for measuring the concentration of dopant elements in the treated water or adjusted water to which the above-mentioned concentration adjusting agent has been added.

[0014] The manufacturing apparatus of this disclosure may include an impurity removal device that selectively removes at least a portion of unintended impurity components, which are different from the target dopant component, from the water to be treated or the concentration adjusting agent to which the above concentration adjusting agent may be added.

[0015] The manufacturing apparatus of this disclosure can produce adjusted water from water such as ultrapure water that contains a target dopant element or dopant component (for example, a metal element or ion) in a wide concentration range, and in one embodiment, has unwanted impurity components (for example, a metal element or ion) removed or reduced in concentration.

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

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

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

[0019] The conditioned water produced using the production apparatus of the present disclosure is transferred to its place of use (use point; UP). Examples of use points include, for example, in the manufacturing process of semiconductors or semiconductor devices, a doping treatment apparatus for applying the above conditioned water to a semiconductor substrate having a metal component exposed on its surface. Examples of semiconductor devices include transistors, diodes, and solar cells.

[0020] <Dopant element concentration adjustment device> The production apparatus of the present disclosure includes a dopant element concentration adjustment device. The above concentration adjustment device is a device for controlling the addition amount and adding a concentration adjusting agent containing a dopant component to water to be treated such as ultrapure water. For example, it is a device for adding an aqueous solution containing a dopant component to water to be treated.

[0021] The concentration adjusting agent contains a dopant component. The dopant component includes 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 adjusting agent and the conditioned water to be produced. One type of dopant component may be used, or two or more types may be used. The concentration adjusting agent is, for example, an aqueous solution containing the above dopant component.

[0022] The dopant component described above is not particularly limited as long as it is a component that has been conventionally used for doping semiconductor substrates. For example, it may be a compound containing an n-type dopant or a compound containing a p-type dopant. The aqueous solution described above is, for example, an aqueous solution containing at least one 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. Preferred dopant components include, for example, phosphorus compounds, arsenic compounds, and boron compounds.

[0024] Examples of phosphorus compounds include phosphoric acid, phosphorous acid, diphosphorous acid, polyphosphoric acid, and diphosphorus pentoxide. Other examples include phosphorous acid esters such as trimethyl phosphate and triethyl phosphate, phosphate esters such as trimethyl phosphate and triethyl phosphate, tris(trialkylsilyl) phosphates such as tris(trimethylsilyl) phosphate, 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] Examples of boron compounds include boric acid, metaboric acid, boronic acid, perboric acid, subboric acid, diboron trioxide, trialkyl borate, tetrahydroxydiborane, monoalkoxytrihydroxydiborane, dialkoxydihydroxydiborane, trialkoxymonohydroxydiborane, and tetraalkoxydiborane.

[0027] The concentration of the dopant element in the adjusted water obtained by the manufacturing apparatus of this disclosure is set appropriately according to the intended use 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 adjustment apparatus, for example, adds a concentration adjusting agent 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 above-described concentration adjustment device is, for example, a device that measures and supplies a concentration adjusting agent to a transfer line of water to be treated, such as ultrapure water. The above-described concentration adjustment device comprises, for example, a tank containing 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 to adjust the supply rate of the concentration adjusting agent, if desired. As will be described later, in one embodiment, the concentration adjustment device may further include a device for removing impurity components. The concentration adjustment device may, for example, include a tank containing a concentration adjusting agent, the removal device, and a supply line that supplies the concentration adjusting agent from the tank through the removal device to a transfer line. The above concentration adjustment device may be equipped with two or more of the above tanks, depending on the type of concentration adjusting agent.

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

[0030] Examples of pumps include diaphragm pumps. Alternatively, a pressurized extrusion pump may be used, in which the concentration adjusting agent is placed in a tank together with an inert gas (e.g., N2 gas), and the concentration adjusting agent is pushed out by the pressure of the inert gas.

[0031] <Device for removing impurities> In one embodiment, the manufacturing apparatus of the present disclosure includes an apparatus for removing impurity components. The above-described removal device selectively removes at least a portion of impurity components (for example, at least one selected from the group consisting of metal elements and ions) different from the dopant components from the water to be treated, which may contain the concentration adjusting agent, or from the concentration adjusting agent itself. The impurity components here are components that are undesirable to be present in the adjusted water produced. In one embodiment, the above-described removal device can allow the dopant component to pass through while selectively removing the impurity component. Examples of impurity components include metallic elements and ions such as Al, Ca, Fe, Mg, Na, Ni, and Zn, as well as unintended dopant components.

[0032] The above-mentioned removal device preferably has a removal section corresponding to the type of impurity component to be removed. The above-mentioned removal device preferably has at least one selected from the group consisting of ion exchange resin, ion exchange membrane, nanofiltration membrane, and reverse osmosis membrane. Among these, ion exchange resin is preferred. Examples of ion exchange resins include cation exchange resin and anion exchange resin, and cation exchange resin is preferred from the standpoint of removing cationic metal ion impurities in the water to be treated or the concentration adjusting agent.

[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 to tertiary amine type.

[0034] As the ion exchange resin, for example, a mixed resin of a cation exchange resin and an anion exchange resin may be used. This makes it possible to selectively remove unwanted dopant components (for example, dopant components other than boron compounds) depending on the type of dopant component being targeted (e.g., boron compounds) and the dopant components being unintended (e.g., dopant components other than boron compounds), for example, using an impurity removal device.

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

[0036] The above-described 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-described removal device is, for example, a device that removes impurity components such 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, still more preferably 0.01 μg / L or less, and particularly preferably 0.001 μg / L or less.

[0038] In one embodiment, the above-described removal device is located on the transfer line of the water to be treated, upstream or downstream of the dopant element concentration adjustment device, 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-described removal device is included in the dopant element concentration adjustment device. That is, in one embodiment, the above-described concentration adjustment device may further include the above-described removal device. Thereby, for example, impurity components in the concentration adjuster 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 Adjustment Device and Redox Potential Adjustment Device> The manufacturing device of the present disclosure further includes at least one adjustment device selected from the group consisting of a pH adjustment device that adjusts the pH of water to be treated such as ultrapure water, and a redox potential adjustment device (hereinafter also referred to as an "ORP adjustment 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-described metal components into the adjusted water during the above-described coating. A pH adjustment device is a device that adjusts the pH of water to be treated by measuring and supplying a pH adjusting agent to the water transfer line. For example, a pH adjustment device comprises a tank containing a pH adjusting agent and a supply line that supplies the pH adjusting agent from the tank to the transfer line, and may further include a pump to adjust the supply rate of the pH adjusting agent, if desired. The ORP adjustment device is preferably located downstream of the pH adjustment device and upstream of the degassing device on the transfer line. Therefore, the ORP of the water to be treated may be adjusted by the ORP adjustment device.

[0041] An ORP adjustment device is a device that adjusts the ORP of water to be treated by measuring and supplying an oxidation-reduction potential adjusting agent (hereinafter also referred to as "ORP adjusting agent") to the transfer line. An ORP adjustment device may further include, for example, a tank containing the ORP adjusting agent and a supply line that supplies the ORP adjusting agent from the tank to the transfer line, and optionally a pump to adjust the supply rate of the ORP adjusting agent.

[0042] pH-adjusted water obtained by adding a pH adjusting agent to ultrapure water has higher electrical conductivity than ultrapure water. Therefore, it is possible to suppress the charging of pipes and the liquid flowing within them, and to suppress the mixing of fine particles into the water being treated.

[0043] The above-mentioned tank may be equipped with at least one selected from the group consisting of a device for purging the inside of the tank using an inert gas (e.g., N2 gas) and a degassing membrane for removing dissolved gases (e.g., dissolved oxygen) from the pH adjusting agent or ORP adjusting agent inside the tank.

[0044] Examples of pumps include diaphragm pumps. Alternatively, a pressurized extrusion pump may be used, in which a pH adjuster or ORP adjuster is placed in a tank together with an inert gas (e.g., N2 gas), and the pH adjuster or ORP adjuster is pushed out by the pressure of the inert gas.

[0045] For pH adjustment devices and ORP adjustment devices, if the pH adjusting agent or ORP adjusting agent is a gas, a direct gas-liquid contact device such as a gas permeable membrane module or ejector may be used.

[0046] Examples of pH adjusting agents used to adjust the pH of the treated water or adjusted water to 7 or higher include aqueous solutions of alkaline compounds and gaseous alkaline compounds. Alkaline compounds are the active ingredients of pH adjusting agents. Examples of alkaline compounds include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. An example of a gaseous alkaline compound is ammonia gas. One or more alkaline compounds 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, an effect of suppressing the dissolution of semiconductor materials and an effect of suppressing static charge can be obtained.

[0048] In one embodiment, the pH adjustment device adjusts the pH of the water to be treated to preferably 7 to 11, more preferably 8 to 11. When the pH is 7 or higher, or 8 or higher, it tends to suppress the generation of static electricity in various devices located downstream of the pH adjustment device. When the pH is 11 or lower, it tends to suppress corrosion of semiconductor substrates and deterioration of membranes contained in degassing devices or gas-dissolution membrane devices.

[0049] Examples of pH adjusting agents used to adjust the pH of the treated water or adjusted water to less than 7 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. Acidic compounds and carbon dioxide (CO2 gas) are the active ingredients of the pH adjusting agent. One type of acidic compound may be used, or two or more types may be used. The pH value is the value obtained when 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 solution of ammonia.

[0051] Examples of ORP adjusting agents for adjusting the oxidation-reduction potential of the treated water or adjusted water to a higher (+) level include aqueous solutions such as hydrogen peroxide, and gases such as ozone and oxygen. Examples of ORP adjusting agents for adjusting the oxidation-reduction potential of the treated water or adjusted water to a lower level 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] In an ORP adjustment device, it is preferable to adjust the oxidation-reduction potential (ORP) of the water to be treated to the following ranges, or to adjust the ORP of the water to be treated so that the ORP of the adjusted water falls within the following ranges. 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 especially preferably 400 mV or higher. The above 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 especially preferably 1000 mV or lower. The above ORP is, for example, 0 to 3000 mV. The ORP is the value measured at 23°C using a known ORP meter. When the ORP is above the above lower limit, the dissolution of the metal component into the adjusted water during coating tends to be further suppressed, and the diffusivity of the dopant element into the semiconductor substrate tends to be increased.

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

[0054] A hydrogen peroxide removal apparatus 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 "carrier resin") and a platinum group metal supported on the resin. In the platinum group metal-supported resin column, hydrogen peroxide in the water to be treated, such as ultrapure water, is decomposed and removed by the catalytic action of the platinum group metal.

[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 do not easily fall off. The exchange groups of the anion exchange resin are preferably of the OH type. 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 individually, in combination of two or more, as an alloy of two or more, or as a refined product of a naturally occurring mixture without separating it into individual elements. Among these, platinum, palladium, platinum / palladium alloys, or mixtures of two or more of these are preferable due to their strong catalytic activity. Nano-order fine particles of these metals are also preferable.

[0057] <pump> The manufacturing apparatus of the present disclosure may further include a pump. Using a pump makes it easier to increase the flow velocity and water pressure. Preferably, the pump is a pump with controllable pressurization. Examples of pumps include rotary positive displacement pumps that continuously perform suction and discharge by volume change, reciprocating positive displacement pumps that repeatedly perform suction and discharge by volume change, and centrifugal pumps that discharge 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 this disclosure may further include a degassing device for degassing the water to be treated. The degassing device removes at least a portion of the dissolved gases in the water to be treated, thereby reducing the amount of dissolved gas. Examples of dissolved gases include dissolved oxygen and dissolved nitrogen.

[0059] The degassing device is preferably located downstream of the pH adjustment device, or downstream of both the pH adjustment device and the ORP adjustment device, on the transfer line described above. Such a manufacturing apparatus includes a degassing device that can suppress the generation of static electricity and prevent the accumulation of fine particles on the gas permeable membrane surface. Therefore, the inclusion of fine particles into the adjusted water can be suppressed.

[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 flows the water to be treated into 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 removing at least a portion of the dissolved gas by allowing it to pass through the gas permeable membrane and move to the gas phase chamber side. The degassing device reduces the dissolved oxygen concentration in the water to be treated supplied to the gas dissolution membrane device to 0.1 mg / L or less.

[0061] By degassing the water to be treated afterward, rather than directly degassing the concentration adjusters, pH adjusters, and ORP adjusters, the risk of chemical leakage during vacuum degassing of these agents can be reduced.

[0062] A gas permeable membrane can be any membrane that allows gases such as oxygen, nitrogen, and vapor to pass through but not water. Examples of materials that make up the gas permeable membrane include polymer materials such as silicone rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyolefin (e.g., polypropylene), and polyurethane. One polymer material may be used, or two or more may be used. Among these, at least one selected from the group consisting of polypropylene and polyvinylidene fluoride is preferred.

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

[0064] Examples of inert gases include nitrogen, argon, and helium.

[0065] In one embodiment, the gas dissolution membrane apparatus allows degassed water to be treated to flow through one side (liquid phase chamber) of a gas permeable membrane, and an inert gas to be supplied to the other side (gas phase chamber). This allows the inert gas to pass through the gas permeable membrane and move to the liquid phase side, where it can be dissolved in the water to be treated.

[0066] Examples of materials constituting the gas permeable membrane are as described above, and further examples are omitted in this section. 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 apparatus includes a hollow fiber membrane unit containing a hollow fiber membrane inside. Inside the hollow fiber membrane unit are connected a liquid supply pipe that supplies the degassed water to be treated to the hollow fiber membrane unit, a gas supply pipe that supplies an inert gas to the hollow fiber membrane unit, and a drain pipe that discharges the adjusted water in which the inert gas has dissolved.

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

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

[0070] The water quality monitoring device is preferably located downstream of the concentration adjustment device on the water transfer line, and either upstream or downstream of the impurity removal device.

[0071] The water quality monitoring device is preferably located downstream of the gas dissolution membrane 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 the pH adjuster, the concentration of the active ingredient of the ORP adjuster, pH, and oxidation-reduction potential (ORP) in the water to be treated or adjusted, or it may measure the concentration of an inert gas and monitor whether the concentration of the active ingredient, pH, ORP, or inert gas is at a desired value. The water quality monitoring device that measures the concentration of the dopant element may perform these measurements, or a different water quality monitoring device may perform these measurements.

[0072] The concentration of dopant elements in the treated water or adjusted water can be measured using a known pH meter or conductivity meter, or a metal element or ion detector. The pH, ORP, and inert gas concentrations in the treated water or adjusted water can be measured using a known pH meter, an 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 this disclosure preferably further includes a control device along with a water quality monitoring device. A control device is, for example, a computer. The water quality monitoring device may be connected to the control device, for example, electrically or wirelessly. The control device may be connected, for example, electrically or wirelessly, to at least one device selected from the group consisting of the concentration adjustment device, pH adjustment device, and ORP adjustment device, and optionally to a gas dissolution membrane type device.

[0074] The control device is, for example, a device that controls the amount or rate at which a concentration adjusting agent containing a dopant component is added to a dopant element concentration adjusting device, based on the water quality of the treated water or adjusted water measured by a water quality monitoring device (e.g., concentration of dopant elements, pH, or conductivity).

[0075] The control device can be used to control the adjusted water so that it has a set concentration of the dopant element. Such control of concentration and other parameters by the control device can be achieved by feedback control such as PI control or PID control, as well as by other well-known methods.

[0076] The control device can, for example, 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 or rate at which the concentration adjusting agent is added to the device using a pump or the like.

[0077] The control device may, for example, control at least one selected from the group consisting of the amount or rate of addition of a pH adjusting agent in a pH adjusting device and the amount or rate of addition of an ORP adjusting agent in an ORP adjusting device, based on the water quality of the water to be treated or adjusted as measured by a water quality monitoring device, and optionally, the amount or rate of addition of an inert gas in a gas-dissolved membrane type device.

[0078] The control device can be used to control the adjusted water so that it has 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, as well as a set concentration of the inert gas. The control of at least one selected from the group consisting of the active ingredient concentration, pH, and ORP, as well as the concentration of the inert gas, by such a control device can be controlled by feedback control such as PI control or PID control, as well as by well known methods.

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

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

[0081] <Coating device> The manufacturing apparatus of this disclosure may further include a coating apparatus for applying the manufactured adjusted water to an object at the point of use of the manufactured adjusted water. The object is, for example, a semiconductor substrate having exposed metallic components on its surface, used in the manufacturing process of semiconductors or semiconductor devices. Any known coating apparatus can be used as the coating apparatus. Examples of coating apparatus include dip coaters, slit coaters, spin coaters, spray coaters, and inkjet coating apparatuses.

[0082] <Flow path> In the manufacturing apparatus of this 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 composed of, for example, piping. The flow paths may be equipped with, for example, tanks, pumps, fittings, and valves.

[0083] Examples of materials used to construct the piping include polymer 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 a manufacturing apparatus> Hereinafter, embodiments of the manufacturing apparatus of the present disclosure will be described in detail with reference to the drawings. Figures 1 to 4 are block diagrams schematically representing the manufacturing apparatus of this disclosure.

[0085] The manufacturing apparatus 1 in Figure 1 comprises a transfer line L1 for the water to be treated W, such as ultrapure water, a dopant element concentration adjustment device 10, an ORP adjustment device 60, an impurity component removal device 20, and a water quality monitoring device 30. The transfer line L1 connects the concentration adjustment device 10 and the ORP adjustment device 60, the ORP adjustment device 60 and the removal device 20, and the removal device 20 and the monitoring device 30. The manufacturing apparatus 1 in Figure 1 is equipped with a concentration adjustment device 10, an ORP adjustment device 60, a removal device 20, and a monitoring device 30 in that order, from upstream to downstream of the transfer line L1 through which the water to be treated W flows. The manufactured adjusted water is sent to the use point (UP) via the transfer line L2. As a modified example of the manufacturing apparatus 1 in Figure 1, there is a manufacturing apparatus equipped with a concentration adjustment device 10, a removal device 20, an ORP adjustment device 60, and a monitoring device 30 in that order, from upstream to downstream of the transfer line L1.

[0086] The manufacturing apparatus 1 in Figure 2 comprises a transfer line L1 for the water to be treated, such as ultrapure water, a dopant element concentration adjustment device 10, an ORP adjustment device 60, a water quality monitoring device 30, and an impurity component removal device 20. The transfer line L1 connects the concentration adjustment device 10 and the ORP adjustment device 60, the ORP adjustment device 60 and the water quality monitoring device 30, and the water quality monitoring device 30 and the removal device 20. The manufacturing apparatus 1 in Figure 2 is equipped with a concentration adjustment device 10, an ORP adjustment device 60, a water quality monitoring device 30, and a removal device 20 in that order, from upstream to downstream of the transfer line L1 through which the water to be treated W flows. The produced adjusted water is sent to the use point (UP) via the transfer line L2. As a modified example of the manufacturing apparatus 1 in Figure 2, there is a manufacturing apparatus equipped with a concentration adjustment device 10, a water quality monitoring device 30, a removal device 20, and an ORP adjustment device 60 in that order, from upstream to downstream of the transfer line L1.

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

[0088] The manufacturing apparatus 1 in Figure 3 comprises a transfer line L1 for the water to be treated, such as ultrapure water, a dopant element concentration adjustment device 10, an ORP adjustment device 60, and a water quality monitoring device 30. The transfer line L1 connects the concentration adjustment device 10 and the ORP adjustment device 60, and connects the ORP adjustment device 60 to the water quality monitoring device 30. The manufacturing apparatus 1 in Figure 3 is equipped with a concentration adjustment device 10, an ORP adjustment device 60, and a water quality monitoring device 30 in that order, from upstream to downstream of the transfer line L1 through which the water to be treated W flows. The manufactured adjusted water is sent to the use point (UP) via the transfer line L2.

[0089] The dopant element concentration adjustment device 10 in Figure 3 comprises a tank 12 containing a concentration adjustment agent containing the dopant component, an impurity component removal device 16, and a supply line 14L connecting the tank 12, the removal device 16, and the transfer line L1. The manufacturing apparatus 1 shown in Figures 1 to 3 and the modified examples described above may also include a pH adjuster 50 instead of, or together with, the ORP adjuster 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 dissolution membrane device 80 in this order on the transfer line L1. Ultrapure water, which is the raw material 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, the pH-adjusted water passes through the ORP adjustment device 60 to adjust the ORP, is degassed by passing through the degassing device 70, and the degassed pH-adjusted water passes through the gas dissolution membrane device 80 to become adjusted water. In the manufacturing apparatus 1 in Figure 4, the position of the water quality monitoring device 30 for measuring the concentration of dopant elements 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 positions B, C, D, E, or F; or it 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; or it 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; or it 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 it 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 Figure 4 may also include a dopant element concentration adjustment device 10, which is equipped with an impurity component removal device 16 at positions A, B, C, D, E, or F.

[0092] The manufacturing apparatus 1 in Figure 4 does not necessarily have to include at least one device selected from the group consisting of a hydrogen peroxide removal device 90, a degassing device 70, and a gas dissolution membrane type device 80, nor does it necessarily have to include either a pH adjustment device 50 or an ORP adjustment device 60.

[0093] In Figures 1 to 4, the control device 40 controls the amount or supply rate of the concentration adjuster added in the concentration adjuster 10, the amount or supply rate of the pH adjuster added in the pH adjuster 50, and the ORP adjuster in the ORP adjuster 60, based on the water quality obtained from the water quality monitoring device 30 (for example, the concentration of the dopant element, the concentration of the active ingredient of the pH adjuster, pH, the concentration of the active ingredient of the ORP adjuster, and ORP). In Figure 4, the control device 40 controls the amount or supply rate of the inert gas added in the gas dissolution membrane type device 80, based on the water quality obtained from the water quality monitoring device 30.

[0094] Although the apparatus for producing adjusted water of this disclosure has been described above based on the above embodiments with reference to the attached drawings, the apparatus for producing adjusted water of this disclosure is not limited to the above embodiments, and various modifications can be made.

[0095] [Method for producing adjusted water] The method for producing the adjusted water disclosed herein is: The process involves adding a concentration adjusting agent containing a dopant component to the water to be treated, while controlling the amount added (hereinafter also referred to as the "addition process"), At least one step selected from the group consisting of a pH adjustment step for adjusting the pH of the water to be treated to which the above concentration adjusting agent may be added, and an oxidation-reduction potential (ORP) adjustment step for adjusting the oxidation-reduction potential (ORP) of the water to be treated to which the above concentration adjusting agent may be added, It holds.

[0096] The method for producing adjusted water according to this disclosure may further include a step of measuring the concentration of dopant elements in the water to be treated to which a concentration adjusting agent has been added, or in the adjusted water (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 to 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 manufactured. The above 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 different from the dopant components are selectively removed from the water to be treated, which may contain a concentration adjusting agent, or from the concentration adjusting agent. Here, it is desirable to remove the impurity components so 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, even more preferably 0.01 μg / L or less, and particularly preferably 0.001 μg / L or less.

[0100] In the water quality monitoring process, the water quality (e.g., concentration of dopant elements) of the treated water to which the concentration adjusting agent has been added, or the resulting adjusted water, is measured to monitor whether or not it has the desired water quality. To ensure that the adjusted water has the desired water quality, a control device is used to control the amount or rate at which the concentration adjusting agent is added during the addition process.

[0101] The above 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] Details regarding the above manufacturing method and the conditions for each process can be applied as described in the [Prepared Water Production Equipment] section above, and are therefore omitted from this section. The manufacturing method disclosed herein can be carried out, for example, using the above-described manufacturing apparatus.

[0103] [Uses of treated water] The prepared 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 for liquid doping the semiconductor substrate. For example, after applying the prepared water to the surface of the semiconductor substrate, the dopant contained in the prepared water is diffused into the semiconductor substrate by heat treatment. Examples of coating methods include dip coating, slit coating, spin coating, spray coating, and inkjet coating. The temperature of the prepared water to be applied is preferably 10 to 90°C, more preferably 20 to 45°C, and the immersion time in the case of dip coating, in which the semiconductor substrate is immersed in the prepared water, is preferably 0.5 to 60 minutes, more preferably 1 to 45 minutes. 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 viewpoint of the diffusivity of the dopant element and thermal budget, and 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, from the viewpoint of the above.

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

[0105] [Example of form] This disclosure relates, for example, to the following [1] to

[17] . [1] A production apparatus for producing adjusted water with an adjusted concentration of dopant elements, used for coating a semiconductor substrate having exposed metal components on its surface in a semiconductor or semiconductor device manufacturing process, the production apparatus comprising: a dopant element concentration adjusting device that adds a concentration adjusting agent containing a dopant component to water to be treated, with control over the amount added; a pH adjusting device that adjusts the pH of water to be treated to which the concentration adjusting agent may be added; and an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of water to which the concentration adjusting agent may be added. [2] The apparatus for producing adjusted water according to [1], wherein a portion of the surface of the semiconductor substrate is a wiring pattern containing the metal component. [3] The apparatus for producing adjusted water according to [1] or [2], wherein the metal component comprises at least one metal element from a group selected from the group consisting of Group 3, Group 4, Group 5, Group 8, Group 9, Group 10, Group 11 and Group 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 for selectively removing at least a portion of impurity components different from the dopant component from the water to be treated or the concentration adjusting agent to which the concentration adjusting agent may be added. [5] The apparatus for producing adjusted 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 dopant element concentration adjustment device on the transfer line of the water to be treated. [7] The apparatus for producing adjusted water according to any one of [4] to [6], wherein the concentration adjustment device has the removal device. [8] The apparatus for producing adjusted water according to 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 adjusting agent is 1 μg / L or less. [9] The apparatus for producing adjusted water according to 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 according to any one of [1] to [9], further comprising: a water quality monitoring device for measuring the concentration of the dopant element in the treated water or adjusted water to which the concentration adjusting agent has been added; and a control device for controlling the amount of the concentration adjusting agent added in the concentration adjusting device based on the concentration of the dopant element measured by the water quality monitoring device.

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

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

[12] The apparatus for producing adjusted water according to

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

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

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

[14] A device for producing adjusted water according to any one of [1] to

[13] , further comprising a gas dissolution membrane device for dissolving an inert gas in the water to be treated via a gas permeable membrane.

[15] An apparatus for producing adjusted water with an adjusted concentration of dopant elements, which is used to dope a semiconductor substrate having metal components exposed on its surface in a semiconductor or semiconductor device manufacturing process, as described in any of [1] to

[14] above.

[16] A method for producing adjusted water in which the concentration of a dopant element is adjusted, which is used for coating a semiconductor substrate having a metal component exposed on its surface in a semiconductor or semiconductor device manufacturing process, comprising: an addition step of adding a concentration adjusting agent containing a dopant component to water to be treated in a controlled amount; a pH adjustment step of adjusting the pH of the water to be treated to which the concentration adjusting agent may be added; and an oxidation-reduction potential adjustment step of adjusting the oxidation-reduction potential of the water to be treated to which the concentration adjusting agent may be added.

[17] The method for producing adjusted water according to

[16] , wherein the production method further comprises a step of selectively removing at least a portion of impurity components different from the dopant component from the water to be treated, which may have the concentration adjusting agent added to it, or the addition step further comprises a step of selectively removing at least a portion of impurity components different from the dopant component from the concentration adjusting agent. [Examples]

[0106] The apparatus for producing adjusted water described herein will be explained based on examples and application examples. The apparatus for producing adjusted water described herein is not limited to the following examples and applications.

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

[0108] [Example 1] Using the above manufacturing apparatus 1, the following adjusted water was produced as follows: To ultrapure water, in the concentration adjustment device 10, amounts of boric acid aqueous solution, arsenous acid aqueous solution, and phosphoric acid aqueous solution were added respectively so that the concentrations of boric acid, arsenous acid, and phosphoric acid in the adjusted water were the values ​​shown in Table 1, and a mixture was prepared. Next, the pH was adjusted by adding a pH adjusting agent (ammonia aqueous solution) in the pH adjustment device. Next, the ORP was adjusted by adding an ORP adjusting agent (H2O2 water) in the OPR adjustment device 60. Next, the mixture after ORP adjustment was passed through a removal device 20 equipped with a cation exchange resin (product name KR-FC). In this way, adjusted water 1 with concentrations of boric acid, arsenous acid, and phosphoric acid of 1% by mass (10000 ppm) each was prepared.

[0109] [Examples 2-4] Adjusted waters 2-4 were prepared in the same manner as in Example 1, except that the amount of boric acid solution and other additives was adjusted to change the concentration of each component in the adjusted water as shown in Table 1.

[0110] [Example 5] Using the above manufacturing apparatus 1 (but without the removal apparatus 20), the following adjusted water was produced as follows: To ultrapure water, an amount of phosphoric acid aqueous solution was added in the concentration adjustment apparatus 10 so that the concentration of phosphoric acid in the adjusted water was the value shown in Table 1. Then, a pH adjusting agent (ammonia aqueous solution) was added in the pH adjustment apparatus to adjust the pH. Then, an ORP adjusting agent (H2O2 water) was added in the ORP adjustment apparatus 60 to adjust the ORP, thereby preparing adjusted water 5.

[0111] [Comparative Example 1] Using the above manufacturing apparatus 1 (but without the removal device 20, pH adjuster, and ORP adjuster 60), the following adjusted water was produced as follows: Adjusted water 6 was prepared by adding an amount of phosphoric acid aqueous solution to ultrapure water in the concentration adjuster 10 such that the concentration of phosphoric acid in the adjusted water was the value shown in Table 1.

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

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

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

[0115] The adjusted water obtained in the examples or comparative examples was filled into a batch tank, and a silicon wafer with a pattern containing the wiring material described in Table 1 was immersed in the adjusted water at a temperature of 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 solution (adjusted water after removing the silicon wafer) was analyzed using an inductively coupled plasma mass spectrometer (ICP-MS, Agilent). Based on the results of the content of each element in the immersion solution, the amount of dissolved pattern (based on thickness) was calculated, and the elution rate (nm / min) of the target material was calculated. Elution rate = [content after immersion - 0 (content before immersion)] / immersion time Evaluation criteria for dissolution rate ○ Less than 0.1 nm / min × 0.1nm / min or more

[0116] The immersed silicon wafers were annealed at 800°C for 20 minutes. The diffusion depth of each element in the silicon wafers after annealing was determined by secondary ion mass spectrometry (SIMS analysis, Cameca). Criteria for evaluating diffusion depth 〇: 50nm or more △: Over 5nm and less than 50nm ×: 5nm or less

[0117] [Table 1] [Explanation of Symbols]

[0118] 1 ... Equipment for producing adjusted water 10 ... Dopant element concentration adjustment device 12... Tank containing concentration adjusting agent 14L… Supply line 16, 20 ... Device for removing impurities 30…Water quality monitoring device 40 ... control device 50...pH adjustment device 60…ORP adjustment device 70 ... Degassing device 80 ...Gas dissolution membrane type apparatus 90... Hydrogen peroxide removal device W... water to be treated, such as ultrapure water. L1, L2...transfer lines UP... Youth Points

Claims

1. A device for producing adjusted water with controlled dopant element concentrations, used for coating a semiconductor substrate having exposed metal components on its surface in the manufacturing process of semiconductors or semiconductor devices. The aforementioned manufacturing apparatus, A dopant element concentration adjustment device that adds a concentration adjusting agent containing a dopant component to the water to be treated, while controlling the amount added, At least one adjustment device selected from the group consisting of a pH adjustment device for adjusting the pH of the water to be treated to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjustment device for adjusting the oxidation-reduction potential of the water to be treated to which the concentration adjusting agent may be added, Equipped with, A device for producing adjusted water.

2. The apparatus for producing adjusted water according to claim 1, wherein a portion of the surface of the semiconductor substrate is a wiring pattern containing the metal component.

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

4. The apparatus for producing adjusted water according to claim 1, comprising an impurity component removal device for selectively removing at least a portion of impurity components different from the dopant component from the water to be treated or the concentration adjusting agent to which the concentration adjusting agent may be added.

5. The apparatus for producing adjusted water according to claim 4, wherein the removal device has at least one selected from the group consisting of ion exchange resin, ion exchange membrane, nanofiltration membrane, and reverse osmosis membrane.

6. The apparatus for producing adjusted water according to claim 4, wherein the removal device is located upstream or downstream of the dopant element concentration adjustment device on the transfer line of the water to be treated.

7. The apparatus for producing adjusted water according to claim 4, wherein the concentration adjustment device has the removal device.

8. The apparatus for producing adjusted water according to claim 4, 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 adjusting agent is 1 μg / L or less.

9. The apparatus for producing adjusted water 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.

10. A water quality monitoring device that measures the concentration of the dopant element in the treated water or adjusted water to which the concentration adjusting agent has been added, A control device that controls the amount of the concentration adjusting agent added to the concentration adjusting device based on the concentration of the dopant element measured by the water quality monitoring device, The apparatus for producing adjusted water according to claim 1, further comprising:

11. The apparatus for producing adjusted water according to claim 1, wherein the concentration adjustment device adds an aqueous solution containing the dopant component as the concentration adjustment agent to the water to be treated.

12. The apparatus for producing adjusted water according to claim 11, wherein the aqueous solution is an aqueous solution containing at least one selected from the group consisting of compounds containing an n-type dopant and compounds containing a p-type dopant.

13. The apparatus for producing adjusted water according to claim 1, further comprising a degasser 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 claim 1, further comprising a gas dissolution membrane type apparatus for dissolving an inert gas in the water to be treated via a gas permeable membrane.

15. An apparatus for producing adjusted water with an adjusted concentration of dopant elements, used for doping a semiconductor substrate having exposed metal components on its surface in a semiconductor or semiconductor device manufacturing process, according to any one of claims 1 to 14.

16. A method for producing adjusted water with a controlled concentration of dopant elements, used for coating a semiconductor substrate having exposed metal components on its surface in the manufacturing process of semiconductors or semiconductor devices. An addition step in which a concentration adjusting agent containing a dopant component is added to the water to be treated, with the amount of addition controlled, At least one step selected from the group consisting of a pH adjustment step for adjusting the pH of the water to be treated to which the concentration adjusting agent may be added, and an oxidation-reduction potential adjustment step for adjusting the oxidation-reduction potential of the water to be treated to which the concentration adjusting agent may be added, Having, A method for producing adjusted water.

17. The manufacturing method further comprises a step of selectively removing at least a portion of impurity components different from the dopant component from the water to be treated, which may contain the concentration adjusting agent, or The addition step further comprises a step of selectively removing at least a portion of impurity components different from the dopant component from the concentration adjusting agent. A method for producing adjusted water according to claim 16.

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